JP2019178443A - Friction anti-melting composite fiber, fabric and clothing - Google Patents
Friction anti-melting composite fiber, fabric and clothing Download PDFInfo
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- JP2019178443A JP2019178443A JP2018067502A JP2018067502A JP2019178443A JP 2019178443 A JP2019178443 A JP 2019178443A JP 2018067502 A JP2018067502 A JP 2018067502A JP 2018067502 A JP2018067502 A JP 2018067502A JP 2019178443 A JP2019178443 A JP 2019178443A
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002844 melting Methods 0.000 title claims abstract description 40
- 239000004744 fabric Substances 0.000 title claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 75
- 229920005989 resin Polymers 0.000 claims abstract description 75
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 57
- 239000010954 inorganic particle Substances 0.000 claims abstract description 36
- 230000008018 melting Effects 0.000 claims abstract description 35
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 4
- 239000004952 Polyamide Substances 0.000 claims description 24
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- 239000004707 linear low-density polyethylene Substances 0.000 claims description 8
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 6
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 6
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- 238000009987 spinning Methods 0.000 description 12
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- -1 silver ions Chemical class 0.000 description 11
- 239000011342 resin composition Substances 0.000 description 10
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- 239000000203 mixture Substances 0.000 description 8
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- 239000000126 substance Substances 0.000 description 7
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
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- 238000000691 measurement method Methods 0.000 description 4
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- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 4
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
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- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
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- 229910052797 bismuth Inorganic materials 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- IQBJFLXHQFMQRP-UHFFFAOYSA-K calcium;zinc;phosphate Chemical compound [Ca+2].[Zn+2].[O-]P([O-])([O-])=O IQBJFLXHQFMQRP-UHFFFAOYSA-K 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- 238000004898 kneading Methods 0.000 description 1
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- Multicomponent Fibers (AREA)
- Woven Fabrics (AREA)
Abstract
Description
本発明は、体育館等での転倒やスライディング時などに、床と布帛との間で生じる摩擦熱によって布帛が溶融することを防止する摩擦防複合融繊維、それを用いた布帛および衣料品に関する。 The present invention relates to a friction-proof composite fused fiber that prevents a fabric from being melted by frictional heat generated between a floor and a fabric during a fall or sliding in a gymnasium or the like, and a fabric and clothing using the same.
ポリエステル繊維は、その優れた力学的特性および化学的特性から、スポーツ衣料分野に数多く利用されている。しかし、ポリエステル等の合成繊維は、綿やレーヨンなどの天然系繊維と異なり、体育館等での転倒やスライディング時、床と布帛との間で生じる摩擦熱によって布帛が溶融し、布帛に穴が空いてしまう欠点を有する。また特にスポーツ衣料分野においては多くの発汗を伴う状況下で使用されるため、汗に含まれる乳酸、尿素などの老廃物や汗をかいた状態で衣服と肌が擦れ合うことで繊維に付着した皮脂などが衣服表面で細菌類により分解されることで悪臭を発することがある。 Polyester fibers are widely used in the sports clothing field because of their excellent mechanical and chemical properties. However, synthetic fibers such as polyester, unlike natural fibers such as cotton and rayon, melt the fabric due to frictional heat generated between the floor and the fabric when falling or sliding in a gymnasium or the like, resulting in a hole in the fabric. Have the disadvantages. Also, especially in the sports clothing field, it is used in situations involving a lot of sweating, so lactic acid, urea, and other waste products contained in sweat, and sebum that adheres to the fibers by rubbing clothes and skin while sweating. May cause a bad odor when decomposed by bacteria on the clothes surface.
このような問題を解決するため、上述の摩擦熱により布帛が溶融することを防止する方法としては、例えば、特許文献１や２では、鞘成分樹脂よりも融点が低い樹脂成分を芯部に配した繊維とすることで、摩擦熱で鞘部が溶融する温度に上昇する前に芯部が溶解し、その際の吸熱により繊維全体の溶融を防ぐ方法が提案されている。また特許文献３では、鞘成分に用いる樹脂に、鞘成分よりも融点が低い低融点成分を分散させた海島型アロイを芯部に配し、芯部を鞘成分にて薄皮で覆った繊維を用いることにより、より効果的に摩擦熱による溶融を防ぐことが提案されている。
In order to solve such a problem, as a method for preventing the fabric from melting due to the frictional heat described above, for example, in
また、繊維に抗菌防臭性を与える方法として、例えば、繊維表面に抗菌剤成分としての銀を担持した二酸化チタン成分を吸尽させる方法（特許文献４）、４級化アンモニウム塩を繊維表面に後加工して付着させる方法（特許文献５）、繊維中に抗菌剤を練り込む方法（特許文献６）等が開示されている。 Further, as a method for imparting antibacterial and deodorant properties to the fiber, for example, a method of exhausting a titanium dioxide component carrying silver as an antibacterial agent component on the fiber surface (Patent Document 4), a quaternized ammonium salt is added to the fiber surface. A method of processing and adhering (Patent Document 5), a method of incorporating an antibacterial agent into fibers (Patent Document 6), and the like are disclosed.
しかしながら、昨今、スポーツ分野の衣料品においても、多種多様な機能を求められているにも拘わらず、摩擦防融性と抗菌防臭性を兼ね備えた繊維についての提案はなかった。 However, in recent years, there have been no proposals for fibers having both anti-fouling properties and antibacterial and deodorizing properties in spite of demand for various functions in sports clothing.
そこで、本発明は、抗菌防臭性と摩擦防融性を同時に満足する、抗菌防臭性を有する摩擦防融複合繊維、それからなる布帛および衣料品を得ることを目的とする。 Therefore, an object of the present invention is to obtain a friction-fusible composite fiber having antibacterial and deodorant properties that satisfies both antibacterial and deodorant properties and friction and fusing properties simultaneously, and a fabric and a clothing product comprising the same.
上記目的を達成するため、本発明は、海成分と島成分とからなり、島成分は海成分を構成する樹脂よりも３０℃以上低融点である樹脂を含む樹脂からなる海島型複合繊維であって、海成分は銀イオン、亜鉛イオンおよび銅イオンの群から選択される１以上のイオンを放出する無機粒子を含有する抗菌防臭機能を有する摩擦防融複合繊維をその第一の要旨とする。 In order to achieve the above object, the present invention is a sea-island composite fiber comprising a sea component and an island component, and the island component is a resin containing a resin having a melting point of 30 ° C. or more lower than that of the resin constituting the sea component. Thus, the sea component is a friction-fusible composite fiber having an antibacterial and deodorizing function containing inorganic particles that release one or more ions selected from the group of silver ions, zinc ions, and copper ions.
また、上記摩擦防融複合繊維において、無機粒子が、水溶性ガラス、リン酸ジルコニウムおよびゼオライトの群から選択される少なくとも１種のものであることをその第二の要旨とする。 The second gist of the friction-fusible composite fiber is that the inorganic particles are at least one selected from the group consisting of water-soluble glass, zirconium phosphate and zeolite.
更に、上記摩擦防融複合繊維において、海成分が、ポリエステルまたはポリアミドからなり、島成分が、高密度ポリエチレン、低密度ポリエチレンおよび直鎖低密度ポリエチレンの群から選択される１以上の樹脂を含むものであることを第三の要旨とする。 Further, in the friction-proof composite fiber, the sea component is made of polyester or polyamide, and the island component contains one or more resins selected from the group of high-density polyethylene, low-density polyethylene, and linear low-density polyethylene. This is the third gist.
上記摩擦防融複合繊維において、島成分は、ポリエステルまたはポリアミドの少なくともいずれか１種の樹脂と、高密度ポリエチレン、低密度ポリエチレンおよび直鎖低密度ポリエチレンの群から選択される１以上の樹脂とを含む、海相と島相からなる海島型アロイ樹脂であることを第四の要旨とする。 In the friction-proof composite fiber, the island component includes at least one resin of polyester or polyamide, and one or more resins selected from the group of high-density polyethylene, low-density polyethylene, and linear low-density polyethylene. It is the fourth gist that it is a sea-island type alloy resin comprising a sea phase and an island phase.
また、上記摩擦防融複合繊維を２０質量％以上含む布帛を第五の要旨とし、当該布帛を含む衣料品を第六の要旨とする。 A fabric containing 20 mass% or more of the above-mentioned friction-fusible composite fiber is a fifth summary, and a clothing article containing the fabric is a sixth summary.
本発明の摩擦防融複合繊維によれば、摩擦防融性が高く、かつ抗菌防臭性を有する布帛や衣料品を提供することができる。 According to the friction-proof composite fiber of the present invention, it is possible to provide a fabric or clothing having a high friction-proof property and an antibacterial and deodorizing property.
以下、本発明を詳細に説明する。
本発明の摩擦防融複合繊維は、海成分と島成分とからなる海島型複合繊維である。
本発明の摩擦防融複合繊維の海成分を構成する樹脂は、繊維形成性樹脂であれば、特に限定するものではないが、例えば、ポリエステル、ポリアミドが好適に挙げられる。
Hereinafter, the present invention will be described in detail.
The friction-fusible composite fiber of the present invention is a sea-island type composite fiber composed of a sea component and an island component.
The resin constituting the sea component of the friction-fusible composite fiber of the present invention is not particularly limited as long as it is a fiber-forming resin, and examples thereof include polyester and polyamide.
本発明におけるポリエステルは、ジカルボン酸またはそのエステル形成性誘導体と、ジオールまたはそのエステル形成性誘導体から合成される樹脂である。このようなポリエステルとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリプロピレンテレフタレート等が挙げられる。 The polyester in the present invention is a resin synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. Examples of such polyester include polyethylene terephthalate, polybutylene terephthalate, and polypropylene terephthalate.
また、これらのポリエステルには、本発明の目的が損なわれない範囲であれば、他の成分が共重合されていてもよい。具体的には、共重合成分としては、ジカルボン酸成分では、イソフタル酸、ナフタレンジカルボン酸、４、４−ジフェニルジカルボン酸、アジピン酸、セバシン酸およびそのエステル形成性誘導体等やスルホネート基含有イソフタル酸成分等の官能基を有する成分が挙げられる。また、ジオール成分としてはジエチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノール等が挙げられる。また、ポリエチレングリコール、ポリプロピレングリコール等のポリオキシアルキレングリコールも挙げられる。共重合量としては、構成する繰り返し単位あたり１０モル％以内が好ましく、５モル％以内がより好ましい。 In addition, other components may be copolymerized with these polyesters as long as the object of the present invention is not impaired. Specifically, as the copolymerization component, dicarboxylic acid component, isophthalic acid, naphthalenedicarboxylic acid, 4,4-diphenyldicarboxylic acid, adipic acid, sebacic acid and ester-forming derivatives thereof, and sulfonate group-containing isophthalic acid component The component which has functional groups, such as, is mentioned. Examples of the diol component include diethylene glycol, hexamethylene glycol, neopentyl glycol, and cyclohexane dimethanol. Further, polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol are also included. The amount of copolymerization is preferably within 10 mol%, more preferably within 5 mol%, per repeating unit.
更に、これらポリエステルには、目的を阻害しない範囲において、つや消し剤や着色剤、耐熱安定剤、紫外線吸収剤等の添加剤を含有していてもよい。
本発明におけるポリエステルの粘度は特に制限されるものではなく、通常のポリエステル繊維に利用されている極限粘度［ＩＶ］のポリエステルを使用することができる。紡糸性および繊維の力学的強度の点から、例えばポリエチレンテレフタレートであれば、極限粘度［ＩＶ］は０．４〜１．５であることが好ましく、極限粘度［ＩＶ］は０．５５〜１．０であることがより好ましい。
Furthermore, these polyesters may contain additives such as a matting agent, a colorant, a heat stabilizer, and an ultraviolet absorber as long as the purpose is not impaired.
The viscosity of the polyester in the present invention is not particularly limited, and a polyester having an intrinsic viscosity [IV] utilized for ordinary polyester fibers can be used. In terms of spinnability and mechanical strength of the fiber, for example, polyethylene terephthalate, the intrinsic viscosity [IV] is preferably 0.4 to 1.5, and the intrinsic viscosity [IV] is 0.55 to 1. More preferably 0.
本発明におけるポリアミドとしては、ε−カプロラクタムを開環重合して得たポリアミド６やジアミンとジカルボン酸を縮重合して得る、例えばヘキサメチレンジアミンとアジピン酸を縮重合して得たポリアミド６６、ヘキサメチレンジアミンとセバシン酸を縮重合して得たポリアミド６１０などが好適である。 Examples of the polyamide in the present invention include polyamide 6 obtained by ring-opening polymerization of ε-caprolactam, polyamide 66 obtained by condensation polymerization of diamine and dicarboxylic acid, for example, polyamide 66 obtained by condensation polymerization of hexamethylenediamine and adipic acid, hexa A polyamide 610 obtained by condensation polymerization of methylenediamine and sebacic acid is preferable.
更にこれらのポリアミドには、目的を阻害しない範囲において、つや消し剤や着色剤、耐熱安定剤、紫外線吸収剤等の添加剤を含有していてもよい。
本発明におけるポリアミドの粘度は特に制限されるものではなく、通常のポリアミド繊維に利用されている相対粘度［ηｒ］のポリアミドを使用することができる。紡糸性および繊維の力学的強度の点から、例えばポリアミド６であれば、相対粘度［ηｒ］は２．０〜３．４であることが好ましく、相対粘度［ηｒ］が２．４〜３．０であることがより好ましい。
Furthermore, these polyamides may contain additives such as a matting agent, a colorant, a heat stabilizer, and an ultraviolet absorber as long as the purpose is not impaired.
The viscosity of the polyamide in the present invention is not particularly limited, and a polyamide having a relative viscosity [ηr] that is used for ordinary polyamide fibers can be used. From the viewpoint of spinnability and mechanical strength of the fiber, for example, in the case of polyamide 6, the relative viscosity [ηr] is preferably 2.0 to 3.4, and the relative viscosity [ηr] is 2.4 to 3. More preferably 0.
次に本発明の摩擦防融複合繊維の島成分について、詳細に説明する。
島成分は、海成分を構成する樹脂より低融点の樹脂（以下、低融点樹脂とよぶことがある）を含むことが肝要である。
Next, the island component of the friction-fusible composite fiber of the present invention will be described in detail.
It is important that the island component includes a resin having a lower melting point than the resin constituting the sea component (hereinafter sometimes referred to as a low melting point resin).
低融点樹脂は、海成分を構成する樹脂よりも、３０℃以上融点が低いものであり、８０℃以上融点が低いものであることが好ましく、１００℃以上融点が低いものであることがより好ましい。海成分を構成する樹脂と低融点樹脂の融点差が小さいと摩擦防融効果が小さくなる傾向があり、その融点差が３０℃未満であると実質的に摩擦防融効果を示さない。 The low melting point resin has a melting point of 30 ° C. or higher, preferably 80 ° C. or higher and lower, and more preferably 100 ° C. or higher and lower melting point than the resin constituting the sea component. . If the melting point difference between the resin constituting the sea component and the low-melting point resin is small, the friction-proofing effect tends to be small, and if the melting point difference is less than 30 ° C., the friction-proofing effect is not substantially exhibited.
低融点樹脂としては、例えば、海成分がポリエステルやポリアミドの場合は、海成分より低融点のポリエステル、ポリアミド、ポリプロピレン、ポリエチレン等が挙げられる。摩擦防融性を良好にする点からは、ポリエチレンであることが好ましく、具体的には、高密度ポリエチレン、低密度ポリエチレンおよび直鎖低密度ポリエチレンが好適に挙げられ、これらの樹脂を単独で用いてもよいし、２以上の混合物として用いてもよい。 As the low melting point resin, for example, when the sea component is polyester or polyamide, polyester, polyamide, polypropylene, polyethylene or the like having a melting point lower than that of the sea component may be used. From the viewpoint of improving the friction-fusibility, polyethylene is preferable, and specific examples include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, and these resins are used alone. It may be used as a mixture of two or more.
島成分は、低融点樹脂のみから構成されてもよいし、一部に低融点樹脂を含むものであってもよい。 The island component may be composed of only a low melting point resin, or may contain a low melting point resin in part.
島成分は、ポリエステルやポリアミド等の海成分の繊維形成性樹脂と、低融点樹脂とを含む、海相と島相からなる海島型アロイ樹脂であってもよい。 The island component may be a sea-island type alloy resin composed of a sea phase and an island phase, including a fiber-forming resin of a sea component such as polyester and polyamide, and a low melting point resin.
なお、海成分がポリエステルまたはポリアミドから構成される場合、島成分は、高密度ポリエチレン、低密度ポリエチレンおよび直鎖低密度ポリエチレンの少なくとも１以上の低融点樹脂を含むことが好ましい。 In addition, when a sea component is comprised from polyester or polyamide, it is preferable that an island component contains at least 1 or more low melting point resin of a high density polyethylene, a low density polyethylene, and a linear low density polyethylene.
島成分が海島型アロイ樹脂の場合は、海成分と島成分との密着性（親和性）を高め、摩擦防融性を良好とする点からは、島成分が海成分と同種の樹脂と、低融点樹脂とを含む混合物からなる海島型アロイ樹脂であることが好ましい。 In the case where the island component is a sea-island type alloy resin, the island component is the same type of resin as the sea component from the viewpoint of improving the adhesion (affinity) between the sea component and the island component and improving the anti-friction property, A sea-island alloy resin made of a mixture containing a low melting point resin is preferred.
島成分が海島型アロイ樹脂の場合の具体的な好適な樹脂の組み合わせとして、ポリエステルまたはポリアミドの少なくともいずれか１種の樹脂と、高密度ポリエチレン、低密度ポリエチレンおよび直鎖低密度ポリエチレンの群から選択される１以上の樹脂とを含むものであることが挙げられる。これらの中でも、ポリエステルまたはポリアミドの少なくともいずれか１種の樹脂が海相、高密度ポリエチレン、低密度ポリエチレンおよび直鎖低密度ポリエチレンの群から選択される１以上の樹脂が島相からなる海島型アロイ樹脂であることが好適である。 When the island component is a sea-island type alloy resin, a specific suitable resin combination is selected from the group consisting of at least one of polyester and polyamide, high-density polyethylene, low-density polyethylene, and linear low-density polyethylene. And one or more resins. Among these, at least one resin of polyester or polyamide is a sea-island type alloy in which one or more resins selected from the group of sea phase, high-density polyethylene, low-density polyethylene, and linear low-density polyethylene are island phases. A resin is preferred.
島成分が海島型アロイ樹脂の場合、安定した摩擦防融性効果発現の点から、低融点樹脂は、島成分に対し、５〜４５質量％であることが好ましく、より好ましくは、１０〜３０質量％である。 In the case where the island component is a sea-island type alloy resin, the low melting point resin is preferably 5 to 45% by mass, more preferably 10 to 30%, based on the island component, from the viewpoint of expressing a stable friction-fusible effect. % By mass.
また、島成分が海島型アロイ樹脂の場合は、相溶化剤を添加して含むものとすることが好ましい。相溶化剤の具体例としては、エチレン／アクリル酸共重合体、エチレン／メタクリル酸共重合体、エチレン／アクリル酸エチル共重合体、エチレン／酢酸ビニル共重合体、エチレン／メタクリル酸グリシジル共重合体、エチレン／酢酸ビニル／メタクリル酸グリシジル共重合体、無水マレイン酸グラフトポリエチレン、アクリル酸グラフトポリエチレン、無水マレイン酸グラフトエチレン／プロピレン共重合体、エチレン／プロピレン−メタクリル酸グラフトグリシジル共重合体、無水マレイン酸グラフトエチレン／プロピレン／１，４−ヘキサジエン共重合体またはアクリル酸グラフトエチレン／酢酸ビニル共重合体などが挙げられる。これらの相溶化剤は１種以上用いることが好ましく、２種以上用いてもよい。
相溶化剤の添加量は、島成分を構成する樹脂全体に対し、０．１〜１０質量％程度が好ましく、より好ましくは０．２〜５質量％である。
In addition, when the island component is a sea-island type alloy resin, it is preferable to include a compatibilizing agent. Specific examples of the compatibilizer include ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer, ethylene / glycidyl methacrylate copolymer. , Ethylene / vinyl acetate / glycidyl methacrylate copolymer, maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, maleic anhydride grafted ethylene / propylene copolymer, ethylene / propylene-methacrylic acid grafted glycidyl copolymer, maleic anhydride Examples thereof include graft ethylene / propylene / 1,4-hexadiene copolymer and acrylic acid graft ethylene / vinyl acetate copolymer. One or more of these compatibilizers are preferably used, and two or more of them may be used.
The addition amount of the compatibilizer is preferably about 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the entire resin constituting the island component.
次に、本発明の摩擦防融複合繊維は、海成分が銀イオン、亜鉛イオンおよび銅イオンの群から選択される１以上のイオンを放出することが可能な無機粒子を含有する。以下、このような無機粒子を本発明における無機粒子という。本発明における無機粒子を含有すると、抗菌防臭効果を有するものとなる。 Next, the friction-proof composite fiber of the present invention contains inorganic particles capable of releasing one or more ions selected from the group consisting of silver ions, zinc ions and copper ions as a sea component. Hereinafter, such inorganic particles are referred to as inorganic particles in the present invention. When the inorganic particles in the present invention are contained, an antibacterial and deodorizing effect is obtained.
本発明における無機粒子としては、例えば、銀、銅、亜鉛、ビスマス、コバルト、ニッケルなどの抗菌性金属を担持した種々の無機化合物が好適に挙げられる。
抗菌性金属を担持する無機化合物（担持体）としては、例えば、以下の（１）、（２）、（３）に示すものが好適に挙げられる。
（１）ゼオライト、リン酸ジルコニウム、ヒドロキシアパタイト、リン酸チタン、チタン酸カリウム、含水酸化ビスマス、含水酸化アンチモン、含水酸化ジルコニウム、ハイドロタルサイト、リン酸カルシウム、リン酸亜鉛カルシウム，ケイ酸カルシウムなどの無機イオン交換体
（２）酸化チタン、活性炭、活性アルミナなどの無機吸着体
（３）シリカ系ガラス、水溶性ガラスまたはシリカゲルなどの無機媒体（無定形ガラス状物質）
これらのなかでも、銀単体、銀と銅または銀と亜鉛を、水溶性ガラス、リン酸ジルコニウム、リン酸チタンおよびゼオライトから選択される少なくとも１種の無機化合物に担持させた無機粒子であることが好ましい。
本発明の摩擦防融複合繊維は、これらの本発明における無機粒子を、単体で用いても、２以上組み合わせて用いてもよい。
As an inorganic particle in this invention, the various inorganic compound which carry | supported antimicrobial metals, such as silver, copper, zinc, bismuth, cobalt, nickel, is mentioned suitably, for example.
Preferred examples of the inorganic compound (support) supporting the antibacterial metal include those shown in the following (1), (2), and (3).
(1) Inorganic ions such as zeolite, zirconium phosphate, hydroxyapatite, titanium phosphate, potassium titanate, hydrous bismuth, hydrous antimony, hydrous zirconium oxide, hydrotalcite, calcium phosphate, zinc calcium phosphate, calcium silicate Exchanger (2) Inorganic adsorbents such as titanium oxide, activated carbon, activated alumina (3) Inorganic medium such as silica glass, water-soluble glass or silica gel (amorphous glassy substance)
Among these, it is an inorganic particle in which silver alone, silver and copper or silver and zinc are supported on at least one inorganic compound selected from water-soluble glass, zirconium phosphate, titanium phosphate and zeolite. preferable.
In the friction-fusible conjugate fiber of the present invention, these inorganic particles in the present invention may be used alone or in combination of two or more.
以下、本発明における無機粒子を得る方法について例示する。
担持体がゼオライトの場合、例えば、特開昭５９−１３３２３５号公報に示されているようにゼオライト微粒子を硝酸銀水溶液で処理してイオン交換反応を行い、ゼオライトに銀を担持させることにより本発明における無機粒子を得ることができる。また市販の製品としては、例えば、シナネンゼオミック社製「ゼオミック（登録商標）」として入手できる。
担持体がリン酸ジルコニウムやリン酸チタンの場合、例えば、特開平３−８３９０５号公報に開示されているように炭酸リチウム、リン酸水素二アンモニウムおよび酸化ジルコニウム、または酸化チタンを所定量混合し、１３００℃で焼結して得た化合物を微粉砕した後、硝酸銀水溶液で処理して、本発明における無機粒子を得ることができる。市販の製品としては、例えば、東亞合成社製「ノバロン（登録商標）（商品名）」として入手できる。
担持体が水溶性ガラスの場合、例えば、特開平３−１２４８１０号公報に開示されているように所定量の酸化銀、酸化ホウ素、シリカおよび酸化ナトリウムを溶融ガラス化し、微粉砕して得た銀イオンを放出する本発明における無機粒子を得たり、特開平７−２５７９３８号公報に開示されているように所定量の酸化亜鉛、酸化ホウ素および酸化ナトリウムを１０００〜１３００℃で溶解ガラス化し、微粉砕して得た亜鉛イオンを放出する本発明における無機粒子を得ることができる。市販の製品としては、例えば、石塚硝子社製「イオンピュア（登録商標）（商品名）」として入手できる。
また、市販の富士ケミカル社製の各種抗菌剤を本発明における無機粒子として用いることができる。更に、富士ケミカル社製の各種抗菌剤をポリエステルやポリアミド中に高濃度で分散させている「バクテキラー（登録商標）マスターバッチ（商品名）」であれば、本発明における無機粒子を含有する本発明の摩擦防融複合繊維を容易に得ることができる。
Hereinafter, the method for obtaining the inorganic particles in the present invention will be exemplified.
When the support is a zeolite, for example, as shown in JP-A-59-133235, the zeolite fine particles are treated with an aqueous silver nitrate solution to carry out an ion exchange reaction, and the zeolite is loaded with silver to thereby support the present invention. Inorganic particles can be obtained. In addition, as a commercially available product, for example, “Zeomic (registered trademark)” manufactured by Sinanen Zeomic Co., Ltd. can be obtained.
When the support is zirconium phosphate or titanium phosphate, for example, as disclosed in JP-A-3-83905, lithium carbonate, diammonium hydrogen phosphate and zirconium oxide, or a predetermined amount of titanium oxide are mixed, The compound obtained by sintering at 1300 ° C. can be finely pulverized and then treated with an aqueous silver nitrate solution to obtain the inorganic particles in the present invention. As a commercially available product, for example, “Novalon (registered trademark) (trade name)” manufactured by Toagosei Co., Ltd. can be obtained.
When the support is water-soluble glass, for example, silver obtained by melting and finely pulverizing a predetermined amount of silver oxide, boron oxide, silica and sodium oxide as disclosed in JP-A-3-124810 Inorganic particles in the present invention that release ions are obtained, or a predetermined amount of zinc oxide, boron oxide, and sodium oxide is dissolved and vitrified at 1000 to 1300 ° C. as disclosed in JP-A-7-257938 and finely pulverized. Thus, inorganic particles in the present invention that release the zinc ions obtained can be obtained. As a commercially available product, for example, “Ion Pure (registered trademark)” (trade name) manufactured by Ishizuka Glass Co., Ltd. is available.
Various antibacterial agents manufactured by Fuji Chemical Co., Ltd. can be used as inorganic particles in the present invention. Furthermore, the present invention containing the inorganic particles in the present invention is "Bactekiller (registered trademark) masterbatch (trade name)" in which various antibacterial agents manufactured by Fuji Chemical are dispersed in polyester or polyamide at a high concentration. This friction-fusible composite fiber can be easily obtained.
本発明の摩擦溶融複合繊維は、このような本発明における無機粒子を海成分に含有することにより抗菌防臭性を有する繊維となる。 The friction-melt composite fiber of the present invention is a fiber having antibacterial and deodorant properties by containing such inorganic particles in the present invention as a sea component.
次に、本発明の本発明の摩擦防融複合繊維の断面形状について説明する。
本発明の摩擦防融複合繊維は、上述のような海成分と、島成分とからなる海島型複合繊維である。本発明において、海島型複合繊維は、１以上の島成分と、１以上の海成分を複合してなる繊維である。
図１〜図４は、本発明の摩擦防融複合繊維の長手方向に垂直な切断面の形状の例である。
図１、図３は、海成分の数が１、島成分の数が１の海島型複合繊維の断面である。
図２、図４は、海成分の数が１、島成分の数が１９の海島型複合繊維の断面である。図２、図４の海島型複合繊維の島成分は、中心に１個、中心の島成分の外周を均等に１例に囲んで６個、その外周を均等に１列に囲んで１２個の合計１９個配されている。
なお、本発明における海島型複合繊維の海成分および島成分の数は１以上であれば、特に制限されるものではないが、口金作製の容易さから、６１島以下が好ましく、３７島以下がより好ましく、１９島以下が最も好ましい。
海成分と、島成分の好適な比率（断面積比率）としては、島成分に低融点樹脂のみを用いる場合は、島成分：海成分比率が、５：９５〜５０：５０が好ましく、より好ましくは１０：９０〜３０：７０である。また、島成分に海島型アロイ樹脂を用いる場合は、島成分：海成分比率が、２０：８０〜７０：３０の範囲が好ましく、より好ましくは、３０：７０〜５０：５０である。この範囲であると、紡糸性も良好であり、本発明の効果も奏しやすい。
Next, the cross-sectional shape of the friction-fusible conjugate fiber of the present invention will be described.
The friction-fusible composite fiber of the present invention is a sea-island type composite fiber composed of the sea component as described above and an island component. In the present invention, the sea-island type composite fiber is a fiber formed by combining one or more island components and one or more sea components.
1-4 is an example of the shape of a cut surface perpendicular | vertical to the longitudinal direction of the friction-proof composite fiber of this invention.
1 and 3 are cross-sections of a sea-island composite fiber having one sea component and one island component.
2 and 4 are cross-sections of a sea-island composite fiber having 1 sea component and 19 island components. 2 and 4, the island component of the sea-island type composite fiber is one in the center, the outer periphery of the central island component is uniformly surrounded by one example in six, and the outer periphery is uniformly surrounded in one row by twelve. A total of 19 are arranged.
The number of sea and island components of the sea-island composite fiber in the present invention is not particularly limited as long as it is 1 or more, but 61 or less is preferable and 37 or less is preferable in terms of ease of manufacturing the die. More preferred is 19 islands or less.
As a suitable ratio (cross-sectional area ratio) between the sea component and the island component, when only a low melting point resin is used for the island component, the ratio of the island component: sea component is preferably 5:95 to 50:50, and more preferably. Is 10: 90-30: 70. Moreover, when sea island type alloy resin is used for the island component, the ratio of the island component: sea component is preferably in the range of 20:80 to 70:30, more preferably 30:70 to 50:50. Within this range, the spinnability is good and the effects of the present invention are easily achieved.
次に、摩擦防融複合繊維の製造方法の好適な例について、説明する。
まず、ポリエステルペレットまたはポリアミドペレット、本発明における無機粒子、低融点樹脂ペレット等を準備する。
Next, a preferred example of a method for producing a friction-proof composite fiber will be described.
First, polyester pellets or polyamide pellets, inorganic particles in the present invention, low melting point resin pellets and the like are prepared.
次に、芯成分を海島型アロイ樹脂とする場合は、海島型アロイ樹脂を製造する。
具体的には、ポリエステルペレットまたはポリアミドペレットと、低融点樹脂ペレットとを予備混合した後、二軸押出混練機にて、ポリエステルまたはポリアミドの融点より１０〜４０℃高く設定して溶融複合混練して、海島型アロイ樹脂を得ることができる。この際、ポリエステルまたはポリアミドペレットと、低融点樹脂ペレットとの混合比率は、９５：５〜５５：４５(質量比)の範囲であることが好ましい。より好ましくは９０：１０〜７０：３０（質量比）の範囲である。海島型アロイ樹脂を製造する際、海島型アロイ樹脂のモルフォロジーを安定化する目的で、相溶化剤を併用することが好ましく、ペレット混合する際に、樹脂ペレット全体に対し、０．１〜１０質量％程度、添加して用いることが好ましく、より好ましい添加量は０．２〜５質量％である。
Next, when the core component is a sea-island type alloy resin, a sea-island type alloy resin is produced.
Specifically, after pre-mixing polyester pellets or polyamide pellets and low-melting point resin pellets, the mixture is melt compounded and kneaded at a temperature 10 to 40 ° C. higher than the melting point of polyester or polyamide in a twin-screw extrusion kneader. A sea-island type alloy resin can be obtained. At this time, the mixing ratio of the polyester or polyamide pellets and the low melting point resin pellets is preferably in the range of 95: 5 to 55:45 (mass ratio). More preferably, it is the range of 90:10 to 70:30 (mass ratio). When producing the sea-island type alloy resin, it is preferable to use a compatibilizer in order to stabilize the morphology of the sea-island type alloy resin. When the pellets are mixed, 0.1 to 10 mass relative to the whole resin pellets. % Is preferably used by adding about 0.2% to 5% by mass.
次に、海成分として、予め本発明における無機粒子を含む樹脂組成物を紡糸に供する場合、海成分のベース樹脂に本発明における無機粒子を含む樹脂組成物を準備する。具体的には、二軸押出混練機の第１フィード口から、海成分を構成するベース樹脂を供給し、溶解したところへサイドフィーダーを用いて、本発明における無機粒子を、所定比率になるように第２フィード口より供給し複合化させて樹脂組成物を得る方法、予め海成分のベース樹脂を粉末化し所定量の無機粒子を予備混合したものを二軸押出混練機または単軸の押出機で溶融混合して樹脂組成物を得る方法等により、製造して得ることができる。また、市販の各種抗菌剤をポリエステルやポリアミド中に高濃度で分散させているマスターバッチ（例えば、富士ケミカル社製の「バクテキラー（登録商標）マスターバッチ（商品名）」）をベース樹脂に希釈混合して樹脂組成物として用いることもできる。 Next, when the resin composition containing the inorganic particles in the present invention is used in advance as a sea component for spinning, a resin composition containing the inorganic particles in the present invention is prepared for the base resin of the sea component. Specifically, the base resin constituting the sea component is supplied from the first feed port of the twin-screw extrusion kneader, and the inorganic particles in the present invention are in a predetermined ratio using the side feeder to the melted place. A method of obtaining a resin composition by supplying from the second feed port and making a composite, a biaxial extrusion kneader or a single screw extruder in which a base resin of a sea component is previously powdered and a predetermined amount of inorganic particles are premixed And can be obtained by a method such as a method of obtaining a resin composition by melt mixing. In addition, a masterbatch in which various commercially available antibacterial agents are dispersed at a high concentration in polyester or polyamide (for example, “Bactekiller (registered trademark) masterbatch (trade name)” manufactured by Fuji Chemical Co., Ltd.) is diluted and mixed in the base resin. It can also be used as a resin composition.
低融点樹脂または海島型アロイ樹脂、本発明における無機粒子を含む樹脂組成物を、押出機により、それぞれの樹脂を溶解し、所謂スピンパック内で、低融点樹脂または海島型アロイ樹脂を島部、本発明における無機粒子を含む樹脂組成物を海部の形状に合して、紡糸口金から吐出する。吐出された糸条を、所望に応じて延伸して、本発明の摩擦防融複合繊維を得ることができる。なお、海部に本発明における無機粒子を含む樹脂組成物を用いず、海成分を構成する樹脂と本発明における無機粒子を紡糸時にブレンドして繊維を製造してもよい。
紡糸延伸方法としては、（１）一旦、吐出された糸条を未延伸糸として巻き取った後、延伸機で延伸して延伸糸を得るコンベンショナル法、（２）吐出された糸条を、一旦巻き取ることなく、第１ローラーと第２ローラーとの間で延伸しながら巻き取るスピンドロー法、（３）吐出された糸条を３０００〜４５００ｍ／分程度で部分延伸糸として巻き取った後、仮撚機で延伸仮撚するＰＯＹ−ＤＴＹ法等、適宜、選択できる。
Low melting point resin or sea-island type alloy resin, resin composition containing inorganic particles in the present invention, each resin is dissolved by an extruder, and in a so-called spin pack, low melting point resin or sea-island type alloy resin The resin composition containing inorganic particles in the present invention is discharged from a spinneret according to the shape of the sea part. The discharged yarn can be stretched as desired to obtain the friction-proof composite fiber of the present invention. In addition, without using the resin composition containing the inorganic particles in the present invention in the sea part, the fiber constituting the sea component and the inorganic particles in the present invention may be blended during spinning to produce fibers.
As the spinning and drawing method, (1) a conventional method in which a discharged yarn is wound up as an undrawn yarn and then drawn by a drawing machine to obtain a drawn yarn; (2) the discharged yarn is temporarily A spin draw method of winding while drawing between the first roller and the second roller without winding, (3) after winding the discharged yarn as a partially drawn yarn at about 3000-4500 m / min, A POY-DTY method of drawing false twisting with a false twisting machine can be appropriately selected.
なお、海成分と島成分の繊維断面積比率（長手方向に垂直な面の面積比率）は、海島型アロイ樹脂を用いる場合は、紡糸性を良好とする点から、島成分：海成分の比率が、２０：８０〜７０：３０の範囲とすることが好ましく、より好ましくは、３０：７０〜５０：５０である。また島成分に低融点樹脂のみを用いる場合、島成分：海成分の比率が、５：９５〜５０：５０の範囲が好ましく、より好ましくは、１０：９０〜３０：７０である。 Note that the ratio of the fiber cross-sectional area between the sea component and the island component (area ratio of the plane perpendicular to the longitudinal direction) is the ratio of the island component to the sea component when sea island-type alloy resin is used from the viewpoint of good spinnability. However, it is preferable to set it as the range of 20: 80-70: 30, More preferably, it is 30: 70-50: 50. When only the low melting point resin is used for the island component, the ratio of the island component: the sea component is preferably in the range of 5:95 to 50:50, more preferably 10:90 to 30:70.
このようにして得られた本発明の摩擦防融複合繊維を、一部または全部に用いて、製編織して、布帛を得ることができる。 The thus obtained friction-fusible conjugate fiber of the present invention can be used for a part or all of it and knitted and woven to obtain a fabric.
本発明の布帛は、摩擦防融性、抗菌防臭性の点から、本発明の摩擦防融複合繊維を２０質量％以上含むことが好ましく、より好ましくは、３３質量％以上、更に好ましくは５０質量％であり、最も好ましくは全量用いることである。 The fabric of the present invention preferably contains 20% by mass or more of the friction-fusible composite fiber of the present invention, more preferably 33% by mass or more, and still more preferably 50% by mass, from the viewpoints of friction resistance and antibacterial deodorization. %, And most preferably the entire amount is used.
本発明の布帛の形態としては、織物、編物、不織布等の繊維構造物が好適に挙げられる。
織物の組織としては、平織、朱子織等が好適に挙げられ、編物の組織としては、丸編み（緯編み）、トリコット（経編）等が好適に挙げられる。
As a form of the fabric of the present invention, a fiber structure such as a woven fabric, a knitted fabric, and a non-woven fabric is preferably exemplified.
Preferred examples of the woven fabric include plain weave and satin weave, and preferred examples of the knitted fabric include circular knitting (weft knitting) and tricot (warp knitting).
本発明の摩擦防融複合繊維を含む布帛は、優れた摩擦防融性と抗菌防臭性を備えたものであるため、ジャージ、バレーボールやハンドボールのゲームシャツ、スポーツ用ウォームウェアー等の衣料品に好適に用いることができる。 The cloth containing the friction-proof composite fiber of the present invention has excellent friction-proof and antibacterial deodorization properties, and is suitable for clothing such as jerseys, volleyball and handball game shirts, and sports warmwear. Can be used.
以下に実施例を挙げて本発明を具体的に説明する。なお、本発明は以下に述べる実施例に限定されるものではない。 The present invention will be specifically described below with reference to examples. In addition, this invention is not limited to the Example described below.
樹脂の粘度の測定方法は以下の通りとした。
（極限粘度［ＩＶ］の測定方法）
所定量のポリエステルをフェノール／１，１，２，２−テトラクロロエタン＝６０／４０（質量比）の混合溶媒に溶解し、ウベローデ粘度計を用い２０℃に設定した株式会社柴山科学機器製作所製自動粘度測定装置ＳＳ−２７０ＬＣにて常法で測定した。
The measurement method of the viscosity of the resin was as follows.
(Measurement method of intrinsic viscosity [IV])
A certain amount of polyester is dissolved in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane = 60/40 (mass ratio) and automatically set to 20 ° C. using an Ubbelohde viscometer. It measured by the conventional method with the viscosity measuring device SS-270LC.
（相対粘度［ηｒ］の測定方法）
所定量のポリアミドを９６質量％の硫酸に溶解し、ウベローデ粘度計を用い２０℃に設定した株式会社柴山科学機器製作所製自動粘度測定装置ＳＳ−２７０ＬＣにて常法で測定した。
(Measurement method of relative viscosity [ηr])
A predetermined amount of polyamide was dissolved in 96% by mass of sulfuric acid, and measured by a conventional method using an automatic viscosity measuring device SS-270LC manufactured by Shibayama Scientific Instruments Co., Ltd., which was set to 20 ° C. using an Ubbelohde viscometer.
本発明における評価方法は、以下の通りとした。
Ａ）摩擦防融性
繊維を英光産業製筒編み機型番：ＮＣＲ-ＥＷを用い２４ゲージで編地化し、布地を２枚重ね合せてＪＩＳ Ｌ１０５６（Ｂ法）に準拠したローター型摩擦溶融試験機を用い摩擦防融性を評価した。ローターに布地を１０秒間押し付けた後の布地状態を次の４段階で分別した。
◎：ほぼ変化が認められないもの
○：擦過痕が認められるもの
△：部分的に溶融が認められるもの
×：溶融により穴あきが認められたもの
Ｂ）抗菌防臭性
得られた繊維を試験片とし、ＪＩＳ Ｌ１９０２−２０１５「繊維製品の抗菌性試験方法及び抗菌効果」の菌液吸収法に準拠して試験を行い、附属書Ｄ「発光測定法による定量法」を用いて抗菌活性値を求めた。１８時間培養後の抗菌活性値が２．２以上の場合を○と分類し、抗菌防臭性を有すると判定した。１８時間培養後の抗菌活性値が２．２未満の場合を×と分類し、抗菌防臭性が無いと判定した。
The evaluation method in the present invention was as follows.
A) Friction-proof Friction Welding Machine Fiber knitting machine Model: NCR-EW is used to make a 24 gauge knitted fabric, and two pieces of fabric are overlapped to form a rotor type friction melting tester compliant with JIS L1056 (Method B) The friction-proof property used was evaluated. The fabric state after pressing the fabric against the rotor for 10 seconds was classified in the following four stages.
◎: Almost no change is observed ○: Scratch mark is observed △: Partial melting is observed ×: Perforation is recognized by melting B) Antibacterial deodorization property JIS L1902-2015 “Testing method and antibacterial effect of textile products” is tested in accordance with the bacterial solution absorption method, and the antibacterial activity value is obtained using Annex D “Quantitative method by luminescence measurement method”. It was. The case where the antibacterial activity value after 18 hours of culture was 2.2 or more was classified as ◯, and determined to have antibacterial and deodorant properties. The case where the antibacterial activity value after 18 hours of culture was less than 2.2 was classified as x, and it was determined that there was no antibacterial and deodorant properties.
〔実施例１〕
島成分として、ＩＶが０．６７のホモポリエステルに、ＭＦＲが７ｇ／１０分の高密度ポリエチレン（ＨＤＰＥ）を８０：２０の割合で混合し、更に混合ペレットに対し０．３質量％の相溶化剤（住友化学製ボンドファースト（商品名））を更に混合したものを２８０℃に温度設定した二軸押出混練機で溶融混練したものを用い、海成分として、ＩＶが０．６７のホモポリエステルに東亞合成社製ノバロン（登録商標）ＡＧ３００（商品名）を１質量％の割合となるように２８０℃に温度設定した二軸押出混練機で溶融混練したものを用い、海成分と島成分の比率（面積比）５０：５０にて、図１の断面形状（海成分の数：１、島成分の数：１）となるように、紡速３８００ｍ／分のスピンドロー法にて紡糸し、８４ｄｔｅｘ／２４ｆの複合繊維を得た。
得られた繊維を用い、摩擦防融性を評価したところ、擦過痕もほとんど無く、◎の判定であった。更に抗菌防臭性を評価したところ、抗菌活性値が２．４で、抗菌防臭性を有するとの判定であった。
[Example 1]
As an island component, high density polyethylene (HDPE) with an MFR of 7 g / 10 min is mixed with a homopolyester with an IV of 0.67 at a ratio of 80:20, and further compatibilized with 0.3% by mass with respect to the mixed pellets. A mixture of the agent (Bond First (trade name) manufactured by Sumitomo Chemical Co., Ltd.) was melt-kneaded with a twin-screw extrusion kneader set at a temperature of 280 ° C., and the sea component was a homopolyester having an IV of 0.67. The ratio of sea component to island component using Nobaron (registered trademark) AG300 (trade name) manufactured by Toagosei Co., Ltd., melted and kneaded with a twin-screw extrusion kneader set at a temperature of 280 ° C. so as to have a ratio of 1% by mass. At an area ratio of 50:50, spinning was performed by a spin draw method with a spinning speed of 3800 m / min so as to have the cross-sectional shape of FIG. 1 (number of sea components: 1, number of island components: 1), and 84 dtex. / 24f composite It was obtained Wei.
When the obtained fiber was used to evaluate the friction-proof property, there was almost no scratch mark, and it was judged as ◎. Furthermore, when antibacterial and deodorant properties were evaluated, the antibacterial activity value was 2.4, and it was determined that the antibacterial and deodorant properties were obtained.
〔実施例２〕
島成分として、ＭＦＲが７ｇ／１０分の高密度ポリエチレン（ＨＤＰＥ）を用い、海成分として、ＩＶが０．６７のホモポリエステルと富士ケミカル製の可溶性ガラス系抗菌剤を２０質量％ポリエステルに複合したバクテキラーマスターバッチとを９５：５の割合でチップ混合したものを用い、図４のような島数が１９となる口金を用いて、海成分と島成分の比率（面積比）が９０：１０の割合で、紡速３８００ｍ／分のスピンドロー法により紡糸を行い、８４ｄｔｅｘ／２４ｆの海島型複合繊維を得た。
得られた繊維を用い、摩擦防融性を評価したところ、擦過痕がわずかに認められ、〇の判定であった。更に抗菌防臭性を評価したところ、抗菌活性値が２．３となり、抗菌防臭性を有するとの判定であった。
[Example 2]
High density polyethylene (HDPE) with an MFR of 7 g / 10 min was used as the island component, and a homopolyester with an IV of 0.67 and a soluble glass-based antibacterial agent made by Fuji Chemical were combined with 20% by mass polyester as the sea component. Using a mixture of chips in a ratio of 95: 5 to a bacter killer masterbatch, using a die having 19 islands as shown in FIG. 4, the ratio of the sea component to the island component (area ratio) is 90:10. Was spun by a spin draw method at a spinning speed of 3800 m / min to obtain 84 dtex / 24f sea-island type composite fiber.
When the resulting fiber was used to evaluate the anti-friction property, slight scratch marks were observed, and the evaluation was “good”. Furthermore, when antibacterial and deodorant properties were evaluated, the antibacterial activity value was 2.3, and it was determined that the antibacterial and deodorant properties were obtained.
〔実施例３〕
島成分として、ＭＦＲが５ｇ／１０分の直鎖状低密度ポリエチレン（ＬＬＤＰＥ）を用い、海成分として、シナネンゼオミック社のゼオミック（登録商標）を２質量％含有したηｒが２．７のポリアミド６を用い、島成分：海成分比率が２５：７５となるように、図３のような島数が１となる口金を用いて、紡速４２００ｍ／分のスピンドロー法にて紡糸し、８４ｄｔｅｘ／２４ｆの複合繊維を得た。
得られた繊維を用い、摩擦防融性を評価したところ、擦過痕が少し認められ、〇の判定であった。更に抗菌防臭性を評価したところ、抗菌活性値が２．５であり、抗菌防臭性を有するとの判定であった。
Example 3
Polyamide 6 having a ηr of 2.7 containing 2% by mass of Zeomic (registered trademark) of Sinanen Zeomic Co., Ltd. as a sea component, using linear low density polyethylene (LLDPE) with an MFR of 5 g / 10 min as an island component. , Using a spinner with a spinning speed of 4200 m / min using a die having an island number of 1 as shown in FIG. 3 so that the ratio of island component: sea component is 25:75, and 84 dtex / 24f conjugate fiber was obtained.
When the obtained fiber was used to evaluate the friction-proof property, a few scratch marks were observed, and the evaluation was “good”. Furthermore, when antibacterial and deodorant properties were evaluated, the antibacterial activity value was 2.5, and it was determined that the antibacterial and deodorant properties were obtained.
〔実施例４〕
島成分として、ＭＦＲが７ｇ／１０分の低密度ポリエチレン（ＬＤＰＥ）と、ＩＶが０．６７のホモポリエステルとを２：８の割合で混合し、更に相溶化剤としてＬＤＰＥとホモポリエステルの合計量に対し０．３質量％の相溶化剤（住友化学製ボンドファースト（商品名））を追加ペレット混合したものを２８０℃に温度設定した二軸押出混練機で溶融混練した樹脂組成物を用い、海成分として、実施例１で用いたＩＶが０．６７のホモポリエステルに東亞合成社製ノバロン（登録商標）ＡＧ３００（商品名）を１質量％の割合になるように２８０℃に温度設定した二軸押出混練機で溶融混練した樹脂組成物を用い、海成分と島成分の比率（面積比）が４０：６０となるように、図２のような島数が１９となる口金を用いて、紡速３８００ｍ／分のスピンドロー法により紡糸し、８４ｄｔｅｘ／２４ｆの海島型複合繊維を得た。
得られた繊維を用い、摩擦防融性を評価したところ、擦過痕もほとんど無く、◎の判定であった。更に抗菌防臭性を評価したところ、抗菌活性値が２．４であり、抗菌防臭性を有するとの判定であった。
Example 4
As an island component, a low density polyethylene (LDPE) having an MFR of 7 g / 10 min and a homopolyester having an IV of 0.67 are mixed in a ratio of 2: 8, and further, the total amount of LDPE and homopolyester as a compatibilizer. Using a resin composition obtained by melt-kneading with a twin-screw extrusion kneader set at a temperature of 280 ° C., a mixture of 0.3% by mass of a compatibilizer (bond first (trade name) manufactured by Sumitomo Chemical Co., Ltd.) As a sea component, the temperature was set to 280 ° C. so that NOVARON (registered trademark) AG300 (trade name) manufactured by Toagosei Co., Ltd. was used in the homopolyester having an IV of 0.67 used in Example 1 at a ratio of 1% by mass. Using a resin composition melt-kneaded with a shaft extrusion kneader, using a die having 19 islands as shown in FIG. 2 so that the ratio of the sea component to the island component (area ratio) is 40:60, Spinning speed 3800 It was spun by / min spin-draw method to obtain sea-island composite fibers of 84 dtex / 24f.
When the obtained fiber was used to evaluate the friction-proof property, there was almost no scratch mark, and it was judged as ◎. Furthermore, when antibacterial and deodorant properties were evaluated, the antibacterial activity value was 2.4 and it was determined that the antibacterial and deodorant properties were obtained.
〔実施例５〕
島成分として、ηｒが２．７のポリアミド６にＭＦＲが７ｇ／１０分の高密度ポリエチレン（ＨＤＰＥ）を８０：２０の割合で混合し、更に混合ペレットに対し０．３質量％の相溶化剤（住友化学製ボンドファースト（商品名））を更に混合したものを２５０℃に温度設定した二軸押出混練機で溶融混練したものを用い、海成分として、ＩＶ が０．６７のホモポリエステルに東亞合成社製ノバロン（登録商標）ＡＧ３００（商品名）を１質量％の割合となるように２８０℃に温度設定した二軸押出混練機で溶融混練したものを用い、海成分と島成分の比率（面積比）５０：５０にて、図１の断面形状（海成分の数：１、島成分の数：１）となるように、紡速４０００ｍ／分のスピンドロー法にて紡糸し、８４ｄｔｅｘ／２４ｆの複合繊維を得た。
得られた繊維を用い、摩擦防融性を評価したところ、擦過痕もほとんど無く、◎の判定であった。更に抗菌防臭性を評価したところ、抗菌活性値が２．４で、抗菌防臭性を有するとの判定であった。
Example 5
As an island component, polyamide 6 having ηr of 2.7 and high density polyethylene (HDPE) having an MFR of 7 g / 10 min are mixed at a ratio of 80:20, and a compatibilizer of 0.3% by mass with respect to the mixed pellets. (A mixture of Sumitomo Chemical's Bond First (trade name)) melt-kneaded with a twin-screw extrusion kneader set at a temperature of 250 ° C., and a sea component with a homopolyester having an IV of 0.67. The ratio of sea component and island component (using a biaxial extrusion kneader set at a temperature of 280 ° C. so that the proportion of NOVALON (registered trademark) AG300 (trade name) manufactured by Synthetic Co., Ltd. is set to a ratio of 1% by mass ( At an area ratio of 50:50, spinning was performed by a spin draw method at a spinning speed of 4000 m / min so as to obtain the cross-sectional shape of FIG. 1 (number of sea components: 1, number of island components: 1), and 84 dtex / 24f composite fiber is obtained .
When the obtained fiber was used to evaluate the friction-proof property, there was almost no scratch mark, and it was judged as ◎. Furthermore, when antibacterial and deodorant properties were evaluated, the antibacterial activity value was 2.4, and it was determined that the antibacterial and deodorant properties were obtained.
〔比較例１〕
実施例１で用いたＩＶが０．６７のホモポリエステルを単独でスピンドロー法により紡糸し、８４ｄｔｅｘ／２４ｆの丸断面繊維を得た。
得られた繊維を用い、摩擦防融性を評価したところ、完全に穴が開き×の判定であった。更に抗菌防臭性を評価したところ、抗菌活性値が０．５であり、抗菌防臭性が無いとの判定であった。
[Comparative Example 1]
The homopolyester having an IV of 0.67 used in Example 1 was spun alone by a spin draw method to obtain a round cross-section fiber of 84 dtex / 24f.
When the obtained fiber was used to evaluate the friction-proof property, the hole was completely opened, and it was judged as x. Furthermore, when antibacterial and deodorant properties were evaluated, the antibacterial activity value was 0.5, and it was determined that there was no antibacterial and deodorant properties.
〔比較例２〕
島成分として、ＩＶが０．６７のホモポリエステルを用い、海成分として、実施例１と同様にＩＶが０．６７のホモポリエステルに東亞合成社製ノバロン（登録商標）ＡＧ３００（商品名）を１質量％の割合となるように２８０℃に温度設定した二軸押出混練機で溶融混練したものを用い、島成分と海成分の比率（面積比）５０：５０にて、紡速３８００ｍ／分のスピンドロー法にて紡糸し、図１のような島数１、海数１の断面の８４ｄｔｅｘ／２４ｆの複合繊維を得た。
得られた繊維を用い、摩擦防融性を評価したところ、容易に穴が開き、×の判定であった。更に抗菌防臭性を評価したところ、抗菌活性値が２．４であり、抗菌防臭性を有するとの判定であった。
[Comparative Example 2]
As an island component, a homopolyester having an IV of 0.67 was used, and as a sea component, Novalon (registered trademark) AG300 (trade name) manufactured by Toagosei Co., Ltd. was added to a homopolyester having an IV of 0.67 as in Example 1. Using a melt-kneaded mixture with a twin-screw extrusion kneader set at a temperature of 280 ° C. so as to have a mass% ratio, the ratio of the island component to the sea component (area ratio) is 50:50, and the spinning speed is 3800 m / min. Spinning was performed by a spin draw method to obtain a 84 dtex / 24f composite fiber having a cross section of 1 island and 1 sea as shown in FIG.
When the obtained fiber was used to evaluate the friction-proof property, a hole was easily opened, and the result was x. Furthermore, when antibacterial and deodorant properties were evaluated, the antibacterial activity value was 2.4 and it was determined that the antibacterial and deodorant properties were obtained.
〔比較例３〕
海成分に、東亜合成社製のノバロン（登録商標）ＡＧ３００を用いなかったこと以外は、実施例１と同様にして８４ｄｔｅｘ／２４ｆの海島型複合繊維を得た。得られた繊維を用い、摩擦防融性を評価したところ、擦過痕もほとんど無く、◎の判定であった。抗菌防臭性を評価したところ、抗菌活性値が０．５で、抗菌防臭性がないとの判定であった。
[Comparative Example 3]
An 84 dtex / 24f sea-island composite fiber was obtained in the same manner as in Example 1 except that NOARON (registered trademark) AG300 manufactured by Toa Gosei Co., Ltd. was not used as the sea component. When the obtained fiber was used to evaluate the friction-proof property, there was almost no scratch mark, and it was judged as ◎. When antibacterial and deodorant properties were evaluated, it was determined that the antibacterial activity value was 0.5 and there was no antibacterial and deodorant properties.
〔比較例４〕
島成分として、ＩＶが０．６７のホモポリエステルを用い、海成分と島成分の比率（面積比）を５０：５０とする以外は、実施例３と同様に紡糸し、８４ｄｔｅｘ／２４ｆの複合繊維を得た。
得られた繊維を用い、摩擦防融性の評価したところ、完全に穴が開き×の判定であった。更に抗菌防臭性を評価したところ、抗菌活性値が２．５であり、〇の判定であった。
[Comparative Example 4]
As the island component, a homopolyester having an IV of 0.67 is used, and the fiber is spun in the same manner as in Example 3 except that the ratio of the sea component to the island component (area ratio) is 50:50, and the composite fiber is 84 dtex / 24f. Got.
When the obtained fiber was used to evaluate the anti-friction property, the hole was completely opened and it was judged as x. Furthermore, when antibacterial and deodorant properties were evaluated, the antibacterial activity value was 2.5, which was judged as ◯.
〔比較例５〕
海成分として実施例１で用いたＩＶが０．６７のホモポリエステルを使用し、島成分として実施例１と同様にＩＶが０．６７のホモポリエステルとＭＦＲが７ｇ／１０分のＨＤＰＥとを８０：２０で混合し、混合ペレットに対し０．３質量％の割合となるように相溶化剤（住友化学製ボンドファースト（商品名））と、更に東亞合成社製ノバロン（登録商標）ＡＧ３００（商品名）を１質量％の割合となるように混合したものを２８０℃に温度設定した二軸押出混練機で溶融混練したものを用い、後は実施例１と同様に紡糸して８４ｄｔｅｘ／２４ｆの複合繊維を得た。
得られた繊維を用い、摩擦防融性を評価したところ、擦過痕もほとんど無く、◎の判定であったが、抗菌防臭性を評価したところ、抗菌活性値が０．５で、抗菌防臭性は認められなかった。
[Comparative Example 5]
The homopolyester having an IV of 0.67 used in Example 1 was used as the sea component, and the homopolyester having an IV of 0.67 and HDPE having an MFR of 7 g / 10 min were used as the island component in the same manner as in Example 1. : Compatibilizer (Bond First (trade name) manufactured by Sumitomo Chemical Co., Ltd.) so as to be a ratio of 0.3% by mass with respect to the mixed pellet, and Novalon (registered trademark) AG300 (product manufactured by Toagosei Co., Ltd.) No.) was mixed with a biaxial extrusion kneader set at a temperature of 280 ° C., and then spun in the same manner as in Example 1 to obtain 84 dtex / 24 f. A composite fiber was obtained.
When the resulting fiber was used to evaluate the friction-proof property, there was almost no scratch mark and it was judged as ◎, but when the antibacterial and deodorant property was evaluated, the antibacterial activity value was 0.5 and the antibacterial and deodorant property Was not recognized.
実施例および比較例から得られた繊維と評価について表１に示す。
以上のように、実施例品はいずれも、抗菌防臭性と摩擦防止融性の兼ね備えた繊維となった。 As described above, all of the examples were fibers having both antibacterial and deodorizing properties and antifriction and fusibility.
摩擦防融性を有する衣料品で、かつ抗菌防臭機能を有するスポーツ用途等に適応可能な複合繊維をいる事が出来る。 It is possible to have a composite fiber that can be applied to sports applications having antibacterial and deodorizing functions, and is a clothing product having friction resistance.
１ 海成分
２、３ 島成分
1
ポリエステル繊維は、その優れた力学的特性および化学的特性から、スポーツ衣料分野に数多く利用されている。しかし、ポリエステル等の合成繊維は、綿やレーヨンなどの天然系繊維と異なり、体育館等での転倒やスライディング時、床と布帛との間で生じる摩擦熱によって布帛が溶融し、布帛に穴が開いてしまう欠点を有する。また特にスポーツ衣料分野においては多くの発汗を伴う状況下で使用されるため、汗に含まれる乳酸、尿素などの老廃物や汗をかいた状態で衣服と肌が擦れ合うことで繊維に付着した皮脂などが衣服表面で細菌類により分解されることで悪臭を発することがある。 Polyester fibers are widely used in the sports clothing field because of their excellent mechanical and chemical properties. However, unlike natural fibers such as cotton and rayon, synthetic fibers such as polyester melt the fabric due to frictional heat generated between the floor and the fabric when falling or sliding in a gymnasium or the like, and open holes in the fabric. Has the disadvantage of Also, especially in the field of sports clothing, it is used in situations involving a lot of sweating, so lactic acid, urea, and other waste products contained in sweat, and sebum that adheres to the fibers by rubbing clothes and skin in a sweaty state May cause a bad odor when decomposed by bacteria on the clothes surface.
以下、本発明における無機粒子を得る方法について例示する。
担持体がゼオライトの場合、例えば、特開昭５９−１３３２３５号公報に示されているようにゼオライト微粒子を硝酸銀水溶液で処理してイオン交換反応を行い、ゼオライトに銀を担持させることにより本発明における無機粒子を得ることができる。また市販の製品としては、例えば、シナネンゼオミック社製「ゼオミック（登録商標）（商品名）」として入手できる。
担持体がリン酸ジルコニウムやリン酸チタンの場合、例えば、特開平３−８３９０５号公報に開示されているように炭酸リチウム、リン酸水素二アンモニウムおよび酸化ジルコニウム、または酸化チタンを所定量混合し、１３００℃で焼結して得た化合物を微粉砕した後、硝酸銀水溶液で処理して、本発明における無機粒子を得ることができる。市販の製品としては、例えば、東亞合成社製「ノバロン（登録商標）（商品名）」として入手できる。
担持体が水溶性ガラスの場合、例えば、特開平３−１２４８１０号公報に開示されているように所定量の酸化銀、酸化ホウ素、シリカおよび酸化ナトリウムを溶融ガラス化し、微粉砕して得た銀イオンを放出する本発明における無機粒子を得たり、特開平７−２５７９３８号公報に開示されているように所定量の酸化亜鉛、酸化ホウ素および酸化ナトリウムを１０００〜１３００℃で溶解ガラス化し、微粉砕して得た亜鉛イオンを放出する本発明における無機粒子を得ることができる。市販の製品としては、例えば、石塚硝子社製「イオンピュア（登録商標）（商品名）」として入手できる。
また、市販の富士ケミカル社製の各種抗菌剤を本発明における無機粒子として用いることができる。更に、富士ケミカル社製の各種抗菌剤をポリエステルやポリアミド中に高濃度で分散させている「バクテキラー（登録商標）マスターバッチ（商品名）」であれば、本発明における無機粒子を含有する本発明の摩擦防融複合繊維を容易に得ることができる。
Hereinafter, the method for obtaining the inorganic particles in the present invention will be exemplified.
When the support is a zeolite, for example, as shown in JP-A-59-133235, the zeolite fine particles are treated with an aqueous silver nitrate solution to carry out an ion exchange reaction, and the zeolite is loaded with silver to thereby support the present invention. Inorganic particles can be obtained. In addition, as a commercially available product, for example, “Zeomic (registered trademark ) ” (trade name) manufactured by Sinanen Zeomic Co., Ltd. can be obtained.
When the support is zirconium phosphate or titanium phosphate, for example, as disclosed in JP-A-3-83905, lithium carbonate, diammonium hydrogen phosphate and zirconium oxide, or a predetermined amount of titanium oxide are mixed, The compound obtained by sintering at 1300 ° C. can be finely pulverized and then treated with an aqueous silver nitrate solution to obtain the inorganic particles in the present invention. As a commercially available product, for example, “Novalon (registered trademark) (trade name)” manufactured by Toagosei Co., Ltd. can be obtained.
When the support is water-soluble glass, for example, silver obtained by melting and finely pulverizing a predetermined amount of silver oxide, boron oxide, silica and sodium oxide as disclosed in JP-A-3-124810 Inorganic particles in the present invention that release ions are obtained, or a predetermined amount of zinc oxide, boron oxide, and sodium oxide is dissolved and vitrified at 1000 to 1300 ° C. as disclosed in JP-A-7-257938 and finely pulverized. Thus, inorganic particles in the present invention that release the zinc ions obtained can be obtained. As a commercially available product, for example, “Ion Pure (registered trademark)” (trade name) manufactured by Ishizuka Glass Co., Ltd. is available.
Various antibacterial agents manufactured by Fuji Chemical Co., Ltd. can be used as inorganic particles in the present invention. Furthermore, the present invention containing the inorganic particles in the present invention is "Bactekiller (registered trademark) masterbatch (trade name)" in which various antibacterial agents manufactured by Fuji Chemical are dispersed in polyester or polyamide at a high concentration. This friction-fusible composite fiber can be easily obtained.
Claims (6)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112575408A (en) * | 2020-12-16 | 2021-03-30 | 江苏华峰超纤材料有限公司 | Adventitious island sea-island fiber and preparation method thereof |
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