JP2012091411A - Moisture-permeable waterproof cloth and fiber product - Google Patents
Moisture-permeable waterproof cloth and fiber product Download PDFInfo
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Images
Abstract
Description
本発明は、蓄熱性に優れた透湿防水性布帛および該透湿防水性布帛を用いてなる繊維製品に関する。 The present invention relates to a moisture-permeable and waterproof fabric excellent in heat storage and a fiber product using the moisture-permeable and waterproof fabric.
従来、スポーツ衣料やユニフォーム衣料などに使用されている透湿防水性布帛において、透湿性および防水性を備えた樹脂製の薄膜が広く使用されている。例えば、織編物などの基布に、多孔質または無孔質ポリウレタンをコーティングしたものや、ポリウレタンなどの多孔質または無孔質樹脂製フィルムを接着剤により基布にラミネーションしたものなどがある（例えば、特許文献１参照）。多孔質樹脂製薄膜はその孔の大きさにより、また、無孔質樹脂製薄膜の場合は孔が無いものの吸湿性物質を含有することで親水性となり、雨やその他の水を通さず、湿気（水蒸気）を通すことにより透湿防水性を呈している。 Conventionally, in a moisture-permeable and waterproof fabric used for sports clothing, uniform clothing, and the like, a resin thin film having moisture permeability and waterproof properties has been widely used. For example, a base fabric such as a woven or knitted fabric is coated with porous or nonporous polyurethane, or a porous or nonporous resin film such as polyurethane is laminated to the base fabric with an adhesive (for example, , See Patent Document 1). Porous resin thin films are hydrophilic due to the size of their pores, and nonporous resin thin films do not have pores but contain moisture-absorbing substances. Moisture permeable and waterproof properties are exhibited by passing (water vapor).
他方、透湿防水性布帛を用いた衣料は、雨天時など比較的寒い環境下で使用されることが多いため、蓄熱性を向上させたり、布帛に付着した水滴を速やかに蒸発させることが望まれていた。
なお、布帛に赤外線吸収剤を付着させることにより保温性を高めることは例えば特許文献２などにより提案されているが、かかる布帛は透湿防水性を有するものではなかった。
On the other hand, clothing using a moisture-permeable and waterproof fabric is often used in a relatively cold environment such as rainy weather, so it is desirable to improve heat storage and to quickly evaporate water droplets adhering to the fabric. It was rare.
It has been proposed, for example, in Patent Document 2 to increase the heat retention by attaching an infrared absorbent to the fabric, but such a fabric is not moisture permeable and waterproof.
本発明は上記の背景に鑑みなされたものであり、その目的は蓄熱性に優れた透湿防水性布帛および該透湿防水性布帛を用いてなる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 background, and an object thereof is to provide a moisture-permeable waterproof fabric excellent in heat storage and a fiber product using the moisture-permeable waterproof fabric.
本発明者は、基布の片面に透湿防水層が積層された透湿防水性布帛において、透湿防水層の表面に赤外線吸収剤を特定のパターンで付着させることにより、透湿防水性を損なわずに優れた蓄熱性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。 In the moisture permeable waterproof fabric in which the moisture permeable waterproof layer is laminated on one side of the base fabric, the inventor has made the moisture permeable waterproof property by attaching an infrared absorbent in a specific pattern to the surface of the moisture permeable waterproof layer. The present inventors have found that excellent heat storage properties can be obtained without impairing the present invention, and have further intensively studied to complete the present invention.
かくして、本発明によれば「基布の片面に透湿防水層が積層され、該透湿防水層の表面に、赤外線吸収剤が部分的に付着していることを特徴とする透湿防水性布帛。」が提供される。 Thus, according to the present invention, “a moisture permeable waterproof layer characterized in that a moisture permeable waterproof layer is laminated on one side of a base fabric, and an infrared absorber is partially attached to the surface of the moisture permeable waterproof layer. Fabric "is provided.
その際、前記赤外線吸収剤が、付着部と非付着部とからなるパターンで付着していることが好ましい。また、前記赤外線吸収剤がカーボンブラックであることが好ましい。また、前記のパターンが格子状パターンであることが好ましい。また、前記基布に、単繊維繊度２．０ｄｔｅｘ以下かつフィラメント数６０本以上のポリエステルマルチフィラメントが含まれることが好ましい。また、前記基布が、下記式により定義されるカバーファクターＣＦが３００〜３５００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
［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。］
In that case, it is preferable that the said infrared absorber has adhered in the pattern which consists of an adhesion part and a non-adhesion part. Moreover, it is preferable that the said infrared absorber is carbon black. The pattern is preferably a lattice pattern. Moreover, it is preferable that the base fabric includes a polyester multifilament having a single fiber fineness of 2.0 dtex or less and a filament number of 60 or more. Further, the base fabric is preferably a woven fabric having a cover factor CF defined by the following formula of 300 to 3500.
CF = (DWp / 1.1) 1/2 × MWp + (DWf / 1.1) 1/2 × MWf
[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). ]
また、前記基布に撥水加工が施されていることが好ましい。また、前記透湿防水層が、厚さ２〜５０μｍの透湿防水性ポリエステル膜であることが好ましい。
また、本発明によれば、前記の透湿防水性布帛を用いてなる、スポーツウェア、アウトドアウェア、レインコート、紳士衣服、婦人衣服、作業衣、防護服、人工皮革、履物、鞄、カーテン、テント、寝袋、防水シート、およびカーシートの群より選ばれるいずれかの繊維製品が提供される。
Moreover, it is preferable that the said base fabric is water-repellent. The moisture-permeable and waterproof layer is preferably a moisture-permeable and waterproof polyester film having a thickness of 2 to 50 μm.
Further, according to the present invention, sportswear, outdoor wear, raincoat, men's clothing, women's clothing, work clothing, protective clothing, artificial leather, footwear, heels, curtains, comprising the moisture permeable and waterproof fabric described above, Any textile product selected from the group of tents, sleeping bags, tarpaulins, and car seats is provided.
本発明によれば、蓄熱性に優れた透湿防水性布帛および該透湿防水性布帛を用いてなる繊維製品が得られる。かかる透湿防水性布帛および該透湿防水性布帛を用いてなる繊維製品によれば、透湿防水性が得られるだけでなく、布帛の蓄熱性を向上させたり、布帛に付着した水滴を速やかに蒸発させることが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, the moisture-permeable waterproof fabric excellent in heat storage property and the textiles using this moisture-permeable waterproof fabric are obtained. According to such a moisture-permeable and waterproof fabric and a textile product using the moisture-permeable and waterproof fabric, not only moisture-permeable and waterproof properties can be obtained, but also the heat storage property of the fabric can be improved, or water droplets attached to the fabric can be quickly removed. Can be evaporated.
本発明の透湿防水性布帛において、基布の片面に透湿防水層が積層され、該透湿防水層の表面に、赤外線吸収剤が部分的に付着している。すなわち、基布の片面に、透湿防水層および赤外線吸収剤がこの順で積層されている。
ここで、前記赤外線吸収剤としては、波長７００〜２０００ｎｍの赤外線領域で１０％以上の吸収率を有する物質であれば特に限定されず、金属酸化物系微粒子、カーボンブラック、有機化合物の赤外線吸収色素などが例示される。特に、優れた赤外線吸収性能を得る上でカーボンブラックが好ましい。
In the moisture permeable waterproof fabric of the present invention, a moisture permeable waterproof layer is laminated on one side of the base fabric, and the infrared absorbent is partially attached to the surface of the moisture permeable waterproof layer. That is, a moisture-permeable waterproof layer and an infrared absorber are laminated in this order on one side of the base fabric.
Here, the infrared absorber is not particularly limited as long as it is a substance having an absorptance of 10% or more in an infrared region having a wavelength of 700 to 2000 nm, and is an infrared absorbing dye of metal oxide fine particles, carbon black, or an organic compound. Etc. are exemplified. In particular, carbon black is preferable for obtaining excellent infrared absorption performance.
また、透湿防水層の表面に赤外線吸収剤が、付着部と非付着部とからなるパターンで付着していることが好ましい。その際、好ましいパターンとしては、格子状パターン、縞状パターン、水玉状パターン、市松パターンなどが例示される。なかでも、パターンの全領域が図１に示すような格子状パターンであることが好ましく、かかる格子状パターンを採用することにより、赤外線吸収剤が太陽光線等の赤外線により加熱された際、熱が格子状パターンに沿って、迅速に伝わり、布帛が速やかに暖められる。 Moreover, it is preferable that the infrared absorber adheres to the surface of a moisture-permeable waterproof layer with the pattern which consists of an adhesion part and a non-adhesion part. In that case, as a preferable pattern, a lattice pattern, a striped pattern, a polka dot pattern, a checkered pattern and the like are exemplified. Especially, it is preferable that the whole area | region of a pattern is a grid | lattice-like pattern as shown in FIG. 1, and when this infrared-absorbing agent is heated by infrared rays, such as a solar ray, heat is generated by employ | adopting this grid-like pattern. Along the grid pattern, it travels quickly and the fabric is warmed up quickly.
また、赤外線吸収剤付着部面積比率としては１０〜８５％（より好ましくは２５〜７０％）であることが好ましい。なお、赤外線吸収剤付着部面積比率は下記式で示されるものである。
赤外線吸収剤付着部面積比率＝（赤外線吸収剤付着部面積）／（赤外線吸収剤付着部面積＋非付着部面積）×１００（％）
Moreover, it is preferable that it is 10-85% (more preferably 25-70%) as an infrared absorber adhesion part area ratio. In addition, an infrared absorber adhesion part area ratio is shown by a following formula.
Infrared absorber adhering part area ratio = (infrared absorber adhering part area) / (infrared absorber adhering part area + non-adhering part area) × 100 (%)
該赤外線吸収剤付着部面積比率が１０％よりも小さいと、布帛に赤外線があたっても、布帛が十分には暖められないおそれがある。逆に、赤外線吸収剤付着部面積比率が８５％よりも大きい場合は、布帛の透湿防水性や風合いが低下する恐れがある。また、上記格子状パターンにおいて、タテ方向またはヨコ方向に互いに隣りあう格子間の間隔Ｗ（一方の付着部端部〜他方の付着部端部までの最短距離）は２〜３０ｍｍ程度が適当である。 If the area ratio of the infrared absorbent adhering portion is smaller than 10%, the fabric may not be sufficiently warmed even when the fabric is irradiated with infrared rays. On the contrary, if the area ratio of the infrared absorbent adhering portion is larger than 85%, the moisture permeability and waterproof property and texture of the fabric may be lowered. In the grid pattern, the interval W between the grids adjacent to each other in the vertical direction or the horizontal direction (the shortest distance from one attached portion end to the other attached portion end) is suitably about 2 to 30 mm. .
本発明の透湿防水性布帛において、基布を構成する繊維は特に限定されず、ポリエステル繊維、アセテート繊維、ポリアミド繊維、アラミド繊維、炭素繊維、綿や羊毛などの天然繊維などいずれでもよい。なかでも、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、ステレオコンプレックスポリ乳酸、第３成分を共重合させたポリエステルなどからなるポリエステル繊維が５０重量％以上（特に好ましくは１００重量％）基布に含まれることがリサイクル性の点で好ましい。なお、かかるポリエステルとしては、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であってもよい。さらには、特開２００４−２７００９７号公報や特開２００４−２１１２６８号公報に記載されているような、特定のリン化合物およびチタン化合物を含む触媒を用いて得られたポリエステルでもよい。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。 In the moisture permeable waterproof fabric of the present invention, the fibers constituting the base fabric are not particularly limited, and may be any of polyester fibers, acetate fibers, polyamide fibers, aramid fibers, carbon fibers, natural fibers such as cotton and wool. Among these, 50% or more (particularly preferably 100% by weight) of polyester fiber made of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polylactic acid, stereocomplex polylactic acid, polyester copolymerized with the third component, or the like. It is preferable that it is contained in the base fabric from the viewpoint of recyclability. The polyester may be material recycled or chemically recycled polyester. Furthermore, the polyester obtained using the catalyst containing the specific phosphorus compound and titanium compound which are described in Unexamined-Japanese-Patent No. 2004-270097 and 2004-21268 may be sufficient. 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.
前記基布を構成する繊維形態は特に限定されないが、透湿防水層との接着性の点で長繊維（マルチフィラメント）であることが好ましい。単繊維の断面形状も特に限定されず、丸、三角、扁平、中空など公知の断面形状でよい。また、通常の空気加工、仮撚捲縮加工が施されていてもさしつかえない。単糸繊維繊度、総繊度、フィラメント数は特に限定されないが、蓄熱性およびソフトな風合いを得る上で、それぞれ単糸繊維繊度２．０ｄｔｅｘ以下（好ましくは０．１〜２．０ｄｔｅｘ）、総繊度３０〜２００ｄｔｅｘ、フィラメント数３０本以上（より好ましくは６０本以上、さらに好ましくは６０〜２００本）の範囲内であることが好ましい。 Although the fiber form which comprises the said base fabric is not specifically limited, It is preferable that it is a long fiber (multifilament) at the point of adhesiveness with a moisture-permeable waterproof layer. The cross-sectional shape of the single fiber is not particularly limited, and may be a known cross-sectional shape such as a circle, a triangle, a flat shape, or a hollow shape. In addition, normal air processing and false twist crimping may be applied. The single yarn fiber fineness, the total fineness, and the number of filaments are not particularly limited, but for obtaining heat storage properties and a soft texture, the single yarn fiber fineness is 2.0 dtex or less (preferably 0.1 to 2.0 dtex), respectively, and the total fineness is It is preferable to be within the range of 30 to 200 dtex and 30 or more filaments (more preferably 60 or more, and still more preferably 60 to 200).
前記基布の布帛組織は特に限定されず織物、編物、不織布などいずれでもよい。なかでも、引裂き強力の強さの点で織物または編物が好ましい。特に織物が好ましい。織物組織としては、平織、綾織、朱子織等の三原組織、変化組織、たて二重織、よこ二重織等の片二重組織、たてビロードなどが例示されるがこれらに限定されない。層数は単層でもよいし、２層以上の多層でもよい。特に、下記式により定義されるカバーファクターＣＦが３００〜３５００（より好ましくは１５００〜３５００）の織物であるとさらに優れた蓄熱性が得られ好ましい。なお、以上のような布帛は常法により製造することが可能である。
ＣＦ＝（ＤＷｐ／１．１）１／２×ＭＷｐ＋（ＤＷｆ／１．１）１／２×ＭＷｆ
［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 fabric structure of the base fabric is not particularly limited, and may be any of woven fabric, knitted fabric, non-woven fabric and the like. Of these, a woven fabric or a knitted fabric is preferable in terms of tear strength. A woven fabric is particularly preferable. Examples of the fabric structure include, but are not limited to, a three-layer structure such as plain weave, twill weave, and satin weave, a change structure, a single double structure such as a vertical double weave and a horizontal double weave, and a vertical velvet. The number of layers may be a single layer or a multilayer of two or more layers. In particular, a woven fabric having a cover factor CF defined by the following formula of 300 to 3500 (more preferably 1500 to 3500) is preferable because further excellent heat storage properties can be obtained. In addition, the above fabrics can be manufactured by a conventional method.
CF = (DWp / 1.1) 1/2 × MWp + (DWf / 1.1) 1/2 × MWf
[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). ]
前記基布の目付けとしては、３０〜９００ｇ／ｍ２（より好ましくは４０〜７００ｇ／ｍ２）の範囲内であることが好ましい。
また、前記基布には、通常の染色加工、減量加工、起毛加工、撥水加工、蓄熱加工、吸汗加工などの後加工を適宜施しても良い。特に、染色加工および撥水加工が好ましい。その際、染色に用いる染料は分散染料、カチオン性染料など特に限定はされないが、カチオン性染料はカチオン性染料で染色可能な繊維を選択する必要があるため、より汎用性が高い分散染料を染色に用いるほうが好適である。また、撥水加工に用いられる撥水剤としては、パラフィン系撥水剤やポリシロキサン系撥水処理剤、フッ素系撥水処理剤などの公知のものが使用でき、その処理も一般に行われているパディング法、スプレー法などの公知の方法で行えばよい。
The basis weight of the base fabric is preferably in the range of 30 to 900 g / m 2 (more preferably 40 to 700 g / m 2 ).
In addition, the base fabric may be appropriately subjected to post-processing such as normal dyeing processing, weight reduction processing, raising processing, water repellent processing, heat storage processing, and sweat absorption processing. In particular, a dyeing process and a water repellent process are preferable. At that time, the dye used for dyeing is not particularly limited, such as a disperse dye or a cationic dye. However, it is necessary to select a fiber that can be dyed with a cationic dye. It is more suitable to use for. In addition, as the water repellent used in the water repellent processing, known ones such as a paraffin water repellent, a polysiloxane water repellent, a fluorine water repellent can be used, and the treatment is generally performed. A known method such as a padding method or a spray method may be used.
本発明の透湿防水性布帛において、基布の片面に積層される透湿防水層としては、透湿性を有するウレタン樹脂からなるフィルム、ウレタン樹脂コーティング、アクリル樹脂コーティング、ポリテトラフロロエチレン樹脂フィルム、ポリエステルフィルムなどがあげられが限定されるものではない。特に、ケミカルリサイクル処理により再度ポリエステルの原料として再生可能であり何度でもリサイクル使用できる点で省資源かつ環境保全できる点より、より好ましくは無色透明のポリエステルフィルムであるほうがよい。 In the moisture permeable waterproof fabric of the present invention, as the moisture permeable waterproof layer laminated on one side of the base fabric, a film made of urethane resin having moisture permeability, urethane resin coating, acrylic resin coating, polytetrafluoroethylene resin film, Examples include, but are not limited to, polyester films. In particular, a colorless and transparent polyester film is more preferable from the viewpoint that it can be recycled as a raw material of polyester again by chemical recycling treatment and can be reused any number of times, thus saving resources and protecting the environment.
かかるポリエステルフィルムとしては、ポリエーテル−エステル系エラストマーやＰＢＴ（ポリブチレンテレフタレート）からなるポリエステルフィルムが好適に用いられる。また、上記フィルムは透湿性を有するが、該フィルムは多孔質でもよいが、透湿性を有するポリエステルを主成分とする無孔質フィルムであることが好ましい。多孔質フィルムである場合、無色透明にはなり得ないからである。ポリエステルに透湿性を付与するには、特に限定されるものではないが、ポリエチレングリコールなどの吸湿性材料をポリエステルに共重合する方法が好適に用いられる。 As such a polyester film, a polyester film made of a polyether-ester elastomer or PBT (polybutylene terephthalate) is preferably used. Moreover, although the said film has moisture permeability, this film may be porous, but it is preferable that it is a nonporous film which has polyester which has moisture permeability as a main component. This is because a porous film cannot be colorless and transparent. To impart moisture permeability to the polyester, although not particularly limited, a method of copolymerizing a hygroscopic material such as polyethylene glycol with the polyester is preferably used.
上記ポリエーテル−エステル系エラストマーは、長鎖エステル単位および短鎖エステル単位からなり、該短鎖エステル単位は、全ポリエーテル−エステル系エラストマーの３０〜７０重量％の範囲にあることが好ましい。上記短鎖エステル単位の割合が、３０重量％未満であるポリエーテル−エステル系エラストマーは比較的低融点であって、加工性が不良であり、また、該短鎖エステル単位が、７０重量％を超えるポリエーテル−エステル系エラストマーの場合には、比較的高融点であり、加工性が不良である。 The polyether-ester elastomer is composed of a long-chain ester unit and a short-chain ester unit, and the short-chain ester unit is preferably in the range of 30 to 70% by weight of the total polyether-ester elastomer. The polyether-ester elastomer having a proportion of the short chain ester unit of less than 30% by weight has a relatively low melting point and poor processability, and the short chain ester unit accounts for 70% by weight. In the case of exceeding polyether-ester elastomer, the melting point is relatively high and the processability is poor.
前記ポリエーテル-エステル系エラストマーの酸成分は、テレフタル酸、イソフタル酸、フタル酸、ナフタレン−２，６−ジカルボン酸、ナフタレン−２，７−ジカルボン酸、ジフェニル−４，４’−ジカルボン酸、ジフェノキシエタンジカルボン酸、３−スルホイソフタル酸ナトリウムなどの芳香族ジカルボン酸、１，４−シクロヘキサンジカルボン酸などの脂環式ジカルボン酸、コハク酸、シュウ酸、アジピン酸、セバシン酸、ドデカンジ酸、ダイマー酸などの脂肪族ジカルボン酸、または、これらのエステル形成性誘導体から選ばれた少なくとも１種が挙げられるが、好ましくは、テレフタル酸、イソフタル酸、ナフタレン−２，６−ジカルボン酸、またはこれらのエステル形成性誘導体が例示される。 The acid component of the polyether-ester elastomer is terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diester Aromatic dicarboxylic acids such as phenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanediic acid, dimer acid And at least one selected from aliphatic dicarboxylic acids such as these or ester-forming derivatives thereof, preferably terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, or ester formation thereof Sex derivatives are exemplified.
もちろん、このような酸成分の一部（通常は、全酸成分を基準として３０モル％以下）は、他のジカルボン酸成分やオキシカルボン酸成分で置換されていてもよい。
なお、上記ポリマー中には、各種安定剤、紫外線吸収剤などが必要に応じて配合されていてもよい。
Of course, a part of these acid components (usually 30 mol% or less based on the total acid components) may be substituted with other dicarboxylic acid components or oxycarboxylic acid components.
In addition, various stabilizers, ultraviolet absorbers, and the like may be blended in the polymer as necessary.
次に、前記ポリエーテル−エステル系エラストマーの長鎖エステル単位のグリコール成分としては、ポリエチレングリコール、ポリ１，２−プロピレングリコール、ポリ１，３−プロピレングリコール、エチレンオキシドとプロピレンオキシドとの共重合体、エチレンオキシドとテトラヒドロフランとの共重合体などのポリアルキレングリコールのうち少なくとも１種が挙げられるが、満足できる透湿性を得るためにはポリエチレングリコールが最も好ましく例示され、その平均分子量が６００〜８,０００の範囲にあるものが好ましい。上記平均分子量が６００未満であると、満足できる機械的物性が得られず、一方、該平均分子量が８,０００を超えた場合には、相分離のためにポリエーテル-エステルの調製において問題を引き起こす場合がある。 Next, as a glycol component of the long-chain ester unit of the polyether-ester elastomer, polyethylene glycol, poly 1,2-propylene glycol, poly 1,3-propylene glycol, a copolymer of ethylene oxide and propylene oxide, Although at least 1 type is mentioned among polyalkylene glycols, such as a copolymer of ethylene oxide and tetrahydrofuran, in order to obtain satisfactory moisture permeability, polyethylene glycol is most preferably exemplified, and its average molecular weight is 600 to 8,000. Those in the range are preferred. If the average molecular weight is less than 600, satisfactory mechanical properties cannot be obtained. On the other hand, if the average molecular weight exceeds 8,000, there is a problem in the preparation of the polyether-ester for phase separation. May cause.
また、ポリエーテル−エステル系エラストマーの短鎖エステル単位のグリコール成分は、エチレングリコールおよびテトラメチレングリコールからなり、該エチレングリコールおよびテトラメチレングリコール中に占めるテトラメチレングリコールのモル分率が７０モル％未満のものが好ましく使用される。上記テトラメチレングリコールが７０モル％を超えると、コート層又はフィルム層自体は柔軟となるが、布帛とのモジュラス差が大きすぎるため、耐揉み性が悪く、コート層またはフィルム層と布帛の界面に剥離が生じやすい。 The glycol component of the short-chain ester unit of the polyether-ester elastomer is composed of ethylene glycol and tetramethylene glycol, and the molar fraction of tetramethylene glycol in the ethylene glycol and tetramethylene glycol is less than 70 mol%. Those are preferably used. When the tetramethylene glycol exceeds 70 mol%, the coat layer or the film layer itself becomes flexible, but the modulus difference from the fabric is too large, so that the sag resistance is poor and the interface between the coat layer or film layer and the fabric is poor. Peeling easily occurs.
上記テトラメチレングリコールのモル分率のさらに好ましい範囲は、７０モル％未満〜５０モル％以上の範囲である。
このようなポリエーテル−エステル系エラストマーが少なくとも布帛の片側面の一部にコーティングされるか、若しくは、ポリエーテル−エステル系エラストマーからなるフィルムが少なくとも基布の片側面にラミネートされていることが好ましい。
A more preferable range of the molar fraction of the tetramethylene glycol is a range of less than 70 mol% to 50 mol% or more.
It is preferable that such a polyether-ester elastomer is coated on at least a part of one side of the fabric, or a film made of a polyether-ester elastomer is laminated on at least one side of the base fabric. .
ポリエーテル−エステル系エラストマーを布帛の片側面の一部にコーティングする方法としては、ポリエーテル−エステル系エラストマーを該エラストマーが溶解可能な溶剤で溶解した後に、該布帛表面上にコーティングし、乾式法、または、湿式法により溶剤を除去することにより得られる。 As a method of coating the polyether-ester elastomer on a part of one side of the fabric, the polyether-ester elastomer is dissolved in a solvent capable of dissolving the elastomer, and then coated on the surface of the fabric, followed by a dry method. Alternatively, it can be obtained by removing the solvent by a wet method.
該ポリエーテル−エステル系エラストマーが溶解可能な溶剤としては、ジメチルホルムアミド、ジオキサン、エチレンホルマール、トルエン、クロロホルム、塩化メチレンの１種、又は、２種以上の有機溶剤があげられるが、低沸点および毒性を考慮した場合、エチレンホルマールを使用するものが最も好ましい。 Solvents in which the polyether-ester elastomer can be dissolved include dimethylformamide, dioxane, ethylene formal, toluene, chloroform, methylene chloride, or two or more organic solvents. In view of the above, it is most preferable to use ethylene formal.
エチレンホルマールを用いる場合は、該ポリエーテル−エステル系エラストマーを２〜３０重量％、好ましくは、５〜２０重量％の範囲で使用して、５０〜６０℃の温度でエチレンホルマールに溶解させ溶液を調合する。 In the case of using ethylene formal, the polyether-ester elastomer is used in the range of 2 to 30% by weight, preferably 5 to 20% by weight, and the solution is dissolved in ethylene formal at a temperature of 50 to 60 ° C. Mix.
また、布帛上にコーティングする方法としては、通常のコーティング法、例えば、ナイフコーター等を用いて行えばよいが、コーティングの量としては、コーティング層が２〜５０μｍ、好ましくは、１０〜２０μｍの範囲となるように行えばよい。該コーティング層が２μｍ未満の場合には、均一な皮膜を形成することが困難であり、また、５０μｍを超える場合には風合として弾性が強くなり、また、透湿性も低下するので好ましくない。 Moreover, as a method of coating on the fabric, a normal coating method, for example, a knife coater or the like may be used. The amount of coating is such that the coating layer is 2 to 50 μm, preferably 10 to 20 μm. It can be done so that When the coating layer is less than 2 μm, it is difficult to form a uniform film, and when it exceeds 50 μm, elasticity is increased as a texture and moisture permeability is also deteriorated.
該エチレンホルマールを除去する方法としては、乾式法と湿式法とがあるが、乾式法においては、温度：７０〜１７０℃の乾熱条件下、好ましくは、温度：７０〜１５０℃の範囲で行われる。湿式法においては、ポリエステル 系エラストマーが不溶で、エチレンホルマールが可溶な溶液、例えば、温水中にてエチレンホルマールを抽出した後、乾燥を行う。 As a method for removing the ethylene formal, there are a dry method and a wet method. In the dry method, the temperature is 70 to 170 ° C., preferably, the temperature is 70 to 150 ° C. Is called. In the wet method, the polyester-based elastomer is insoluble and the ethylene formal is soluble, for example, the ethylene formal is extracted in warm water and then dried.
また、ポリエーテル−エステル系エラストマーからなるフィルムを作成する方法としては、公知の方法、例えば、インフレーション法やダイ押出し法により得た、厚さが好ましくは２〜５０μｍ、さらに好ましくは５〜２０μｍの均一なフィルムを使用するものがよい。上記フィルムの厚さが２μｍ未満の場合には、ラミネートの作業が困難となり均一な耐水圧が得られないおそれがあり、また透湿防水層の強度が著しく低下してしまい、一方、フィルムの厚さが５０μｍを超える場合には、透湿性が低下するおそれがあり、また防水透湿層の曲げ硬さが硬くなってしまうことで布帛全体が硬くなってしまう。 Moreover, as a method of producing a film comprising a polyether-ester elastomer, a thickness obtained by a known method, for example, an inflation method or a die extrusion method, is preferably 2 to 50 μm, more preferably 5 to 20 μm. It is preferable to use a uniform film. When the thickness of the film is less than 2 μm, the laminating operation becomes difficult and there is a possibility that uniform water pressure resistance may not be obtained, and the strength of the moisture permeable waterproof layer is significantly reduced. If the thickness exceeds 50 μm, the moisture permeability may be lowered, and the bending hardness of the waterproof and moisture-permeable layer becomes hard, so that the entire fabric becomes hard.
なお、ポリエステルフィルムに用いられるポリエステルとしては、上記以外に、例えば「主として結晶性芳香族ポリエステル単位からなるハードセグメントと、主として脂肪族ポリエーテル単位および／または脂肪族ポリエステル単位からなるソフトセグメントとを主たる構成成分とするポリエステルブロック共重合体」であってもよい。このポリエステルブロック共重合体の詳細は、例えば特開平１１−１７０４６１号公報の段落「０００９」〜「００１５」に詳述されている。 In addition to the above, the polyester used for the polyester film mainly includes, for example, “a hard segment mainly composed of a crystalline aromatic polyester unit and a soft segment mainly composed of an aliphatic polyether unit and / or an aliphatic polyester unit. It may be a “polyester block copolymer as a constituent”. Details of this polyester block copolymer are described in detail in paragraphs “0009” to “0015” of JP-A-11-170461, for example.
得られたフィルムは、種々の方法、例えば、熱処理、ミシン掛け、あるいは、接着剤の使用により、基布となる布帛とラミネートすることができる。好ましくは、接着剤である。
上記基布となる布帛と透湿防水性フィルムとの接着剤としては、ポリエーテルエステル系エラストマーなどのポリエステル樹脂からなる接着剤がリサイクル効率の上で好適ではあるが、重量比率が少ないので、ポリウレタン系接着剤であってもよい。
The obtained film can be laminated with a fabric to be a base fabric by various methods, for example, heat treatment, sewing, or use of an adhesive. Preferably, it is an adhesive.
As an adhesive between the fabric to be the base fabric and the moisture permeable waterproof film, an adhesive made of a polyester resin such as a polyetherester elastomer is suitable in terms of recycling efficiency, but the polyurethane has a low weight ratio. It may be a system adhesive.
また、前記透湿防水層の上に、例えば無機微粒子を含む透湿性高分子樹脂が全面にまたは部分的に積層されていてもよい。また、透湿防水層には目止めテープが貼られていてもよい。
本発明の透湿防水性布帛において、前記透湿防水層上に前記赤外線吸収剤が積層されている。すなわち、本発明の透湿防水性布帛において、基布、透湿防水層、赤外線吸収剤がこの順に配されている。
Further, on the moisture permeable waterproof layer, for example, a moisture permeable polymer resin containing inorganic fine particles may be laminated on the entire surface or partially. Moreover, the sealing tape may be affixed on the moisture-permeable waterproof layer.
In the moisture-permeable and waterproof fabric of the present invention, the infrared absorbent is laminated on the moisture-permeable and waterproof layer. That is, in the moisture permeable waterproof fabric of the present invention, the base fabric, the moisture permeable waterproof layer, and the infrared absorber are arranged in this order.
本発明の透湿防水性布帛は、例えば以下の製造方法により製造することができる。
まず、前記のように、基布の片面に透湿防水層を積層した後、該透湿防水層の表面に、
例えば、特開２００３−９６６６３号公報に記載された方法により、赤外線吸収剤を付着部と非付着部とからなるパターンで付着させる。
The moisture-permeable and waterproof fabric of the present invention can be produced, for example, by the following production method.
First, as described above, after laminating a moisture permeable waterproof layer on one side of the base fabric, on the surface of the moisture permeable waterproof layer,
For example, the infrared absorber is adhered in a pattern composed of an adhering portion and a non-adhering portion by a method described in JP-A-2003-96663.
すなわち、布帛に対して０．０２〜５０ｇ／ｍ2（より好ましくは０．５〜２０ｇ／ｍ2）の範囲内の前記赤外線吸収剤を用意する。赤外線吸収剤の付着量が該範囲よりも少ないと、布帛に太陽光等の赤外線があたっても、布帛が十分には暖められないおそれがある。逆に赤外線吸収剤の固着量が該範囲よりも多いと保温効果は十分であるものの経済的でない。 That is, the infrared absorber in the range of 0.02 to 50 g / m 2 (more preferably 0.5 to 20 g / m 2 ) is prepared for the fabric. If the adhesion amount of the infrared absorber is less than the above range, the fabric may not be sufficiently warmed even when the fabric is exposed to infrared rays such as sunlight. On the contrary, if the amount of fixing of the infrared absorber is larger than the above range, the heat retaining effect is sufficient, but it is not economical.
一方、ウレタン樹脂、アクリル樹脂、ポリエステル樹脂、シリコーン樹脂、塩化ビニル樹脂、ナイロン樹脂などのバインダー樹脂を用意する。バインダー樹脂の付着量は、樹脂固形分基準で、布帛に対して０．０１〜４０ｇ／ｍ2（より好ましくは５〜３０ｇ／ｍ2
）の範囲内であることが好ましい。
Meanwhile, a binder resin such as a urethane resin, an acrylic resin, a polyester resin, a silicone resin, a vinyl chloride resin, or a nylon resin is prepared. The adhesion amount of the binder resin is 0.01 to 40 g / m 2 (more preferably 5 to 30 g / m 2) based on the resin solid content with respect to the fabric.
) Is preferable.
次いで、前記赤外線吸収剤とバインダー樹脂とを、両者の配合組成物として布帛に付与される。その際、かかる配合組成物は水系、溶剤系のいずれで構成してもよいが、加工工程の作業環境上水系の方が好ましい。溶剤としては、トルエン、イソプロピルアルコール、ジメチルホルムアミド、メチルエチルケトン、酢酸エチルなどが例示される。この配合組成物には、エポキシ系などの架橋剤を併用してもよい。さらに、布帛本体に対する付着性を向上させる等の目的で適当な添加剤をさらに配合してもよい。 Subsequently, the said infrared absorber and binder resin are provided to a fabric as a compounding composition of both. In this case, the blended composition may be composed of either an aqueous system or a solvent system, but an aqueous system is preferable in view of the working environment of the processing step. Examples of the solvent include toluene, isopropyl alcohol, dimethylformamide, methyl ethyl ketone, ethyl acetate and the like. This blended composition may be used in combination with an epoxy-based crosslinking agent. Furthermore, you may further mix | blend a suitable additive for the objective of improving the adhesiveness with respect to a fabric main body.
前記赤外線吸収剤とバインダー樹脂（樹脂固形分基準）との配合比率として１：０．５〜１：５０（好ましくは１：５〜１：４０）の範囲内であることが好ましい。バインダー樹脂の配合比率が該範囲よりも少ないと、布帛を製品となした後、洗濯時に赤外線吸収剤が脱落しやすいため、保温性の洗濯耐久性が低下する恐れがある。逆に、バインダー樹脂の配合比率を該範囲よりも多くしても、洗濯耐久性の効果はあまり変わらず経済的でない。 The blending ratio of the infrared absorber to the binder resin (resin solid content basis) is preferably in the range of 1: 0.5 to 1:50 (preferably 1: 5 to 1:40). If the blending ratio of the binder resin is less than the above range, the infrared absorbent is likely to fall off during washing after the fabric is made into a product, so that there is a possibility that the heat-resistant washing durability may be lowered. On the contrary, even if the blending ratio of the binder resin is larger than the above range, the effect of washing durability is not changed so much and it is not economical.
次に、前述のように、前記赤外線吸収剤とバインダー樹脂とを、部分的に（すなわち、全面ではなく）、好ましくは、付着部と非付着部とからなるパターンで、前記透湿防水層上に付着させる。
布帛への、赤外線吸収剤とバインダー樹脂の付与手段として、まず両者を前述のような配合組成物となした後、該配合組成物を、グラビヤコーテイング法、スクリーンプリント法などの、公知の付与手段を用いることができる。
かくして得られた透湿防水性布帛において、基布の片面に透湿防水層が積層され、さらにその上に、赤外線吸収剤が付着しているので蓄熱性に優れる。さらには、赤外線吸収剤が付着部と非付着部とからなるパターンで付着しているので透湿防水性が損なわれることがない。
Next, as described above, the infrared absorbent and the binder resin are partially (that is, not over the entire surface), preferably in a pattern including an adhering portion and a non-adhering portion on the moisture permeable waterproof layer. Adhere to.
As a means for imparting an infrared absorber and a binder resin to a fabric, first, both are made into a blended composition as described above, and then the blended composition is applied to a known imparting means such as a gravure coating method or a screen printing method. Can be used.
In the moisture-permeable and waterproof fabric thus obtained, a moisture-permeable and waterproof layer is laminated on one side of the base fabric, and an infrared absorber is further deposited thereon, so that the heat storage property is excellent. Furthermore, since the infrared absorbent is adhered in a pattern comprising an adhering portion and a non-adhering portion, the moisture permeability and waterproofness is not impaired.
次に、本発明によれば、前記の透湿防水性布帛を用いてなる、スポーツウェア、アウトドアウェア、レインコート、紳士衣服、婦人衣服、作業衣、防護服、人工皮革、履物、鞄、カーテン、テント、寝袋、防水シート、およびカーシートの群より選ばれるいずれかの繊維製品が提供される。
ここで、繊維製品がスポーツウェア、アウトドアウェア、レインコート、紳士衣服、婦人衣服、作業衣、防護服の場合、通常、赤外線吸収剤が人体側となるよう使用される。
かかる繊維製品は前記の透湿防水性布帛を用いているので、透湿防水性だけでなく蓄熱性にも優れる。
Next, according to the present invention, sportswear, outdoor wear, raincoat, men's clothing, women's clothing, work clothing, protective clothing, artificial leather, footwear, bags, curtains, using the moisture permeable and waterproof fabric described above. Any fiber product selected from the group consisting of a tent, a sleeping bag, a tarpaulin, and a car seat is provided.
Here, when the textile product is sportswear, outdoor wear, raincoat, men's clothing, women's clothing, work clothing, or protective clothing, the infrared absorbent is usually used on the human body side.
Since such a textile product uses the moisture permeable waterproof fabric, it is excellent not only in moisture permeable and waterproof properties but also in heat storage.
次に、本発明の実施例およ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。
＜目付＞
ＪＩＳＬ１０９６ ６．４により測定した。
＜蓄熱性＞
２３℃、４５％ＲＨの環境下で、発泡スチロール製試料台の上に試料を設置し、該試料と試料台との間に熱電対温度センサーを挿入した。
次いで、試料表面（基布表面）の上方３０ｃｍの距離から試料表面を、Ｐａｎａｓｏｎｉｃ社製写真用ランプ「ＰＲＦ−５００ＷＢ」で１０分間照射し、前記熱電対温度センサーで温度を測定した。
＜通気性＞
ＪＩＳ Ｌ１０９６ ６．２７．１ Ａ法（フラジール法）により通気性（ｃｃ／ｃｍ２・ｓｅｃ）を測定した。
＜織物のカバーファクターＣＦ＞
下記式により、織物のカバーファクターＣＦを算出した。
ＣＦ＝（ＤＷｐ／１．１）１／２×ＭＷｐ＋（ＤＷｆ／１．１）１／２×ＭＷｆ
［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。］
Next, although the Example and comparative example of this invention are explained in full detail, this invention is not limited by these.
<Unit weight>
It was measured according to JISL1096 6.4.
<Heat storage>
In an environment of 23 ° C. and 45% RH, a sample was placed on a polystyrene foam sample table, and a thermocouple temperature sensor was inserted between the sample and the sample table.
Next, the sample surface was irradiated for 10 minutes with a photographic lamp “PRF-500WB” manufactured by Panasonic, from a distance of 30 cm above the sample surface (base fabric surface), and the temperature was measured with the thermocouple temperature sensor.
<Breathability>
The air permeability (cc / cm 2 · sec) was measured by JIS L1096 6.27.1 A method (Fragile method).
<Fabric cover factor CF>
The cover factor CF of the woven fabric was calculated from the following formula.
CF = (DWp / 1.1) 1/2 × MWp + (DWf / 1.1) 1/2 × MWf
[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). ]
［実施例１］
基布としてポリエチレンテレフタレートマルチフィラメント仮撚捲縮加工糸８４ｄｔｅｘ／７２ｆｉｌを経糸および緯糸に用いて公知の平組織の生機を織成した後、撥水加工を含む通常の染色工程にて分散染料により黒色に染色することにより、基布としてポリエステル織物（カバーファクターＣＦ１６６０、目付９３ｇｒ／ｍ２）を得た。その後、デュポン(株)製無孔質透湿性透明ポリエステルフィルム（商品名：アクティブレイヤー、厚み１０μｍ）を前記基布の片面にラミネーションすることにより透湿防水層を形成した。
次いで、赤外線吸収剤としてカーボンブラック（平均１次粒子径０．１μｍ）を固形分比で１５重量％含有するウレタン系樹脂（バインダー樹脂）を、通常のグラビアプリントロール機を使用して、前記基布のカレンダー加工を施された面に、図１に示す縦横格子状パターン（付着部の面積比率５０％、格子間の間隔１０ｍｍ、すなわち１０ｍｍ×１０ｍｍの正方形状の非付着部が飛島状に散在している）でプリントすることにより赤外線吸収剤を透湿防水層の表面に付着させ、透湿防水性布帛を得た。
得られた布帛において、赤外線吸収剤の付着量は０．８ｇ／ｍ２であった。該布帛は、蓄熱性評価で温度が下記の比較例１対比６．５℃高く、蓄熱性に優れたものであった。
次いで、前記透湿防水性布帛を用いて、赤外線吸収剤を基布よりも人体側に位置するようスポーツウェアを縫製して着用したところ、透湿防湿性に優れ、また、蓄熱性にも優れるものであった。
[Example 1]
After weaving a known plain texture using a polyethylene terephthalate multifilament false-twist crimped yarn 84dtex / 72fil as a base fabric for warp and weft, it is blackened with a disperse dye in a normal dyeing process including water-repellent processing By dyeing, a polyester fabric (cover factor CF1660, weight per unit area 93 gr / m 2 ) was obtained as a base fabric. Thereafter, a non-porous moisture-permeable transparent polyester film (trade name: active layer, thickness 10 μm) manufactured by DuPont Co., Ltd. was laminated on one side of the base fabric to form a moisture-permeable waterproof layer.
Next, a urethane-based resin (binder resin) containing carbon black (average primary particle size 0.1 μm) as an infrared absorber in a solid content ratio of 15% by weight is obtained using the above gravure printing roll machine. A vertical and horizontal grid pattern shown in FIG. 1 (area ratio of the adhering portions is 50%, the interval between the lattices is 10 mm, that is, 10 mm × 10 mm square non-adhering portions are scattered in a flying island shape on the surface of the cloth subjected to calendering Infrared absorbent was adhered to the surface of the moisture permeable waterproof layer to obtain a moisture permeable waterproof fabric.
In the obtained fabric, the adhesion amount of the infrared absorber was 0.8 g / m 2 . The fabric had a heat storage evaluation of 6.5 ° C. higher than that of Comparative Example 1 below, and was excellent in heat storage.
Next, when the sportswear is sewn and worn so that the infrared absorbent is positioned on the human body side with respect to the base fabric using the moisture-permeable and waterproof fabric, the moisture-permeable and moisture-proof property is excellent and the heat storage property is also excellent. It was a thing.
［比較例１］
実施例１において、赤外線吸収剤を含む樹脂層を積層しないこと以外は実施例１と同様にした。
[Comparative Example 1]
In Example 1, it carried out similarly to Example 1 except not laminating | stacking the resin layer containing an infrared absorber.
［比較例２］
実施例１において、カーボンブラックを含有するウレタン系樹脂を、透湿防水層の全表面（図５のパターン）に付着させること以外は実施例１と同様にした。
次いで、該布帛を用いて、赤外線吸収剤を基布よりも人体側に位置するようスポーツウェアを縫製して着用したところ、蓄熱性にも優れるものであったが、透湿防湿性には劣るものであった。
[Comparative Example 2]
In Example 1, the same procedure as in Example 1 was performed except that a urethane-based resin containing carbon black was attached to the entire surface (pattern in FIG. 5) of the moisture-permeable and waterproof layer.
Next, when the sportswear was sewn and worn so that the infrared absorbent was positioned on the human body side with respect to the base fabric using the fabric, it was excellent in heat storage, but inferior in moisture permeability and moisture resistance. It was a thing.
本発明によれば、蓄熱性に優れた透湿防水性布帛および該透湿防水性布帛を用いてなる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 moisture-permeable waterproof fabric excellent in heat storage and the textiles using this moisture-permeable waterproof fabric are provided, The industrial value is very large.
Claims (9)
ＣＦ＝（ＤＷｐ／１．１）１／２×ＭＷｐ＋（ＤＷｆ／１．１）１／２×ＭＷｆ
［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 moisture-permeable waterproof fabric according to any one of claims 1 to 5, wherein the base fabric is a woven fabric having a cover factor CF defined by the following formula of 300 to 3500.
CF = (DWp / 1.1) 1/2 × MWp + (DWf / 1.1) 1/2 × MWf
[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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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101322602B1 (en) * | 2013-05-27 | 2013-10-29 | (주)지비테크놀리지 | Dry fabric and manufacturing method for absorb and water repellency of antithetic property using |
| KR101612077B1 (en) | 2015-07-30 | 2016-04-12 | 아이비에스인터내셔널 주식회사 | A fabric with good flame retardant, waterproof, vapor permeability and fluorescence, and manufacturing method thereof |
| US20210291483A1 (en) * | 2017-11-10 | 2021-09-23 | Chen-Cheng Huang | Composite cloth |
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| KR101612077B1 (en) | 2015-07-30 | 2016-04-12 | 아이비에스인터내셔널 주식회사 | A fabric with good flame retardant, waterproof, vapor permeability and fluorescence, and manufacturing method thereof |
| US20210291483A1 (en) * | 2017-11-10 | 2021-09-23 | Chen-Cheng Huang | Composite cloth |
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| JP5788661B2 (en) | 2015-10-07 |
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