JP4922654B2 - Nanofiber fiber structure, method for producing the same, and fiber product - Google Patents
Nanofiber fiber structure, method for producing the same, and fiber product Download PDFInfo
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Images
Description
単繊維径が１０００ｎｍ以下のナノファイバーを含むナノファイバー繊維構造体およびその製造方法および該ナノファイバー繊維構造体を用いてなる繊維製品に関する。 The present invention relates to a nanofiber fiber structure including nanofibers having a single fiber diameter of 1000 nm or less, a manufacturing method thereof, and a fiber product using the nanofiber fiber structure.
従来、ナノファイバーで構成され、織物や編物などの形態を有するナノファイバー繊維構造体が提案されている（例えば、特許文献１、特許文献２参照）。かかるナノファイバー繊維構造体は、通常、海成分と島成分とからなり、かつ島成分の径が１０００ｎｍ以下の海島型複合繊維を用いて繊維構造体を得た後、前記の島成分をアルカリ等の溶剤により溶解除去することにより得られる。 Conventionally, nanofiber fiber structures composed of nanofibers and having forms such as woven fabrics and knitted fabrics have been proposed (see, for example, Patent Document 1 and Patent Document 2). Such a nanofiber fiber structure is usually composed of a sea component and an island component, and after obtaining a fiber structure using a sea-island type composite fiber having an island component diameter of 1000 nm or less, the island component is converted to an alkali or the like. It is obtained by dissolving and removing with a solvent.
しかしながら、単糸（島成分）が細いほど、海成分を除去した後の単糸どうしが凝集密着しやすいため、単糸塊が発生し、人工皮革調の肌触りや柔らかさなどの風合い的特徴、および防風性、吸水性、防透性などの機能が十分に発現されないという問題があった。 However, as the single yarn (island component) is thinner, the single yarn after removing the sea component is more likely to agglomerate and adhere to each other, resulting in the formation of a single yarn lump, and texture features such as artificial leather-like feel and softness, In addition, there is a problem that functions such as wind resistance, water absorption, and permeability are not sufficiently exhibited.
本発明は上記の背景に鑑みなされたものであり、その目的は、人工皮革調の肌触りや柔らかさなどの風合い的特徴、および防風性、吸水性、防透性などの機能性に優れたナノファイバー繊維構造体およびその製造方法および繊維製品を提供することにある。 The present invention has been made in view of the above-mentioned background, and its purpose is to provide nano-materials having excellent texture characteristics such as artificial leather-like touch and softness, and functionality such as wind-proof property, water absorption property, and water-proof property. It is providing a fiber fiber structure, its manufacturing method, and a fiber product.
本発明者らは上記の課題を達成するため鋭意検討した結果、海成分と島成分とからなり、かつ島成分の径が１０００ｎｍ以下の海島型複合繊維を用いて繊維構造体を得た後、前記の島成分を溶解除去し、次いで高圧水で該繊維構造体を噴射処理することにより、単糸（ナノファイバー）同士をばらけた状態にすることにより、人工皮革調の肌触りや柔らかさなどの風合い的特徴、および防風性、吸水性、防透性などの機能性に優れたナノファイバー繊維構造体が得られることを見出し、さらに鋭意検討を重ねることにより本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors obtained a fiber structure using a sea-island composite fiber composed of a sea component and an island component, and the island component having a diameter of 1000 nm or less. By dissolving and removing the island components, and then spraying the fiber structure with high-pressure water, the single yarns (nanofibers) are separated from each other, thereby providing an artificial leather-like feel and softness. The present inventors have found that a nanofiber fiber structure excellent in texture characteristics and functions such as wind resistance, water absorption, and permeability can be obtained, and has further completed the present invention by intensive studies.
かくして、本発明によれば「有機繊維からなり単繊維径が１０００ｎｍ以下のナノファイバーを、ナノファイバー数２０００〜１００００のマルチフィラメント糸条として含む繊維構造体であって、該繊維構造体中において、ナノファイバー同士が凝集密着することなく、ばらけた状態で存在することを特徴とするナノファイバー繊維構造体。」が提供される。
その際、ナノファイバー繊維構造体が前記のナノファイバーを２０重量%以上含むこと
が好ましい。また、繊維構造体が織編物であることが好ましい。
Thus, according to the present invention, a fiber structure comprising nanofibers made of organic fibers and having a single fiber diameter of 1000 nm or less as multifilament yarns having 2000 to 10,000 nanofibers , There is provided a nanofiber fiber structure characterized in that the nanofibers are present in a separated state without agglomerating and adhering to each other. "
At that time, the nanofiber fiber structure preferably contains 20% by weight or more of the nanofiber. The fiber structure is preferably a woven or knitted fabric.
特に、繊維構造体が、Ｄ１／２×Ｃｏ×Ｗｅが１００００〜２０００００の範囲内の編物であることが好ましい。ただし、Ｄは前記マルチフィラメント糸条の総繊度（ｄｔｅｘ）、Ｃｏは２．５４ｃｍあたりのコース数、Ｗｅは２．５４ｃｍあたりのウエール数である。 In particular, the fiber structure is preferably a knitted fabric having a D 1/2 × Co × We of 10,000 to 200,000. However, D is the total fineness (dtex) of the multifilament yarn, Co is the number of courses per 2.54 cm, and We is the number of wales per 2.54 cm.
また、繊維構造体が、下記式により算出されるカバーファクターＣＦが１７００〜３８００の範囲内の織物であることが好ましい。
ＣＦ＝（ＤＷｐ／１．１）１／２×ＭＷｐ＋（ＤＷｆ／１．１）１／２×ＭＷｆ
ただし、ＤＷｐは経糸総繊度（ｄｔｅｘ）、ＭＷｐは経糸織密度（本／２．５４ｃｍ）、ＤＷｆは緯糸総繊度（ｄｔｅｘ）、ＭＷｆは緯糸織密度（本／２．５４ｃｍ）である。
Moreover, it is preferable that the fiber structure is a woven fabric having a cover factor CF calculated by the following formula within a range of 1700 to 3800.
CF = (DWp / 1.1) 1/2 × MWp + (DWf / 1.1) 1/2 × MWf
However, DWp is the total warp fineness (dtex), MWp is the warp weave density (main / 2.54 cm), DWf is the total weft fineness (dtex), and MWf is the weft weave density (main / 2.54 cm).
本発明のナノファイバー繊維構造体において、ナノファイバーがポリエステルからなることが好ましい。その際、ポリエステルが、艶消し剤をポリエステル重量に対して０．３重量％以上含有することが好ましい。 In the nanofiber fiber structure of the present invention, the nanofiber is preferably made of polyester. In that case, it is preferable that polyester contains 0.3 weight% or more of matting agents with respect to the polyester weight.
本発明のナノファイバー繊維構造体において、通気性が５０ｃｃ／ｃｍ２／ｓ以下であることが好ましい。また、防透性の指標であるΔＬ値が１．００以下であることが好ましい。また、飽和吸水率が２００％以上であることが好ましい。 In the nanofiber fiber structure of the present invention, the air permeability is preferably 50 cc / cm 2 / s or less. Further, it is preferable that the ΔL value which is an index of permeation resistance is 1.00 or less. The saturated water absorption is preferably 200% or more.
また、本発明によれば、「海成分と島成分とからなり、かつ島成分の径が１０００ｎｍ以下の海島型複合繊維を用いて繊維構造体を得た後、前記の海成分を溶解除去することにより、前記海島型複合繊維を、単繊維径が１０００ｎｍ以下のナノファイバーからなり、かつナノファイバー数２０００〜１００００のマルチフィラメント糸条とし、次いで高圧水で該繊維構造体を噴射処理することを特徴とするナノファイバー繊維構造体の製造方法。」が提供される。 Further, according to the present invention, after obtaining a fiber structure using a sea-island type composite fiber composed of a sea component and an island component and having an island component diameter of 1000 nm or less, the sea component is dissolved and removed . Thus, the sea-island type composite fiber is made of a nanofilament having a single fiber diameter of 1000 nm or less and a multifilament yarn having 2000 to 10,000 nanofibers, and then the fiber structure is jetted with high-pressure water. A method for producing a featured nanofiber fiber structure ”is provided.
また、本発明によれば、「前記のナノファイバー繊維構造体を用いてなる、アウター用衣料、スポーツ用衣料、インナー用衣料、靴材、おしめや介護用シーツの医療・衛生用品、寝装寝具、椅子やソファーの表皮材、カーペット、カーシート地、インテリア用品、空気清浄機用や浄水器用のフィルター製品、電池セパレータ、ワイピングクロスなどの生活資材、ハードデイスク用研磨布、および細胞吸着剤などのメデイカル材料からなる群より選択されるいずれかの繊維製品。」が提供される。 Further, according to the present invention, “an outer garment, a sports garment, an inner garment, a shoe material, a medical / hygienic article for a diaper or a care sheet, and bedding bedding, comprising the nanofiber fiber structure described above. , Chairs and sofa skins, carpets, car seats, interior goods, filter products for air purifiers and water purifiers, daily life materials such as battery separators, wiping cloths, hard disk polishing cloths, and cell adsorbents Any fiber product selected from the group consisting of materials "is provided.
本発明によれば、人工皮革調の肌触りや柔らかさなどの風合い的特徴、および防風性、吸水性、防透性などの機能性に優れたナノファイバー繊維構造体およびその製造方法および繊維製品が得られる。 According to the present invention, a nanofiber fiber structure excellent in texture characteristics such as artificial leather-like touch and softness, and functions such as windproof property, water absorption property, and water permeability property, a method for producing the same, and a fiber product are provided. can get.
以下、本発明の実施の形態について詳細に説明する。
まず、本発明のナノファイバー繊維構造体には、単繊維径（単繊維の直径）が１０００ｎｍ以下（好ましくは１００〜８００ｎｍ）のナノファイバーが含まれる。単繊維の断面形状が丸断面以外の異型断面である場合には、丸断面に換算した直径を単繊維径とする。単繊維径は、透過型電子顕微鏡で繊維の横断面を撮影することにより測定が可能である。なお、該単繊維径を単糸繊度に換算すると、０．０１ｄｔｅｘ以下に相当する。
Hereinafter, embodiments of the present invention will be described in detail.
First, the nanofiber fiber structure of the present invention includes nanofibers having a single fiber diameter (single fiber diameter) of 1000 nm or less (preferably 100 to 800 nm). When the cross-sectional shape of the single fiber is an atypical cross section other than the round cross section, the diameter converted to the round cross section is defined as the single fiber diameter. The single fiber diameter can be measured by photographing the cross section of the fiber with a transmission electron microscope. In addition, when this single fiber diameter is converted into the single yarn fineness, it corresponds to 0.01 dtex or less.
本発明のナノファイバー繊維構造体において、ナノファイバー単糸（以下、単に「ナノファイバー」という。）同士が凝集密着することなく、ばらけた状態で存在することが肝要である。ここで、本発明でいう「ばらけた状態」とは、図１（繊維構造体の側面写真）および図２（繊維構造体の断面写真）に示すように、ナノファイバーが互いに独立していることをいう。ナノファイバーがこのようにばらけた状態で存在することにより、ナノファイバー繊維構造体は、人工皮革調の肌触りや柔らかさなどの風合い的特徴、および防風性、吸水性、防透性などの機能を十分に発現できる。これに対して、図３（繊維構造体の側面写真）および図４（繊維構造体の断面写真）に示された、従来のナノファイバー繊維構造体では、ナノファイバー同士が凝集密着しているため、人工皮革調の肌触りや柔らかさなどの風合いが十分発揮されないばかりか、防風性、吸水性、防透性などの機能があまり発現されない。なお、本発明において、「ばらけた状態」とは１００本以上のナノファイバーが密着凝集した単糸塊がないという意味であり、ナノファイバー同士は完全に独立している必要はなく、１００本未満のナノファイバーが凝集密着した単糸塊が存在してもよい。 In the nanofiber fiber structure of the present invention, it is important that nanofiber single yarns (hereinafter simply referred to as “nanofibers”) are present in a dispersed state without agglomeration and adhesion. Here, the “disengaged state” as used in the present invention means that the nanofibers are independent from each other as shown in FIG. 1 (side view of the fiber structure) and FIG. 2 (cross section of the fiber structure). Say. With the presence of nanofibers in such a state, the nanofiber fiber structure has texture features such as artificial leather-like touch and softness, and functions such as windproof, water absorption, and permeability. It can be fully expressed. On the other hand, in the conventional nanofiber fiber structure shown in FIG. 3 (side view photograph of the fiber structure) and FIG. 4 (cross section photograph of the fiber structure), the nanofibers are agglomerated and adhered to each other. In addition, the texture such as artificial leather-like touch and softness is not sufficiently exhibited, and functions such as wind resistance, water absorption, and permeability are not so expressed. In the present invention, the “disjoint state” means that there is no single yarn lump in which 100 or more nanofibers are closely aggregated and aggregated, and the nanofibers do not need to be completely independent, but less than 100. There may be a single yarn mass in which the nanofibers are agglomerated and adhered.
本発明のナノファイバー繊維構造体において、前記のナノファイバーが２０重量%以上（より好ましくは５０重量％以上、さらに好ましくは７０重量%以上、特に好ましくは１００重量％）含まれることが好ましい。ナノファイバーの含有量が２０重量％未満では、防風性、吸水性、防透性などの機能が発現されないおそれがある。 In the nanofiber fiber structure of the present invention, the nanofiber is preferably contained in an amount of 20% by weight or more (more preferably 50% by weight or more, further preferably 70% by weight or more, particularly preferably 100% by weight). If the nanofiber content is less than 20% by weight, functions such as windproof, water-absorbing and anti-permeability may not be exhibited.
本発明のナノファイバー繊維構造体において、繊維構造体の形態としては特に限定されず、織編物、フェルト、糸条、不織布などが例示される。なかでも織編物が好適である。
編物の場合では、Ｄ１／２×Ｃｏ×Ｗｅが１００００〜２０００００（より好ましくは２００００〜１０００００）の範囲内であると、優れた防風性、吸水性、防透性が得られ好ましい。ただし、Ｄは前記マルチフィラメント糸条の総繊度（ｄｔｅｘ）、Ｃｏは２．５４ｃｍあたりのコース数、Ｗｅは２．５４ｃｍあたりのウエール数である。
In the nanofiber fiber structure of the present invention, the form of the fiber structure is not particularly limited, and examples thereof include woven and knitted fabric, felt, yarn, and nonwoven fabric. Of these, woven or knitted fabric is preferred.
In the case of a knitted fabric, it is preferable that D 1/2 × Co × We is in the range of 10,000 to 200,000 (more preferably 20000 to 100,000) because excellent windproof properties, water absorption, and permeability are obtained. However, D is the total fineness (dtex) of the multifilament yarn, Co is the number of courses per 2.54 cm, and We is the number of wales per 2.54 cm.
一方、織物の場合では、下記式により算出されるカバーファクターＣＦが１７００〜３８００の範囲内であると、優れた防風性、吸水性、防透性が得られ好ましい。
ＣＦ＝（ＤＷｐ／１．１）１／２×ＭＷｐ＋（ＤＷｆ／１．１）１／２×ＭＷｆ
ただし、ＤＷｐは経糸総繊度（ｄｔｅｘ）、ＭＷｐは経糸織密度（本／２．５４ｃｍ）、ＤＷｆは緯糸総繊度（ｄｔｅｘ）、ＭＷｆは緯糸織密度（本／２．５４ｃｍ）である。
On the other hand, in the case of a woven fabric, it is preferable that the cover factor CF calculated by the following formula is in the range of 1700 to 3800 because excellent windproof properties, water absorption properties, and permeability properties are obtained.
CF = (DWp / 1.1) 1/2 × MWp + (DWf / 1.1) 1/2 × MWf
However, DWp is the total warp fineness (dtex), MWp is the warp weave density (main / 2.54 cm), DWf is the total weft fineness (dtex), and MWf is the weft weave density (main / 2.54 cm).
なお、ナノファイバー繊維構造体が織編物である場合、ナノファイバーはマルチフィラメント糸条として織編物中に配される。その際、マルチフィラメント糸条のナノファイバー数は、５００以上（より好ましくは２０００〜１００００）であることが好ましい。 When the nanofiber fiber structure is a woven or knitted fabric, the nanofibers are arranged in the woven or knitted fabric as multifilament yarns. At that time, the number of nanofibers of the multifilament yarn is preferably 500 or more (more preferably 2000 to 10000).
また、織編物の目付けとしては１０〜３００ｇ／ｍ２の範囲であることは好ましい。
前記のナノファイバーの種類としては、レーヨンなどの再生繊維、アセテートなどの半合成繊維、ポリエチレンテレフタレートやポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリ乳酸などのポリエステル系繊維、第３成分を共重合させたポリエステル系繊維、ポリエーテルエステル系繊維、アクリル繊維、ナイロン繊維、アラミド繊維などの合成繊維が例示される。これらの繊維は１種類でもよいし、複数の組合せであってもよい。なかでも、リサクル性の点でポリエステル系繊維が好適である。かかるポリエステル系繊維には、マテリアルリサイクルまたはケミカルリサイクルされたポリエステル系繊維が含まれる。また、用途によっては、チタン化合物およびリン化合物を触媒として得られたポリエステルからなるポリエステル系繊維も好ましい。なお、かかるナノファイバー中には、本発明の目的を損なわない範囲内で必要に応じて、微細孔形成剤、カチオン染料可染剤、着色防止剤、熱安定剤、蛍光増白剤、艶消し剤、着色剤、吸湿剤、無機微粒子が１種または２種以上含まれていてもよい。なかでも、ナノファイバーが、艶消し剤をポリエステル重量に対して０．３重量％以上（より好ましくは０．４〜２．０重量％）含むポリエステル系繊維であると、特に優れた防透性が得られ好ましい。もちろん、ポリエステル系繊維に艶消し剤がまったく含まれていない（含有量が０重量％）場合であっても、十分防透性が得られる。
Further, it is preferred basis weight of the woven or knitted fabric is in the range of 10 to 300 g / m 2.
As the types of the nanofibers, recycled fibers such as rayon, semi-synthetic fibers such as acetate, polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polylactic acid, and a third component were copolymerized. Examples thereof include synthetic fibers such as polyester fibers, polyether ester fibers, acrylic fibers, nylon fibers, and aramid fibers. These fibers may be one type or a plurality of combinations. Of these, polyester fibers are preferred from the viewpoint of recyclability. Such polyester fiber includes material-recycled or chemical-recycled polyester fiber. Further, depending on the use, a polyester fiber made of polyester obtained using a titanium compound and a phosphorus compound as a catalyst is also preferable. In such nanofibers, a fine pore-forming agent, a cationic dye dyeing agent, a coloring inhibitor, a heat stabilizer, a fluorescent brightening agent, a matte, and the like may be included in the nanofiber as long as the object of the present invention is not impaired. 1 type (s) or 2 or more types of an agent, a coloring agent, a hygroscopic agent, and inorganic fine particles may be contained. Especially, when the nanofiber is a polyester fiber containing a matting agent in an amount of 0.3% by weight or more (more preferably 0.4 to 2.0% by weight) with respect to the weight of the polyester, particularly excellent permeation resistance. Is preferable. Of course, even when the matting agent is not contained in the polyester fiber at all (content is 0% by weight), sufficient permeability can be obtained.
本発明のナノファイバー繊維構造体において、ナノファイバー以外の他糸条が含まれる場合、かかる他糸条の繊維種類は限定されないが、リサクル性の点でポリエステル繊維糸条が好ましい。 In the nanofiber fiber structure of the present invention, when other yarns other than nanofibers are included, the fiber type of the other yarns is not limited, but polyester fiber yarns are preferable in terms of recyclability.
本発明のナノファイバー繊維構造体は、例えば以下の製造方法により製造することができる。すなわち、海成分と島成分とからなり、かつ島成分の径が１０００ｎｍ以下の海島型複合繊維を用いて繊維構造体を得た後、前記の海成分を溶解除去し、次いで高圧水で該繊維構造体を噴射処理することを特徴とする製造方法である。 The nanofiber fiber structure of the present invention can be produced, for example, by the following production method. That is, after obtaining a fiber structure using a sea-island type composite fiber composed of a sea component and an island component and having an island component diameter of 1000 nm or less, the sea component is dissolved and removed, and then the fiber is added with high-pressure water. A manufacturing method is characterized in that a structure is sprayed.
ここで、高圧水で該繊維構造体を噴射処理することが特に肝要である。海成分を溶解除去した直後、島成分（ナノファイバー）同士は凝集密着しているが、前記の噴射処理により、凝集密着した複数のナノファイバーがばらけた状態で存在することになる。その際、高圧水の圧力としては、３〜１０ＭＰａ（３０〜１００ｋｇｆ／ｃｍ２）の範囲が好ましく、装置としては、スパンレース用ウオーターニードル装置（噴射孔径は０．２ｍｍ以下が好ましい。）や超音波水が好適である。 Here, it is particularly important to spray the fiber structure with high-pressure water. Immediately after the sea component is dissolved and removed, the island components (nanofibers) are coherently adhered to each other, but a plurality of coherently adhered nanofibers are present in a dispersed state by the spraying process. At that time, the pressure of the high-pressure water is preferably in the range of 3 to 10 MPa (30 to 100 kgf / cm 2 ), and the device is a spunlace water needle device (injection hole diameter is preferably 0.2 mm or less) or super. Sonic water is preferred.
また、海島型複合繊維としては、以下のものが好適である。すなわち、ポリマーの組合せは、海成分ポリマーが島成分ポリマーよりも溶解性が高い組合せであれば任意であるが、特に溶解速度比（海／島）が２００以上であることが好ましい。かかる溶解速度比が２００未満の場合には、繊維断面中央部の海成分を溶解させている間に繊維断面表層部の島成分の一部も溶解されるため、海成分を完全に溶解除去するためには、島成分の何割かも減量されてしまうことになり、島成分の太さ斑や溶剤浸食による強度劣化が発生して、毛羽やピリングなどの品位に問題が生じやすくなる。 Further, as the sea-island type composite fibers, the following are suitable. That is, the combination of the polymers is arbitrary as long as the sea component polymer is a combination having higher solubility than the island component polymer, but the dissolution rate ratio (sea / island) is preferably 200 or more. When the dissolution rate ratio is less than 200, part of the island component of the fiber cross-section surface layer portion is dissolved while the sea component of the fiber cross-section central portion is dissolved, so the sea component is completely dissolved and removed. For this reason, the island component is reduced by a percentage, and strength deterioration due to the thickness variation of the island component and solvent erosion occurs, and problems such as fluff and pilling are likely to occur.
海成分ポリマーは、好ましくは島成分との溶解速度比が２００以上であればいかなるポリマーであってもよいが、特に繊維形成性の良好なポリエステル、ポリアミド、ポリスチレン、ポリエチレンなどが好ましい。例えば、アルカリ水溶液易溶解性ポリマーとしては、ポリ乳酸、超高分子量ポリアルキレンオキサイド縮合系ポリマー、ポリエチレングルコール系化合物共重合ポリエステル、ポリエチレングリコール系化合物と５−ナトリウムスルホン酸イソフタル酸の共重合ポリエステルが好適である。また、ナイロン６は、ギ酸溶解性があり、ポリスチレン・ポリエチレンはトルエンなど有機溶剤に非常によく溶ける。なかでも、アルカリ易溶解性と海島断面形成性とを両立させるため、ポリエステル系のポリマーとしては、５−ナトリウムスルホイソフタル酸６〜１２モル％と分子量４０００〜１２０００のポリエチレングルコールを３〜１０重量％共重合させた固有粘度が０．４〜０．６のポリエチレンテレフタレート系共重合ポリエステルが好ましい。ここで、５−ナトリウムイソフタル酸は親水性と溶融粘度向上に寄与し、ポリエチレングリコール（ＰＥＧ）は親水性を向上させる。なお、ＰＥＧは分子量が大きいほど、その高次構造に起因すると考えられる親水性増加効果が大きくなるが、反応性が悪くなってブレンド系になるため、耐熱性・紡糸安定性などの点から好ましくなくなる。また、共重合量が１０重量％以上になると、本来溶融粘度低下作用があるので、あまり好ましくなく、上記の範囲で、両成分を共重合することが好ましい。 The sea component polymer may be any polymer as long as the dissolution rate ratio with respect to the island component is 200 or more, but polyesters, polyamides, polystyrenes, polyethylenes, and the like having good fiber forming properties are particularly preferable. For example, as an easily soluble polymer in an alkaline aqueous solution, polylactic acid, an ultra-high molecular weight polyalkylene oxide condensation polymer, a polyethylene glycol compound copolymer polyester, a copolymer polyester of polyethylene glycol compound and 5-sodium sulfonic acid isophthalic acid may be used. Is preferred. Nylon 6 is soluble in formic acid, and polystyrene and polyethylene are very well soluble in organic solvents such as toluene. Among them, in order to achieve both easy alkali solubility and sea-island cross-section formability, the polyester-based polymer is 3 to 10% by weight of polyethylene glycol having 6 to 12 mol% of 5-sodium sulfoisophthalic acid and a molecular weight of 4000 to 12000. % Copolymerized polyethylene terephthalate copolymer polyester having an intrinsic viscosity of 0.4 to 0.6 is preferred. Here, 5-sodium isophthalic acid contributes to improving hydrophilicity and melt viscosity, and polyethylene glycol (PEG) improves hydrophilicity. PEG has a higher hydrophilicity effect, which is thought to be due to its higher order structure, as the molecular weight increases, but it is preferable from the viewpoints of heat resistance and spinning stability because the reactivity becomes poor and a blend system is formed. Disappear. Further, when the copolymerization amount is 10% by weight or more, it is not preferable because it originally has an effect of decreasing the melt viscosity, and it is preferable to copolymerize both components within the above range.
一方、島成分ポリマーは、海成分との溶解速度差があればいかなるポリマーであってもよいが、前記のように繊維形成性のポリエチレンテレフタレートやポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリ乳酸、第３成分を共重合させたポリエステルなどのポリエステルが好ましい。該ポリマー中には、本発明の目的を損なわない範囲内で必要に応じて、微細孔形成剤、カチオン染料可染剤、着色防止剤、熱安定剤、蛍光増白剤、艶消し剤、着色剤、吸湿剤、無機微粒子が１種または２種以上含まれていてもよい。 On the other hand, the island component polymer may be any polymer as long as it has a difference in dissolution rate from the sea component, but as described above, fiber-forming polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, Polyester such as polyester copolymerized with three components is preferred. In the polymer, a fine pore forming agent, a cationic dye dyeing agent, an anti-coloring agent, a heat stabilizer, a fluorescent whitening agent, a matting agent, a coloring agent may be added as necessary within the range not impairing the object of the present invention. 1 type, or 2 or more types of an agent, a hygroscopic agent, and inorganic fine particles may be contained.
上記の海成分ポリマーと島成分ポリマーからなる海島型複合繊維は、溶融紡糸時における海成分の溶融粘度が島成分ポリマーの溶融粘度よりも大きいことが好ましい。かかる関係にある場合には、海成分の複合重量比率が４０％未満と少なくなっても、島同士が接合したり、島成分の大部分が接合して海島型複合繊維とは異なるものになり難い。 The sea-island composite fiber composed of the sea component polymer and the island component polymer preferably has a sea component melt viscosity higher than that of the island component polymer during melt spinning. In such a relationship, even if the composite weight ratio of the sea component is less than 40%, the islands are joined together, or the majority of the island components are joined to be different from the sea-island type composite fiber. hard.
好ましい溶融粘度比（海／島）は、１．１〜２．０、特に１．３〜１．５の範囲である。この比が１．１倍未満の場合には溶融紡糸時に島成分が接合しやすくなり、一方２．０倍を越える場合には、粘度差が大きすぎるために紡糸調子が低下しやすい。 A preferred melt viscosity ratio (sea / island) is in the range of 1.1 to 2.0, especially 1.3 to 1.5. If this ratio is less than 1.1 times, the island components are likely to be joined during melt spinning, whereas if it exceeds 2.0 times, the viscosity difference is too large and the spinning tone tends to be lowered.
次に島数は、多いほど海成分を溶解除去して極細繊維を製造する場合の生産性が高くなり、しかも得られるナノファイバーの細さも顕著となってナノファイバー特有の柔らかさ、滑らかさを表現することができる点で１００以上（より好ましくは３００〜１０００）であることが好ましい。ここで、島数が１００未満の場合には、海成分を溶解除去しても極細繊度の単糸からなるハイマルチフィラメント糸を得ることができず本発明の目的を達成することができないおそれがある。なお、島数があまりに多くなりすぎると紡糸口金の製造コストが高くなるだけでなく、加工精度自体も低下しやすくなるので１００００以下とするのが好ましい。 Next, the greater the number of islands, the higher the productivity when producing ultrafine fibers by dissolving and removing sea components, and the fineness of the resulting nanofibers becomes remarkable, and the softness and smoothness that is unique to nanofibers. It is preferable that it is 100 or more (more preferably 300 to 1000) in that it can be expressed. Here, when the number of islands is less than 100, there is a possibility that even if the sea component is dissolved and removed, a high multifilament yarn composed of a single yarn having a very fineness cannot be obtained and the object of the present invention cannot be achieved. is there. If the number of islands is too large, not only the production cost of the spinneret increases, but also the processing accuracy itself tends to decrease.
次に、島成分の径は、１０００ｎｍ以下（好ましくは１０〜１０００ｎｍ）とする必要がある。また、海島複合繊維断面内の各島は、その径が均一であるほど海成分を除去して得られる編地の品位や耐久性が向上するので好ましい。 Next, the diameter of the island component needs to be 1000 nm or less (preferably 10 to 1000 nm). Further, each island in the cross section of the sea-island composite fiber is more preferable as the diameter is uniform because the quality and durability of the knitted fabric obtained by removing the sea components are improved.
前記の海島型複合繊維において、その海島複合重量比率（海：島）は、４０：６０〜５：９５の範囲が好ましく、特に３０：７０〜１０：９０の範囲が好ましい。かかる範囲であれば、島間の海成分の厚みを薄くすることができ、海成分の溶解除去が容易となり、島成分の極細繊維への転換が容易になるので好ましい。ここで海成分の割合が４０％を越える場合には海成分の厚みが厚くなりすぎ、一方５％未満の場合には海成分の量が少なくなりすぎて、島間に接合が発生しやすくなる。 In the sea-island composite fiber, the sea-island composite weight ratio (sea: island) is preferably in the range of 40:60 to 5:95, and particularly preferably in the range of 30:70 to 10:90. Within such a range, the thickness of the sea component between the islands can be reduced, the sea component can be easily dissolved and removed, and the conversion of the island component into ultrafine fibers is facilitated. Here, when the proportion of the sea component exceeds 40%, the thickness of the sea component becomes too thick. On the other hand, when the proportion is less than 5%, the amount of the sea component becomes too small, and joining between the islands easily occurs.
前記の海島型複合繊維において、その島間の海成分厚みが５００ｎｍ以下、特に２０〜２００ｎｍの範囲が適当であり、該厚みが５００ｎｍを越える場合には、該厚い海成分を溶解除去する間に島成分の溶解が進むため、島成分間の均質性が低下するだけでなく、毛羽やピリングなど着用時の欠陥や染め斑も発生しやすくなる。 In the above-mentioned sea-island type composite fiber, the thickness of the sea component between the islands is suitably 500 nm or less, particularly in the range of 20 to 200 nm. When the thickness exceeds 500 nm, the thick sea component is dissolved and removed. As the dissolution of the components progresses, not only the homogeneity between the island components decreases, but defects and dyeing spots such as fuzz and pilling are likely to occur.
前記の海島型複合繊維は、例えば以下の方法により容易に製造することができる。すなわち、まず溶融粘度が高く且つ易溶解性であるポリマーと溶融粘度が低く且つ難溶解性のポリマーとを、前者が海成分で後者が島成分となるように溶融紡糸する。ここで、海成分と島成分の溶融粘度の関係は重要で、海成分の比率が小さくなって島間の厚みが小さくなると、海成分の溶融粘度が小さい場合には島間の一部の流路を海成分が高速流動するようになり、島間に接合が起こりやすくなるので好ましくない。 The sea-island type composite fiber can be easily produced, for example, by the following method. That is, first, a polymer having a high melt viscosity and an easily soluble polymer and a polymer having a low melt viscosity and a hardly soluble polymer are melt-spun so that the former is a sea component and the latter is an island component. Here, the relationship between the melt viscosity of the sea component and the island component is important.If the ratio of the sea component decreases and the thickness between the islands decreases, if the melt viscosity of the sea component is small, some of the flow paths between the islands This is not preferable because sea components flow at high speed and joining between islands easily occurs.
溶融紡糸に用いられる紡糸口金としては、島成分を形成するための中空ピン群や微細孔群を有するものなど任意のものを用いることができる。例えば中空ピンや微細孔より押し出された島成分とその間を埋める形で流路を設計されている海成分流とを合流し、これを圧縮することにより海島断面形成がなされるいかなる紡糸口金でもよい。 As the spinneret used for melt spinning, any one such as a hollow pin group for forming an island component or a group having a fine hole group can be used. For example, any spinneret that forms a cross section of the sea island by joining the island component extruded from the hollow pin or the fine hole and the sea component flow designed to fill the gap between the sea component flow may be used. .
吐出された海島型断面複合繊維は、冷却風によって固化され、好ましくは４００〜６０００ｍ／分で溶融紡糸された後に巻き取られる。得られた未延伸糸は、別途延伸工程をとおして所望の強度・伸度・熱収縮特性を有する複合繊維とするか、あるいは、一旦巻き取ることなく一定速度でローラーに引き取り、引き続いて延伸工程をとおした後に巻き取る方法のいずれでも構わない。 The discharged sea-island type cross-section composite fiber is solidified by cooling air, and is preferably wound after being melt-spun at 400 to 6000 m / min. The obtained undrawn yarn is made into a composite fiber having desired strength, elongation, and heat shrinkage properties through a separate drawing process, or is taken up by a roller at a constant speed without being wound once, and subsequently drawn. Any of the methods of winding after passing through may be used.
ここで、特に微細な島径を有する海島型複合繊維を高効率で製造するために、通常のいわゆる配向結晶化を伴うネック延伸（配向結晶化延伸）に先立って、繊維構造は変化させないで繊維径のみを極細化する流動延伸工程を採用することが好ましい。流動延伸を容易とするため、熱容量の大きい水媒体を用いて繊維を均一に予熱し、低速で延伸することが好ましい。このようにすることにより延伸時に流動状態を形成しやすくなり、繊維の微細構造の発達を伴わずに容易に延伸することができる。このプロセスでは、特に海成分および島成分が共にガラス転移温度１００℃以下のポリマーであることが好ましく、なかでも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、ポリ乳酸、ポリトリメチレンテレフタレート等のポリエステルに好適である。具体的には６０〜１００℃、好ましくは６０〜８０℃の範囲の温水バスに浸漬して均一加熱を施し、延伸倍率は１０〜３０倍、供給速度は１〜１０ｍ／分、巻取り速度は３００ｍ／分以下、特に１０〜３００ｍ／分の範囲で実施することが好ましい。予熱温度不足および延伸速度が速すぎる場合には、目的とする高倍率延伸を達成することができなくなる。 Here, in order to produce a sea-island type composite fiber having a particularly fine island diameter with high efficiency, the fiber structure is not changed prior to neck stretching (orientation crystallization stretching) with ordinary so-called orientation crystallization. It is preferable to employ a fluid stretching process in which only the diameter is extremely reduced. In order to facilitate fluid drawing, it is preferable to preheat the fiber uniformly using an aqueous medium having a large heat capacity and draw at a low speed. By doing so, it becomes easy to form a fluid state at the time of stretching, and it can be easily stretched without development of the fine structure of the fiber. In this process, both the sea component and the island component are preferably polymers having a glass transition temperature of 100 ° C. or less, and particularly suitable for polyesters such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid, and polytrimethylene terephthalate. Specifically, it is immersed in a hot water bath in the range of 60 to 100 ° C., preferably 60 to 80 ° C., and uniformly heated, the draw ratio is 10 to 30 times, the supply speed is 1 to 10 m / min, and the winding speed is It is preferable to carry out in the range of 300 m / min or less, particularly 10 to 300 m / min. If the preheating temperature is insufficient and the stretching speed is too high, the desired high-magnification stretching cannot be achieved.
得られた流動状態で延伸された延伸糸は、その強伸度などの機械的特性を向上させるため、定法にしたがって６０〜２２０℃の温度で配向結晶化延伸する。該延伸条件がこの範囲外の温度では、得られる繊維の物性が不十分なものとなる。なお、この延伸倍率は、溶融紡糸条件、流動延伸条件、配向結晶化延伸条件などによって変わってくるが、該配向結晶化延伸条件で延伸可能な最大延伸倍率の０．６〜０．９５倍で延伸すればよい。 The drawn yarn drawn in the fluidized state is oriented, crystallized and drawn at a temperature of 60 to 220 ° C. in accordance with a conventional method in order to improve mechanical properties such as the strength and elongation. If the drawing conditions are outside this range, the properties of the resulting fiber will be insufficient. The draw ratio varies depending on the melt spinning conditions, flow-stretching conditions, orientation crystallization stretching conditions, and the like. What is necessary is just to extend | stretch.
以上に説明した海島型複合繊維を、無撚あるいは必要に応じて追撚した上で、必要に応じて他糸条とともに織編物などの繊維構造体を得た後、前記の海成分をアルカリ水溶液で溶解除去し、前記のように高圧水で該繊維構造体を噴射処理することにより、ナノファイバー同士をばらけた状態にすることができる。 After the sea-island type composite fiber described above is untwisted or twisted as necessary, a fiber structure such as a woven or knitted fabric is obtained together with other yarns as necessary, and then the sea component is mixed with an alkaline aqueous solution. And the nanofibers can be separated from each other by spraying the fiber structure with high-pressure water as described above.
なお、前記のアルカリ水溶液による海成分の溶解除去処理の前および／または後に染色加工を施してもよい。さらに、常法の親水加工、起毛加工、紫外線遮蔽あるいは制電剤、さらには、抗菌剤、消臭剤、防虫剤、蓄光剤、再帰反射剤、マイナスイオン発生剤等の機能を付与する各種加工を付加適用してもよい。 In addition, you may give a dyeing process before and / or after the melt | dissolution removal process of the sea component by the said alkaline aqueous solution. In addition, conventional processing such as hydrophilic processing, brushed processing, ultraviolet shielding or antistatic agent, and various processing that provides functions such as antibacterial agent, deodorant agent, insect repellent agent, phosphorescent agent, retroreflective agent, negative ion generator, etc. May be additionally applied.
かくして得られたナノファイバー繊維構造体において、ナノファイバー同士が凝集密着することなく、ばらけた状態で存在しているので、人工皮革調の肌触りや柔らかさなどの風合いを呈するだけでなく、防風性、吸水性、防透性などのナノファイバー繊維構造体が本来有する機能が十分発現される。 In the nanofiber fiber structure obtained in this way, the nanofibers exist in a loose state without agglomerating and sticking to each other, so they not only exhibit a texture such as artificial leather-like texture and softness, but also have a windproof property. The functions inherent to the nanofiber fiber structure such as water absorption and permeation are sufficiently expressed.
その際、通気性が５０ｃｃ／ｃｍ２／ｓ以下（より好ましくは２０ｃｃ／ｃｍ２／ｓ以下）であることが好ましい。また、防透性の指標であるΔＬ値が１．００以下（より好ましくは０．０５以下）であることが好ましい。さらに、飽和吸水率が２００％以上（より好ましくは２００〜５００％）であることが好ましい。このような機能は、高圧水で噴射処理するナノファイバー繊維構造体の織編密度などを適宜最適化することにより、容易に得ることができる。 At that time, the air permeability is preferably 50 cc / cm 2 / s or less (more preferably 20 cc / cm 2 / s or less). Moreover, it is preferable that the ΔL value, which is an index of permeation resistance, is 1.00 or less (more preferably 0.05 or less). Furthermore, the saturated water absorption is preferably 200% or more (more preferably 200 to 500%). Such a function can be easily obtained by appropriately optimizing the weaving and knitting density of the nanofiber fiber structure to be jetted with high-pressure water.
本発明のナノファイバー繊維構造体は、アウター用衣料、スポーツ用衣料、インナー用衣料、靴材、おしめや介護用シーツの医療・衛生用品、寝装寝具、椅子やソファーの表皮材、カーペット、カーシート地、インテリア用品、空気清浄機用や浄水器用のフィルター製品、電池セパレータ、ワイピングクロスなどの生活資材、ハードデイスク用研磨布、および細胞吸着剤などのメデイカル材料の繊維製品として好適に用いることができる。さらには、本発明のナノファイバー繊維構造体は優れた吸着、吸収特性をも有するため、特開２００４−１６２２４４号公報に開示されたような種々の機能性薬剤を担持させて使用してもよい。 The nanofiber fiber structure of the present invention includes outer garments, sports garments, inner garments, shoes, medical and hygiene products for diapers and nursing sheets, bedding, chairs and sofas, carpets, cars It can be suitably used as textile products for seating materials, interior goods, filter products for air purifiers and water purifiers, life materials such as battery separators and wiping cloths, hard disk polishing cloths, and medical materials such as cell adsorbents. . Furthermore, since the nanofiber fiber structure of the present invention has excellent adsorption and absorption characteristics, it may be used with various functional agents as disclosed in JP-A-2004-162244. .
次に本発明の実施例及び比較例を詳述するが、本発明はこれらによって限定されるものではない。なお、実施例中の各測定項目は下記の方法で測定した。 Next, although the Example and comparative example of this invention are explained in full detail, this invention is not limited by these. In addition, each measurement item in an Example was measured with the following method.
＜溶融粘度＞乾燥処理後のポリマーを紡糸時のルーダー溶融温度に設定したオリフィスにセットして５分間溶融保持したのち、数水準の荷重をかけて押し出し、そのときのせん断速度と溶融粘度をプロットする。そのプロットをなだらかにつないで、せん断速度−溶融粘度曲線を作成し、せん断速度が１０００秒−１の時の溶融粘度を見る。
＜溶解速度＞海・島成分の各々０．３φ−０．６Ｌ×２４Ｈの口金にて１０００〜２０００ｍ/分の紡糸速度で糸を巻き取り、さらに残留伸度が３０〜６０％の範囲になるように延伸して、８４ｄｔｅｘ／２４ｆｉｌのマルチフィラメントを作製する。これを各溶剤にて溶解しようとする温度で浴比１００にて溶解時間と溶解量から、減量速度を算出した。
＜ナノファイバーのばらけ状態＞ナノファイバー繊維構造体を液体窒素に浸漬して固まらせた後カットした後、断面（縦６１μｍ×横８０μｍ、面積４８８０μｍ２）を電子顕微鏡で１０箇所撮影し（倍率１５００倍）、１００本以上のナノファイバーが凝集密着したナノファイバー塊の合計個数をカウントした。合計個数が０個の場合は合格、１個以上の場合は不合格である。
＜通気性＞温度２０℃、湿度６５％ＲＨに２４時間放置し調質した試料について、ＪＩＳ Ｌ １０９６−１９９８、６．２７．１、Ａ法（フラジール形通気性試験機法）により通気性（ｃｃ／ｃｍ２／ｓｅｃ）を測定した。なお、ｎ数は５でその平均を求めた。
＜保温性＞温度２０℃、湿度６５％ＲＨの環境下において、カトーテック社製のサーモラボＩＩにて保温率を測定した。
＜防透性＞ＪＩＳ Ｚ ８７２９−１９９４、Ｌ＊ａ＊ｂ＊表色系において、試料を白色板上に載置したときのＬ＊値（Ｌ＊ｗと記す。）と、黒色板上に載置したときのＬ＊値（Ｌ＊ｂと記す。）との差ΔＬ（Ｌ＊ｗ−Ｌ＊ｂ）を求め、このΔＬをもって、防透性の指標とした。なお、ΔＬの値が小さいほど防透性が良好である。
＜吸水率＞ＪＩＳ Ｌ １０９６ ６．２５．２ Ｂ法により、面積２０２．５ｃｍ２の試料を採取し、これを水中に浸漬して十分に吸水させた後水中から引き上げ、水滴が滴り落ちなくなった時の重量をｗｗとし、これと乾燥時の試料重量ｗｄとから、下記式により吸水率を算出した。
吸水率（％）＝（ｗｗ−ｗｄ）／ｗｄ×１００
＜目付＞ＪＩＳ Ｌ１０９６ ６．４．２に従って測定した。
<Melting viscosity> The polymer after drying is set in the orifice set to the ruder melting temperature at the time of spinning, melted and held for 5 minutes, extruded with several levels of load, and the shear rate and melt viscosity at that time are plotted. To do. By gently connecting the plots, a shear rate-melt viscosity curve is created, and the melt viscosity when the shear rate is 1000 sec- 1 is observed.
<Dissolution rate> The yarn is wound at a spinning speed of 1000 to 2000 m / min with a 0.3φ-0.6L × 24H base of each of the sea and island components, and the residual elongation is in the range of 30 to 60%. To produce a 84 dtex / 24 fil multifilament. The weight loss rate was calculated from the dissolution time and the dissolution amount at a bath ratio of 100 at a temperature at which the solvent was dissolved in each solvent.
<Dispersed state of nanofibers> After the nanofiber fiber structure was dipped in liquid nitrogen and solidified and then cut, 10 cross-sections (length 61 μm × width 80 μm, area 4880 μm 2 ) were photographed with an electron microscope (magnification) 1500 times), the total number of nanofiber lumps in which 100 or more nanofibers aggregated and adhered was counted. When the total number is 0, it is acceptable, and when it is 1 or more, it is unacceptable.
<Breathability> A sample that was tempered by leaving it at a temperature of 20 ° C. and a humidity of 65% RH for 24 hours according to JIS L 1096-1998, 6.27.1, Method A (Fragile Breathability Tester Method) cc / cm 2 / sec). In addition, the number of n was 5, and the average was calculated | required.
<Heat retention> The heat retention rate was measured with Thermolab II manufactured by Kato Tech Co., Ltd. in an environment of a temperature of 20 ° C. and a humidity of 65% RH.
<Permeability> In JIS Z 8729-1994, L * a * b * color system, L * value (denoted as L * w) when a sample is placed on a white plate, and on a black plate A difference ΔL (L * w−L * b) from the L * value (denoted as L * b) when placed was obtained, and this ΔL was used as an index of permeation resistance. The smaller the value of ΔL, the better the permeation resistance.
<Water absorption rate> According to JIS L 1096 6.25.2 B method, a sample having an area of 202.5 cm 2 was collected, immersed in water to sufficiently absorb water, then pulled up from water, and water droplets did not drip. The weight at the time was defined as ww, and the water absorption rate was calculated from the following formula from this and the sample weight wd at the time of drying.
Water absorption rate (%) = (ww−wd) / wd × 100
<Mass weight> It was measured according to JIS L1096 6.4.2.
［実施例１］
島成分としてポリエチレンテレフタレート（２８０℃における溶融粘度が１２００ポイズ、艶消し剤の含有量：０重量％）、海成分として５−ナトリウムスルホイソフタル酸６モル％と数平均分子量４０００のポリエチレングリコール６重量％を共重合したポリエチレンテレフタレート（２８０℃における溶融粘度が１７５０ポイズ）を用い（溶解速度比（海／島）＝２３０）、海：島＝３０：７０、島数＝８３６の海島型複合未延伸繊維を、紡糸温度２８０℃、紡糸速度１５００ｍ／分で溶融紡糸して一旦巻き取った。
[Example 1]
Polyethylene terephthalate (melt viscosity at 280 ° C., 1200 poise, matting agent content: 0% by weight) as an island component, and 6% by weight of polyethylene glycol having 6 mol% of 5-sodium sulfoisophthalic acid and a number average molecular weight of 4000 as a sea component A sea-island type composite unstretched fiber having a melt rate of 1750 poise at 280 ° C. (dissolution rate ratio (sea / island) = 230), sea: island = 30: 70, and number of islands = 836 This was melt-spun at a spinning temperature of 280 ° C. and a spinning speed of 1500 m / min, and then wound up.
得られた未延伸糸を、延伸温度８０℃、延伸倍率２．５倍でローラー延伸し、次いで１５０℃で熱セットして巻き取った。得られた海島型複合延伸糸は５５ｄｔｅｘ／１０ｆｉｌであり、透過型電子顕微鏡ＴＥＭによる繊維横断面を観察したところ、島の形状は丸形状でかつ島の径は７１０ｎｍであった。 The obtained undrawn yarn was roller-drawn at a drawing temperature of 80 ° C. and a draw ratio of 2.5 times, and then heat-set at 150 ° C. and wound up. The obtained sea-island type composite drawn yarn was 55 dtex / 10 fil. When the fiber cross section was observed with a transmission electron microscope TEM, the shape of the island was round and the diameter of the island was 710 nm.
次いで、３６ゲージの通常の丸編ダブル機を使用して、スムース編物を編成した。そして、得られた編地を海島型複合延伸糸の海成分を除去するために、２５ｇ／リットルのＮＡＯＨ水溶液で、７０℃にて３０重量％アルカリ減量した後、常法の染色加工を行った。
次いで、この編地に対し、スパンレース用のウオーターニードル装置（噴射孔径：０．１ｍｍ、孔ピッチ：１．０ｍｍ、孔配列：２列千鳥）にて、水圧６０ｋｇ／ｃｍ２、編地の送り速度２ｍ／分、編地の支持メッシュ：５０メッシュの条件で高圧水を噴射した。
Next, a smooth knitted fabric was knitted using a 36 gauge ordinary circular knitting double machine. Then, in order to remove the sea component of the sea-island type composite drawn yarn, the obtained knitted fabric was subjected to an ordinary dyeing process after reducing the alkali weight by 30% by weight at 70 ° C. with a 25 g / liter NAOH aqueous solution. .
Next, a water pressure of 60 kg / cm 2 is fed to the knitted fabric with a water needle device for spunlace (injection hole diameter: 0.1 mm, hole pitch: 1.0 mm, hole arrangement: two rows zigzag). High-pressure water was jetted under the conditions of a speed of 2 m / min and a support mesh of the knitted fabric: 50 mesh.
得られた編地の密度は８３コース／８０ウエール、編地中のマルチフィラメント糸条の総繊度は４０ｄｔｅｘ、単繊維径が７１０ｎｍ、単糸数８３６０、目付け１２０ｇ／ｍ２であった。該編地において、図１および図２に示すように、ナノファイバー同士が凝集密着することなく、ばらけた状態で存在しており、ナノファイバー塊の個数は０個であった。また、通気性１５ｃｃ／ｃｍ２／ｓ、保温率１４％、防透性０．０１、吸水率２５０％と、防風性、吸水性、防透性に優れるものであった。
また、かかる編地は、人工皮革調の肌触りや柔らかさなどの風合いを有するものであった。
The density of the obtained knitted fabric was 83 course / 80 wale, the total fineness of the multifilament yarn in the knitted fabric was 40 dtex, the single fiber diameter was 710 nm, the number of single yarns 8360, and the basis weight was 120 g / m 2 . In the knitted fabric, as shown in FIGS. 1 and 2, the nanofibers existed in a dispersed state without agglomeration and adhesion, and the number of nanofiber masses was zero. Further, the air permeability was 15 cc / cm 2 / s, the heat retention rate was 14%, the water permeability was 0.01, the water absorption rate was 250%, and the wind resistance, water absorption, and water permeability were excellent.
Further, such a knitted fabric has a texture such as an artificial leather-like touch and softness.
［実施例２］
３６ゲージの通常のトリコット編機を使用して、実施例１で用いた海島型複合延伸糸をフルセットでバック筬およびフロント筬に通し、ハーフ組織（バック１０−１２、フロント２３−１０）で機上コース５０コース／２．５４ｃｍの編条件で編地を編成した。そして、得られた編地を海島型複合延伸糸の海成分を除去するために、２５ｇ／リットルのＮＡＯＨ水溶液で、７０℃にて３０重量％アルカリ減量した後、常法の染色加工を行った。
次いで、この編地に対し、実施例１と同じようにウオーターニードル処理を行った。
[Example 2]
Using a normal tricot knitting machine of 36 gauge, the sea-island type composite drawn yarn used in Example 1 was passed through the back heel and the front heel with a full set, and with a half structure (back 10-12, front 23-10). The knitted fabric was knitted under an on-machine course of 50 courses / 2.54 cm. Then, in order to remove the sea component of the sea-island type composite drawn yarn, the obtained knitted fabric was subjected to an ordinary dyeing process after reducing the alkali weight by 30 wt% at 70 ° C. with a 25 g / liter NAOH aqueous solution. .
Next, the water needle treatment was performed on the knitted fabric in the same manner as in Example 1.
得られた編地の密度は６３コース／５１ウエール、編地中のマルチフィラメント糸条の総繊度は４０ｄｔｅｘ、単繊維径が７１０ｎｍ、単糸数８３６０、目付け９０ｇ／ｍ２であった。該編地において、ナノファイバー同士が凝集密着することなく、ばらけた状態で存在しており、ナノファイバー塊の個数は０個であった。また、通気性２ｃｃ／ｃｍ２／ｓ、保温率１８％、防透性０．０１、吸水率２１０％と、防風性、吸水性、防透性に優れるものであった。
また、かかる編地は、人工皮革調の肌触りや柔らかさなどの風合いを有するものであった。
The density of the obtained knitted fabric was 63 course / 51 wale, the total fineness of the multifilament yarn in the knitted fabric was 40 dtex, the single fiber diameter was 710 nm, the single yarn number was 8360, and the basis weight was 90 g / m 2 . In the knitted fabric, the nanofibers existed in a dispersed state without agglomeration and adhesion, and the number of nanofiber masses was zero. Further, the air permeability was 2 cc / cm 2 / s, the heat retention rate was 18%, the permeation resistance was 0.01, and the water absorption rate was 210%.
Further, such a knitted fabric has a texture such as an artificial leather-like touch and softness.
［比較例１］
実施例１において、ウオーターニードル処理を行わないこと以外は、実施例１と同様にした。
かかる編地において、図３および図４に示すように、ナノファイバー同士が凝集密着しており、ナノファイバー塊の個数は２０個以上であった。また、通気性９０ｃｃ／ｃｍ２／ｓ、保温率９％、防透性１．３６、吸水率１４０％と、防風性、吸水性、防透性に劣るものであった。
また、かかる編地は、人工皮革調の肌触りや柔らかさなどの風合い的特徴が十分発揮されないものであった。
[Comparative Example 1]
In Example 1, it carried out similarly to Example 1 except not performing a water needle process.
In such a knitted fabric, as shown in FIGS. 3 and 4, the nanofibers were agglomerated and adhered, and the number of nanofiber masses was 20 or more. Further, the air permeability was 90 cc / cm 2 / s, the heat retention rate was 9%, the permeation resistance was 1.36, and the water absorption rate was 140%.
In addition, such knitted fabrics do not sufficiently exhibit texture features such as artificial leather-like touch and softness.
［比較例２］
実施例２において、ウオーターニードル処理を行わないこと以外は、実施例２と同様にした。
かかる編地において、ナノファイバー同士が凝集密着しており、ナノファイバー塊の個数は２０個以上であった。また、通気性１２０ｃｃ／ｃｍ２／ｓ、保温率１０％、防透性１．５３、吸水率１２０％と、防風性、吸水性、防透性に劣るものであった。
また、かかる編地は、人工皮革調の肌触りや柔らかさなどの風合い的特徴が十分発揮されないものであった。
[Comparative Example 2]
In Example 2, it was made to be the same as that of Example 2 except not performing water needle processing.
In such a knitted fabric, the nanofibers were agglomerated and adhered, and the number of nanofiber masses was 20 or more. Further, the breathability was 120 cc / cm 2 / s, the heat retention rate was 10%, the permeation resistance was 1.53, and the water absorption rate was 120%.
In addition, such knitted fabrics do not sufficiently exhibit texture features such as artificial leather-like touch and softness.
本発明によれば、人工皮革調の肌触りや柔らかさなどの風合い、および防風性、吸水性、防透性などの機能性に優れたナノファイバー繊維構造体およびその製造方法および繊維製品が提供され、その工業的価値は極めて大である。 ADVANTAGE OF THE INVENTION According to this invention, the nanofiber fiber structure excellent in texture, such as the touch and softness of the artificial leather tone, and functions, such as windproof property, water absorption property, and water-proof property, its manufacturing method, and a textile product are provided. The industrial value is extremely large.
Claims (12)
ただし、Ｄは前記マルチフィラメント糸条の総繊度（ｄｔｅｘ）、Ｃｏは２．５４ｃｍあたりのコース数、Ｗｅは２．５４ｃｍあたりのウエール数である。 The nanofiber fiber structure according to claim 3, wherein the fiber structure is a knitted fabric having a D 1/2 × Co × We of 10,000 to 200,000.
However, D is the total fineness (dtex) of the multifilament yarn, Co is the number of courses per 2.54 cm, and We is the number of wales per 2.54 cm.
ＣＦ＝（ＤＷｐ／１．１）１／２×ＭＷｐ＋（ＤＷｆ／１．１）１／２×ＭＷｆ
ただし、ＤＷｐは経糸総繊度（ｄｔｅｘ）、ＭＷｐは経糸織密度（本／２．５４ｃｍ）、ＤＷｆは緯糸総繊度（ｄｔｅｘ）、ＭＷｆは緯糸織密度（本／２．５４ｃｍ）である。 The nanofiber fiber structure according to claim 3, wherein the fiber structure is a woven fabric having a cover factor CF calculated by the following formula within a range of 1700 to 3800.
CF = (DWp / 1.1) 1/2 × MWp + (DWf / 1.1) 1/2 × MWf
However, DWp is the total warp fineness (dtex), MWp is the warp weave density (main / 2.54 cm), DWf is the total weft fineness (dtex), and MWf is the weft weave density (main / 2.54 cm).
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