JP5548344B2 - Moisture permeable waterproof fabric - Google Patents
Moisture permeable waterproof fabric Download PDFInfo
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- JP5548344B2 JP5548344B2 JP2008122309A JP2008122309A JP5548344B2 JP 5548344 B2 JP5548344 B2 JP 5548344B2 JP 2008122309 A JP2008122309 A JP 2008122309A JP 2008122309 A JP2008122309 A JP 2008122309A JP 5548344 B2 JP5548344 B2 JP 5548344B2
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- 239000004744 fabric Substances 0.000 title claims description 132
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- 239000000843 powder Substances 0.000 claims description 47
- 239000012982 microporous membrane Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 64
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- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 1
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 229920000459 Nitrile rubber Polymers 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
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- 229920001225 polyester resin Polymers 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
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- 229910052710 silicon Chemical group 0.000 description 1
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- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Manufacturing Of Multi-Layer Textile Fabrics (AREA)
Description
本発明は、透湿防水性布帛に関するものである。 The present invention relates to a moisture-permeable and waterproof fabric.
透湿性と防水性とを併せ持つ透湿防水性布帛は、身体からの発汗による水蒸気を衣服外へ放出する機能と、雨が衣服内に侵入するのを防ぐ機能とを有するものであり、スポーツ衣料や防寒衣料などに広く用いられている。 A moisture-permeable and waterproof fabric having both moisture permeability and waterproof properties has a function of releasing water vapor generated by perspiration from the body to the outside of clothes and a function of preventing rain from entering the clothes. It is widely used for cold clothing.
このような透湿防水性布帛としては、糸を高密度に織り込んだ高密度織物や、繊維布帛の片面にポリウレタン、ポリエステル、ポリアミド又はポリテトラフルオロエチレンなどの樹脂からなる樹脂膜を形成した透湿防水性布帛がよく知られている。その中でも、汎用性並びにコストや性能面からポリウレタン樹脂が好ましく用いられている。 As such a moisture-permeable and waterproof fabric, a moisture-permeable fabric having a high-density woven fabric in which yarns are woven in high density or a resin film made of a resin such as polyurethane, polyester, polyamide or polytetrafluoroethylene is formed on one side of a fiber fabric. Waterproof fabrics are well known. Among these, polyurethane resins are preferably used in view of versatility, cost, and performance.
透湿防水性布帛の一例として、下記特許文献１には、繊維布帛上に、平均粒子径が１μｍ以下で、Ｎ，Ｎ−ジメチルホルムアミドの吸着量の多い無機微粉末を１質量％以上含有させたポリウレタン樹脂を湿式凝固することで、ポリウレタン樹脂特有のハニカムスキンコア構造の他にサブミクロンオーダーの微細孔を多数有する樹脂膜を備えた透湿防水性布帛が開示されている。同文献によれば、当該透湿防水性布帛は、透湿度７０００ｇ／ｍ２・２４ｈｒｓ、耐水圧０．６ｋｇｆ／ｃｍ２を満足する。 As an example of a moisture-permeable and waterproof fabric, Patent Document 1 below contains 1% by mass or more of inorganic fine powder having an average particle diameter of 1 μm or less and a large amount of N, N-dimethylformamide adsorbed on a fiber fabric. In addition to the honeycomb skin core structure peculiar to polyurethane resin, a moisture-permeable and waterproof fabric including a resin film having a large number of fine holes on the order of submicrons is disclosed. According to this document, the moisture-permeable and waterproof fabric satisfies a moisture permeability of 7000 g / m 2 · 24 hrs and a water pressure resistance of 0.6 kgf / cm 2 .
このように、一口に透湿防水性布帛といっても、上記のようにある一定レベル以上の透湿防水性能を具備するものもあれば、透湿性能及び防水性能のうち一方だけが特に優れるといったものまで、様々なタイプがある。とりわけ、透湿防水性能に優れるものは、一般にスポーツ衣料に供される傾向が強い。 As described above, even if a breathable waterproof fabric is used in one bite, there are some which have a moisture permeable waterproof performance of a certain level or more as described above, and only one of the moisture permeable performance and the waterproof performance is particularly excellent. There are various types. In particular, those excellent in moisture permeability and waterproof performance generally tend to be used for sports clothing.
一般に、運動時は、身体からの発汗により衣服内温度が外気に比して高くなる傾向にある。そのため、衣服内側には一般に結露が付着し、これが着用不快感を引き起こすことがある。この着用感の低下は、程度の差こそあれ透湿防水性布帛を用いた場合であっても例外でなく、これを解決のため手段が多数提案されている。 In general, during exercise, the temperature in clothes tends to be higher than the outside air due to sweating from the body. For this reason, condensation generally adheres to the inside of the garment, which may cause discomfort. This decrease in the feeling of wearing is not an exception even when a moisture-permeable waterproof fabric is used to some extent, and many means have been proposed to solve this problem.
例えば、特許文献２には、布帛上に形成されたポリウレタン樹脂層の上から、さらに接着剤層を介して、特定の吸放湿特性を有する裏地を貼り付けた透湿防水性布帛が開示されている。また、引用文献３には、布帛上に形成された、特定の無機微粉末を含有するポリウレタン微多孔質膜の上から、さらに接着剤層を介して裏地を貼り付けた透湿防水性布帛が開示されている。これらはいずれも結露防止性に優れており、結果、ムレ感、冷え感といった着用不快感を解消するに至っている。
近年、アウトドアブームの高まりによって、透湿防水性布帛の用途が従来のようにスポーツ衣料や防寒衣料を主とするものから、広くレジャー分野全般に渡るようになってきた。このため、透湿防水性布帛に対し、より高い透湿防水性能と併せ良好な風合いや高い洗濯耐久性なども要望されている。 In recent years, with the growing outdoor boom, the use of moisture-permeable and waterproof fabrics has been widespread in the leisure field from the past, mainly from sports clothing and cold clothing. For this reason, there is a demand for moisture permeable and waterproof fabrics that have higher moisture permeable and waterproof performance, as well as good texture and high washing durability.
透湿防水性布帛を広くレジャー分野全般に適用するには、一般に防水性能として耐水圧２００ｋＰａ以上を有することが好ましく、この数値範囲を達成するには、布帛上にポリウレタン微多孔質膜とポリウレタン無孔質膜とを順次形成させる手段を採用するのが最も一般的であるといわれている。しかし、２つの樹脂層を形成することは、防水性能向上に資する一方で、透湿性能を透湿度（Ａ−１法）４０００〜５０００ｇ／ｍ２・２４ｈｒｓクラスまで低下させてしまう場合もある。 In order to widely apply a moisture-permeable waterproof fabric to the leisure field in general, it is generally preferable to have a water pressure resistance of 200 kPa or more as a waterproof performance. To achieve this numerical range, a polyurethane microporous membrane and a polyurethane-free fabric are provided on the fabric. It is said that it is most common to adopt means for sequentially forming a porous membrane. However, while forming two resin layers contributes to improvement in waterproof performance, the moisture permeability may be lowered to a moisture permeability (A-1 method) 4000 to 5000 g / m 2 · 24 hrs class.
そこで、樹脂層を貼り合わせるときに用いる接着剤層として、水膨潤性を有する樹脂層を使用することが提案されており、これにより、透湿防水性布帛の透湿度は、Ｂ−１法ながら所望のレベルまで引き上げることが可能となった。しかし、このような透湿防水性布帛は、洗濯耐久性や質量感などに難点があり、Ｂ−１法ながら所望の透湿度を達成できるものの、依然として着用時の衣服内湿度は高いままであり、着用感に劣るという課題を残している。 Therefore, it has been proposed to use a water-swellable resin layer as an adhesive layer used when the resin layers are bonded together. As a result, the moisture permeability of the moisture-permeable and waterproof fabric is B-1 method. It became possible to raise to a desired level. However, such a moisture-permeable and waterproof fabric has drawbacks in washing durability and a feeling of mass and can achieve a desired moisture permeability while using the B-1 method, but the moisture in the clothes when worn still remains high. , Leaving the problem of inferior wear.
本発明はこのような現状に鑑みて行われたもので、高い透湿性能と防水性能とを備えると共に、風合いや耐久性などにも優れた透湿防水性布帛を提供することを目的とする。 The present invention has been made in view of such a situation, and an object thereof is to provide a moisture-permeable and waterproof fabric having high moisture permeability and waterproof performance, and having excellent texture and durability. .
本発明は、上記の目的を達成するもので、次の構成よりなるものである。
（１）布帛、ポリウレタン微多孔質膜、接着剤層及び布帛の順に積層貼合されてなり、該ポリウレタン微多孔質膜は、厚みが１０〜５０μｍであると共に、フュームドシリカ系微粉末として疎水性フュームドシリカ系微粉末のみを２０〜４５質量％含有し、かつ孔径１μｍ以下の多数の微細孔が膜全体に渡り均等に配された構造を呈しており、さらに、布帛全体として、耐水圧が２５０〜５００ｋＰａであり、かつＪＩＳＬ１０９９（Ａ−１法）に準じて測定される透湿度が７０００〜１１０００ｇ／ｍ ２ ・２４ｈｒｓであることを特徴とする透湿防水性布帛。
（２）前記接着剤層がパターン状で設けられていることを特徴とする請求項１記載の透湿防水性布帛。
The present invention achieves the above-mentioned object and has the following configuration.
(1) A fabric, a polyurethane microporous membrane, an adhesive layer, and a fabric are laminated and bonded in this order. The polyurethane microporous membrane has a thickness of 10 to 50 μm and is hydrophobic as a fumed silica-based fine powder. 20% to 45% by mass of fine fumed silica-based fine powder, and a structure in which a large number of micropores having a pore diameter of 1 μm or less are uniformly distributed over the entire membrane , Is a moisture permeable and waterproof fabric characterized by having a moisture permeability of 7000 to 11000 g / m 2 · 24 hrs measured according to JIS L1099 (A-1 method) .
(2) moisture-permeable waterproof fabric according to claim 1, wherein said adhesive layer is characterized by being provided with a pattern.
本発明の透湿防水性布帛は、高い透湿性能と防水性能とを備えると共に、風合い及び洗濯耐久性などに非常に優れている。そのため、本発明の透湿防水性布帛は、スポーツ衣料だけでなく、広くレジャー分野全般に用いることができる。 The moisture-permeable and waterproof fabric of the present invention has high moisture permeability and waterproof performance, and is very excellent in texture and washing durability. Therefore, the moisture-permeable waterproof fabric of the present invention can be widely used not only for sports clothing but also in the general leisure field.
また、本発明の透湿防水性布帛が備えてなる微多孔質膜は、構造としてハニカムスキン構造をとるのではなく、ナノオーダーの微細な孔を多数有する微多孔質なものであるから、厚みを抑えることができ、結果、風合い向上や質量感低減などに非常に有利である。 In addition, the microporous membrane provided in the moisture-permeable and waterproof fabric of the present invention does not have a honeycomb skin structure as a structure, but is a microporous film having many nano-order fine pores. As a result, it is very advantageous for improving texture and reducing mass feeling.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の透湿防水性布帛に用いうる布帛としては、例えば、ナイロン６、ナイロン６６で代表されるポリアミド系合成繊維、ポリエチレンテレフタレートで代表されるポリエステル系合成繊維、ポリアクリルニトリル系合成繊維、ポリビニルアルコール系合成繊維などの合成繊維、トリアセテートなどの半合成繊維、あるいはナイロン６／綿、ポリエチレンテレフタレート／綿などの混合繊維からなる織物、編物又は不織布などがあげられる。 Examples of the fabric that can be used in the moisture permeable waterproof fabric of the present invention include, for example, polyamide synthetic fibers represented by nylon 6 and nylon 66, polyester synthetic fibers represented by polyethylene terephthalate, polyacrylonitrile synthetic fibers, and polyvinyl. Examples include synthetic fibers such as alcohol-based synthetic fibers, semi-synthetic fibers such as triacetate, and woven fabrics, knitted fabrics, and nonwoven fabrics made of mixed fibers such as nylon 6 / cotton and polyethylene terephthalate / cotton.
本発明の透湿防水性布帛は、２枚の布帛の間に特定のポリウレタン微多孔質膜を備えてなるものである。 The moisture-permeable and waterproof fabric of the present invention comprises a specific polyurethane microporous membrane between two fabrics.
ポリウレタン微多孔質膜は、厚みとして１０〜５０μｍの範囲を満足する必要があり、１５〜４０μｍが好ましい。厚みが１０μｍ未満になると、防水性能が低減する傾向にあり、一方、５０μｍを超えると、ハニカムスキンコア構造に近い形態を呈しやすくなる他、風合いを悪化させやすい傾向にあり、いずれも好ましくない。 The polyurethane microporous membrane needs to satisfy a thickness range of 10 to 50 μm, and preferably 15 to 40 μm. When the thickness is less than 10 μm, the waterproof performance tends to be reduced. On the other hand, when the thickness is more than 50 μm, a form close to the honeycomb skin core structure tends to be exhibited and the texture tends to be deteriorated.
本発明におけるポリウレタン微多孔質膜は、基本的に、凝固液として水又はＮ，Ｎ−ジメチルホルムアミドを少量含有する水混合液を使用して、所定のポリウレタン樹脂を凝固させる、いわゆる湿式法により形成する。つまり、樹脂溶液中の溶媒と、凝固液中に含まれる水との間で生じる溶媒置換を利用することで、製膜するのである。したがって、ポリウレタン樹脂は固形のままで使用されるのではなく、溶液にして用いるのが一般的である。このとき、ポリウレタン樹脂を溶解させる溶媒としては、ポリウレタン樹脂を溶解する極性有機溶媒であれば特段限定されないが、後述するフュームドシリカ系微粉末がＮ，Ｎ−ジメチルホルムアミドを多量に吸着しやすい特性を有することから、Ｎ，Ｎ−ジメチルホルムアミドが好適である。 The polyurethane microporous membrane in the present invention is basically formed by a so-called wet method in which a predetermined polyurethane resin is coagulated using water or a water mixed solution containing a small amount of N, N-dimethylformamide as a coagulating solution. To do. That is, a film is formed by utilizing solvent substitution that occurs between the solvent in the resin solution and the water contained in the coagulation liquid. Therefore, the polyurethane resin is generally used as a solution, not as a solid. At this time, the solvent for dissolving the polyurethane resin is not particularly limited as long as it is a polar organic solvent that dissolves the polyurethane resin, but the fumed silica-based fine powder described later has a characteristic of easily adsorbing a large amount of N, N-dimethylformamide. N, N-dimethylformamide is preferable.
上記ポリウレタン樹脂としては、例えば、イソシアネート成分とポリオール成分とを反応させて得られる重合体があげられる。イソシアネート成分としては、例えば、芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環族ジイソシアネートなどが単独で又は混合して用いられる。具体的には、トリレン−２，４−ジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、１，６−ヘキサンジイソシアネート又は１，４−シクロヘキサンジイソシアネートなどを主成分として用い、必要に応じ３官能以上のイソシアネートを使用してもよい。一方、ポリオール成分としては、例えば、ポリエーテルポリオールやポリエステルポリオールなどが用いられる。ポリエーテルポリオールとしては、例えば、ポリエチレングリコール、ポリプロピレングリコール又はポリテトラエチレングリコールなどが用いられる。ポリエステルポリオールとしては、例えば、エチレングリコールやプロピレングリコールなどのジオールと、アジピン酸やセバチン酸などの二塩基酸との反応生成物、又はカプロラクトンなどの開環重合物を用いることができ、勿論、オキシ酸モノマーあるいはそのプレポリマーの重合物も用いることができる。 Examples of the polyurethane resin include a polymer obtained by reacting an isocyanate component and a polyol component. As an isocyanate component, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, etc. are used individually or in mixture, for example. Specifically, tolylene-2,4-diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,6-hexane diisocyanate or 1,4-cyclohexane diisocyanate is used as a main component, and trifunctional or higher functional isocyanate is used as necessary. May be used. On the other hand, as a polyol component, polyether polyol, polyester polyol, etc. are used, for example. As the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetraethylene glycol or the like is used. As the polyester polyol, for example, a reaction product of a diol such as ethylene glycol or propylene glycol and a dibasic acid such as adipic acid or sebacic acid, or a ring-opening polymer such as caprolactone can be used. A polymer of an acid monomer or a prepolymer thereof can also be used.
本発明の透湿防水性布帛は主に衣料用途に適用するものであるから、微多孔質膜は当然、使用に耐えうるだけの強伸度を有していることが好ましい。そのため、かかるポリウレタン樹脂の強伸度として、具体的に１００％モジュラスが１〜２０ＭＰａの範囲を満足することが好ましく、２〜１５ＭＰａを満足することがより好ましい。１００％モジュラスが１ＭＰａ未満では、布帛の耐水圧や透湿性能などが低下する傾向にあり、一方、２０ＭＰａを超えると、微多孔質膜の形態安定性が低下するだけでなく、布帛の風合いも硬くなる傾向にあり、いずれも好ましくない。なお、この強伸度は、樹脂を無孔質膜となして測定されるものである。 Since the moisture-permeable and waterproof fabric of the present invention is mainly applied to apparel use, it is naturally preferable that the microporous membrane has a high elongation enough to withstand use. Therefore, it is preferable that the 100% modulus specifically satisfies the range of 1 to 20 MPa, and more preferably 2 to 15 MPa as the strong elongation of the polyurethane resin. If the 100% modulus is less than 1 MPa, the water pressure resistance or moisture permeability of the fabric tends to be reduced. On the other hand, if it exceeds 20 MPa, not only the shape stability of the microporous membrane is lowered but also the texture of the fabric is reduced. It tends to be hard and neither is preferable. In addition, this strong elongation is measured by using a resin as a nonporous film.
また、本発明では、繊維布帛との接着性向上の観点から、ポリウレタン樹脂が架橋されたものであることが好ましい。架橋に用いる架橋剤としては、イソシアネート化合物などが好適であり、一般には、ポリウレタン樹脂に対し１〜１０質量％程度の割合で用いる。この他、樹脂中には、目的に応じ、顔料、フィラーなどの各種添加剤、抗菌剤、消臭剤、難燃剤などの各種機能材を含有させてもよい。 Moreover, in this invention, it is preferable that a polyurethane resin is bridge | crosslinked from a viewpoint of an adhesive improvement with a fiber fabric. As a crosslinking agent used for crosslinking, an isocyanate compound or the like is suitable, and in general, it is used at a ratio of about 1 to 10% by mass with respect to the polyurethane resin. In addition, the resin may contain various functional materials such as various additives such as pigments and fillers, antibacterial agents, deodorants, and flame retardants, depending on the purpose.
本発明に使用しうるポリウレタン樹脂は、純然たるポリウレタン樹脂であってよいことは当然であるが、何らこれに限定されず、少量であればポリウレタン樹脂以外の重合体が含まれていてもよい。具体的には、ポリウレタン樹脂中に含まれる当該重合体の比率としては、２０質量％以下が好ましい。 The polyurethane resin that can be used in the present invention may of course be a pure polyurethane resin, but is not limited to this, and a small amount of a polymer other than the polyurethane resin may be included as long as the amount is small. Specifically, the proportion of the polymer contained in the polyurethane resin is preferably 20% by mass or less.
かかる重合体としては、例えば、ポリアクリル酸、ポリ塩化ビニル、ポリスチレン、ポリブタジエン、ポリアミノ酸、ポリカーボネートなどの他、これらの共重合体、あるいは、これらをフッ素やシリコンなどで変成したものなどがあげられる。なお、これらの重合体の１００％モジュラスも、前述の範囲を満足するのが好ましいことはいうまでもない。 Examples of such a polymer include polyacrylic acid, polyvinyl chloride, polystyrene, polybutadiene, polyamino acid, polycarbonate and the like, copolymers thereof, and those modified with fluorine or silicon. . Needless to say, the 100% modulus of these polymers also preferably satisfies the aforementioned range.
かかる微多孔質膜は、以上のような所定のポリウレタン樹脂から形成されてなるものであるが、本発明では、この微多孔質膜にフュームドシリカ系微粉末が１５〜４５質量％、好ましくは２０〜４０質量％含有されている。これにより、孔径１μｍ以下のナノオーダーレベルにある多数の孔が膜全体に渡って略均等に配された構造の微多孔質膜が形成される。つまり、かかる微粉末の含有量が１５質量％未満であると、上記構造を呈する微多孔質膜を形成することができず、ハニカムスキンコア構造を呈する従来のものと同様の構造となることがある。加えて、布帛に対し透湿、防水の両機能を同時に付与することが困難となる。一方、４５質量％を超えると、微多孔質膜が脆くなる傾向にあり、結果、洗濯耐久性の低下などを招く恐れがある。また、布帛の質量が過度に増える傾向にあり、用途が限られる恐れがある。 Such a microporous membrane is formed from a predetermined polyurethane resin as described above. In the present invention, fumed silica-based fine powder is contained in the microporous membrane in an amount of 15 to 45% by mass, preferably It is contained in an amount of 20 to 40% by mass. As a result, a microporous membrane having a structure in which a large number of pores having a pore diameter of 1 μm or less at a nano-order level are arranged substantially uniformly over the entire membrane is formed. That is, when the content of the fine powder is less than 15% by mass, it is not possible to form a microporous film exhibiting the above structure, and a structure similar to the conventional one exhibiting a honeycomb skin core structure may be obtained. is there. In addition, it becomes difficult to simultaneously impart both moisture permeability and waterproof functions to the fabric. On the other hand, if it exceeds 45% by mass, the microporous membrane tends to become brittle, and as a result, the washing durability may be lowered. Moreover, there exists a tendency for the mass of a fabric to increase excessively and there exists a possibility that a use may be restricted.
ここで、フュームドシリカ系超微粉末とは、アモルファス構造で細孔のない球状二酸化珪素粒子が凝集した一次粒子からなるものである。 Here, the fumed silica ultrafine powder is composed of primary particles in which spherical silicon dioxide particles having an amorphous structure and no pores are aggregated.
具体的に、フュームドシリカ系超微粉末の一次粒子径としては、７〜４０ｎｍが好ましく、１０〜３０ｎｍがより好ましい。粒子径が７ｎｍ未満であると、取り扱いが煩雑になることに加え、均一分散性の点で不利となり易い傾向にあり、好ましくない。一方、４０ｎｍを超えると、膜内に孔径の大きな孔が形成される結果、布帛の防水性能を低下させてしまうことがあり、好ましくない。 Specifically, the primary particle size of the fumed silica-based ultrafine powder is preferably 7 to 40 nm, and more preferably 10 to 30 nm. If the particle diameter is less than 7 nm, handling becomes complicated, and it tends to be disadvantageous in terms of uniform dispersibility, which is not preferable. On the other hand, if the thickness exceeds 40 nm, pores having a large pore diameter are formed in the membrane, and as a result, the waterproof performance of the fabric may be deteriorated.
また、フュームドシリカ系微粉末が微多孔質膜形成に寄与する点を考慮し、当該微粉末はＮ，Ｎ−ジメチルホルムアミドを吸着するものであることが好ましい。具体的な吸着量としては、１５０ｍＬ／１００ｇ以上が好ましく、２００ｍＬ／１００ｇ以上がより好ましい。Ｎ，Ｎ−ジメチルホルムアミドの吸着量が１５０ｍＬ／１００ｇ未満であると、ナノオーダーレベルの孔を形成し難くなる傾向にあり、布帛に優れた透湿性能を付与し難くなるので好ましくない。 In consideration of the fact that the fumed silica-based fine powder contributes to the formation of the microporous film, the fine powder preferably adsorbs N, N-dimethylformamide. As a specific adsorption amount, 150 mL / 100 g or more is preferable, and 200 mL / 100 g or more is more preferable. When the amount of N, N-dimethylformamide adsorbed is less than 150 mL / 100 g, it tends to be difficult to form nano-order level pores, and it becomes difficult to impart excellent moisture permeability to the fabric.
ここで、Ｎ，Ｎ−ジメチルホルムアミドの吸着量は、以下の方法で測定されるものである。すなわち、フュームドシリカ系微粉末５ｇをガラス平板上におき、Ｎ，Ｎ−ジメチルホルムアミドを１滴滴下するごとにステンレス製のへらを用いて練り合わせる作業を繰り返し、Ｎ，Ｎ−ジメチルホルムアミドの１滴で急激に柔らかくなる直前までに要したＮ，Ｎ−ジメチルホルムアミドの体積（単位：ｍＬ）を測定する。つまり、この測定方法は、ＪＩＳ Ｋ５１０１Ｋを準用したものであり、煮あまに油に代えてＮ，Ｎ−ジメチルホルムアミドを用いた方法である。 Here, the adsorption amount of N, N-dimethylformamide is measured by the following method. That is, 5 g of fumed silica-based fine powder was placed on a glass plate and kneaded with a stainless steel spatula each time one drop of N, N-dimethylformamide was added to repeat 1 of N, N-dimethylformamide. Measure the volume (unit: mL) of N, N-dimethylformamide required until immediately before dripping and softening. That is, this measuring method is a method using JIS K5101K, and using N, N-dimethylformamide instead of boiled sesame oil.
本発明におけるフュームドシリカ系微粉末は、上記の物性を有するものであれば、基本的にどのようなものでも使用できる。例えば、粒子表面に多数のシラノール基を有する親水性フュームドシリカ微粉末や、この粒子にジメチルジクロロシランなどの有機珪素ハロゲン化物を反応させることで疎水改質した、疎水性フュームドシリカ系微粉末などが使用できる。また、フュームド金属酸化物も、かかる微粉末の一態様といえ、例えば、親水又は疎水性のフュームド酸化アルミニウム微粉末、フュームド酸化チタン微粉末、酸化ジルコニウム微粉末などが使用可能である。さらに、例示したこれらの微粉末と各種金属酸化物とを混合して得た微粉末も有効である。 As the fumed silica-based fine powder in the present invention, basically any fine powder can be used as long as it has the above physical properties. For example, a hydrophilic fumed silica fine powder having a large number of silanol groups on the particle surface, or a hydrophobic fumed silica fine powder that is hydrophobically modified by reacting this particle with an organosilicon halide such as dimethyldichlorosilane. Etc. can be used. A fumed metal oxide is also an embodiment of such a fine powder. For example, a hydrophilic or hydrophobic fumed aluminum oxide fine powder, a fumed titanium oxide fine powder, a zirconium oxide fine powder, or the like can be used. Furthermore, fine powders obtained by mixing these exemplified fine powders with various metal oxides are also effective.
このような微粉末を具体的に例示すれば、日本アエロジル（株）製、「ＡＥＲＯＳＩＬ ９０（商品名）」、「ＡＥＲＯＳＩＬ １３０（商品名）」、「ＡＥＲＯＳＩＬ １５０（商品名）」、「ＡＥＲＯＳＩＬ ２００（商品名）」、「ＡＥＲＯＳＩＬ３００（商品名）」といった親水性フュームドシリカ系微粉末、「ＡＥＲＯＳＩＬ Ｒ１０４（商品名）」、「ＡＥＲＯＳＩＬ Ｒ１０６（商品名）」、「ＡＥＲＯＳＩＬ Ｒ２０２（商品名）」、「ＡＥＲＯＳＩＬ Ｒ８０５（商品名）」、「ＡＥＲＯＳＩＬ ＲＸ２００（商品名）」、「ＡＥＲＯＳＩＬ ＲＸ３００（商品名）」、「ＡＥＲＯＳＩＬ Ｒ９７２（商品名）」、「ＡＥＲＯＳＩＬ Ｒ９７４（商品名）」、「ＡＥＲＯＳＩＬ Ｒ９７６（商品名）」、「ＡＥＲＯＳＩＬ Ｒ７２００（商品名）」、「ＡＥＲＯＳＩＬ Ｒ８２００（商品名）」、「ＡＥＲＯＳＩＬ Ｒ９２００（商品名）」といった疎水性フュームドシリカ系微粉末などがあげられ、この他にも、フュームドシリカとフュームド酸化アルミニウムを混合させた微粉末として「ＡＥＲＯＳＩＬ ＣＯＫ８４（商品名）」、疎水性フュームド酸化アルミニウム微粉末として「ＡＥＲＯＸＩＤＥ Ａｌｕ Ｃ ８０５（商品名）」などがあげられる。 Specific examples of such fine powder include “AEROSIL 90 (trade name)”, “AEROSIL 130 (trade name)”, “AEROSIL 150 (trade name)”, “AEROSIL 200” manufactured by Nippon Aerosil Co., Ltd. (Trade name) ”,“ AEROSIL 300 (trade name) ”, such as hydrophilic fumed silica fine powder,“ AEROSIL R104 (trade name) ”,“ AEROSIL R106 (trade name) ”,“ AEROSIL R202 (trade name) ”, “AEROSIL R805 (product name)”, “AEROSIL RX200 (product name)”, “AEROSIL RX300 (product name)”, “AEROSIL R972 (product name)”, “AEROSIL R974 (product name)”, “AEROSIL R976 (product name) Name) ”,“ AEROSIL R720 Hydrophobic fumed silica-based fine powders such as “0 (trade name)”, “AEROSIL R8200 (trade name)”, “AEROSIL R9200 (trade name)”, and the like. In addition, fumed silica and fumed aluminum oxide "AEROSIL COK84 (trade name)" as a fine powder mixed with, and "AEROXIDE Alu C 805 (trade name)" as a hydrophobic fumed aluminum oxide fine powder.
本発明では、上記に列挙したフュームドシリカ系超微粉末を、目的に応じ単独又は複数選択し、使用すればよい。例えば、膜形態を均一にさせ、微多孔質膜の透湿性能を向上させる観点からは、親水性又は疎水性フュームドシリカ系微粉末が好ましく、中でも漏水性や防水耐久性の点で疎水性フュームドシリカ系微粉末が好ましい。また、微多孔質膜の負帯電防止性や微多孔質膜形成の際に用いる樹脂溶液の分散性、流動性及び安定性などを考慮すれば、親水性及び／又は疎水性フュームドシリカ系微粉末と他の金属酸化したものとを混用して用いるのがよい。 In the present invention, the fumed silica ultrafine powder listed above may be used alone or in combination depending on the purpose. For example, hydrophilic or hydrophobic fumed silica-based fine powder is preferable from the viewpoint of making the membrane form uniform and improving the moisture permeability of the microporous membrane, and in particular, hydrophobicity in terms of water leakage and waterproof durability. Fumed silica fine powder is preferred. Further, considering the negative antistatic property of the microporous membrane and the dispersibility, fluidity, and stability of the resin solution used for forming the microporous membrane, hydrophilic and / or hydrophobic fumed silica-based fine particles are used. It is preferable to use a mixture of powder and other metal oxides.
また、上記フュームドシリカ系超微粉末の製法としては、公知の方法が採用でき、例えば、燃焼加水分解法により得ることができる。具体的には、公知の乾式法シリカの一種たる珪素塩化物を気化し、高温の炎中において気層状態で酸化すれば、容易に目的の微粉末を得ることができる。 Moreover, as a manufacturing method of the said fumed silica type | system | group ultra fine powder, a well-known method is employable, For example, it can obtain by a combustion hydrolysis method. Specifically, the desired fine powder can be easily obtained by evaporating silicon chloride, which is a kind of known dry-process silica, and oxidizing it in a gas phase in a high-temperature flame.
このように、本発明おけるポリウレタン微多孔質膜は、フュームドシリカ系微粉末を特定質量含有するものである。これにより、かかる微多孔質膜は、孔径１μｍ以下のナノオーダーレベルにある多数の孔が膜全体に渡って略均等に配された構造を呈し、その結果、厚みを薄くしても、優れた防水性能と透湿性能とを同時に実現させることができる。この点、本発明の透湿防水性布帛は、風合いの向上や質量感の低減などにも効果があり、従来の透湿防水性布帛のように、ハニカムスキンコア構造をした厚い樹脂膜（厚み５０〜１００μｍ、孔径５〜５０μｍ）を備えてなるものとは大きく異なる。 Thus, the polyurethane microporous membrane in the present invention contains a specific mass of fumed silica-based fine powder. As a result, such a microporous membrane has a structure in which a large number of pores having a pore size of 1 μm or less at a nano-order level are arranged substantially evenly over the entire membrane, and as a result, even if the thickness is reduced, it is excellent. Waterproof performance and moisture permeability performance can be realized at the same time. In this respect, the moisture-permeable waterproof fabric of the present invention is also effective in improving the texture and reducing the mass feeling, and has a thick resin film (thickness) having a honeycomb skin core structure as in the conventional moisture-permeable waterproof fabric. 50-100 μm, pore diameter 5-50 μm).
ここで、かかる微多孔質膜が、ハニカムスキンコア構造ではなく、なぜこのような構造を呈するかについては、詳細は不明であるものの、本発明者らは以下のように推測している。 Here, although the details are unknown as to why such a microporous film exhibits such a structure instead of the honeycomb skin core structure, the present inventors presume as follows.
すなわち、後述する樹脂溶液中に含まれる固形分の濃度を好ましくは１５〜３５％とする点、固形分中に含まれるフュームドシリカ系微粉末の割合を１５〜４５質量％とする点、並びに溶媒置換をフュームドシリカ系微粉末の周囲で先行させる点、並びに厚み（乾燥時）を１０〜５０μｍとする点などが有機的に作用し、相乗効果として、均一構造の微多孔質膜が形成されるものと推測している。 That is, the point which makes the density | concentration of the solid content contained in the resin solution mentioned later preferably 15-35%, the point which makes the ratio of the fumed silica type fine powder contained in solid content 15-45 mass%, and The point that solvent substitution precedes the fumed silica fine powder and the point that the thickness (when dried) is 10 to 50 μm function organically, forming a microporous film with a uniform structure as a synergistic effect I guess it will be.
そして、本発明の透湿防水性布帛では、上記のポリウレタン微多孔質膜の裏面側（上記布帛側の反対面側）に接着剤層（接着剤からなる層）を介して別のもう一枚の布帛が貼りあわされている。 In the moisture-permeable and waterproof fabric of the present invention, another sheet is provided on the back side of the polyurethane microporous membrane (the side opposite to the fabric side) via an adhesive layer (a layer made of an adhesive). This fabric is pasted.
このもう一枚の布帛としては、特に限定されるものでなく、例えば、既述の布帛と同一のものでも使用可能である。ただし、得られる透湿防水性布帛の質量感、風合いの他、製造コストなども勘案すれば、好ましくはトータル繊度１５〜７８ｄｔｅｘ、より好ましくは１５〜４４ｄｔｅｘの合成繊維糸条からなる布帛とし、特に合成繊維として好ましくはナイロン６、ナイロン６６を使用する。 The other fabric is not particularly limited, and for example, the same fabric as that described above can be used. However, considering the mass feeling and texture of the moisture permeable and waterproof fabric obtained, considering the production cost, etc., it is preferably a fabric composed of synthetic fiber yarns with a total fineness of 15 to 78 dtex, more preferably 15 to 44 dtex, Nylon 6 and nylon 66 are preferably used as synthetic fibers.
この他、ここに用いる布帛は、透湿防水性布帛の裏面を構成するものであるところ、自身が吸湿性を具備していることや、縫製部分の目張りを確実なものとするためシームテープ接着性を有していることも、好ましい態様に含まれる。 In addition, the fabric used here constitutes the back surface of the moisture-permeable and waterproof fabric, and has seam tape bonding to ensure that the fabric itself is hygroscopic and that the stitching of the sewn portion is reliable. It is included in a preferable aspect that it has property.
他方、上記もう一枚の布帛を微多孔質膜に接着させるための接着剤としては、従来公知のものであれば、どのようなものでも使用しうる。具体的には、天然ゴム、ニトリルゴム系、クロロプレンゴム系などの合成ゴム、酢酸ビニル系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、エチレン−酢酸ビニル共重合樹脂、ポリウレタン系樹脂などを、単独で又は混合して用いることができる。また、樹脂のタイプとしても特に限定されるものでなく、エマルジョン型、溶剤型、ホットメルト型、硬化型などいずれも使用可能であるが、特に接着耐久性の観点から硬化型が好ましい。 On the other hand, any conventionally known adhesive may be used as the adhesive for adhering the other fabric to the microporous membrane. Specifically, synthetic rubber such as natural rubber, nitrile rubber, chloroprene rubber, vinyl acetate resin, acrylic resin, polyamide resin, polyester resin, ethylene-vinyl acetate copolymer resin, polyurethane resin, etc. These can be used alone or in combination. Also, the type of resin is not particularly limited, and any of an emulsion type, a solvent type, a hot melt type, and a curable type can be used, but a curable type is particularly preferable from the viewpoint of adhesion durability.
例えば、水酸基、イソシアネート基、アミノ基、カルボキシル基などの反応基を持ついわゆる架橋性を有したポリウレタン、ポリエステル、ポリアミド、ポリエチレン−酢酸ビニルなどが自己架橋するか、又はイソシアネート系、エポキシ系などの架橋剤と架橋して、接着剤が硬化型となるものが好ましい。中でも、ポリウレタン系樹脂接着剤が柔軟性に富み、かつ透湿性にも優れているので特に好ましい。 For example, so-called crosslinkable polyurethane having a reactive group such as hydroxyl group, isocyanate group, amino group, carboxyl group, polyester, polyamide, polyethylene-vinyl acetate, or the like, or cross-linking of isocyanate type, epoxy type, etc. It is preferable to crosslink with the agent to make the adhesive curable. Among these, polyurethane resin adhesives are particularly preferable because they are flexible and have excellent moisture permeability.
また、接着剤層の形状としては、得られる透湿防水性布帛の機能を損なわない限り、任意の形状が採用できる。例えば、得られる透湿防水性布帛の防水性能を向上させることを考慮すれば、微多孔質膜上の全面又は略全面に該接着剤層を設けるのが好ましく、一方、透湿性能や風合いを考慮すれば、かかる接着剤層の形状としては、点状又は部分的、あるいは一定模様を呈するパターン状のものが好ましいことになる。ただ、透湿防水性布帛の防水性能は、ポリウレタン微多孔質膜の厚みを調整するなどして所望のものとなすことが可能なので、一般に、接着剤層の形状としては後者の態様が好ましく、特に剥離強度の点からパターン状のものが好ましい。 Moreover, as a shape of an adhesive bond layer, arbitrary shapes can be employ | adopted unless the function of the moisture-permeable waterproof fabric obtained is impaired. For example, in consideration of improving the waterproof performance of the resulting moisture-permeable waterproof fabric, it is preferable to provide the adhesive layer on the entire surface or substantially the entire surface of the microporous membrane, while the moisture-permeable performance and texture are improved. In consideration of this, the shape of the adhesive layer is preferably a dot shape, a partial shape, or a pattern having a certain pattern. However, since the waterproof performance of the moisture-permeable waterproof fabric can be made desired by adjusting the thickness of the polyurethane microporous membrane, in general, the latter aspect is preferable as the shape of the adhesive layer. A pattern-like one is particularly preferable from the viewpoint of peel strength.
パターン状の形状としては、例えば、点状（ドット状）、線状、格子状、市松模様、亀甲模様などがあげられ、剥離強度の点から、パターンのなす柄が全体として均一性あるものが好ましい。また、微多孔質膜に対する接着剤層の占有面積としては、２０〜７０％の範囲が好ましく、３０〜５０％がより好ましい。 Examples of the pattern shape include a dot shape (dot shape), a line shape, a lattice shape, a checkered pattern, a turtle shell pattern, and the like. From the viewpoint of peeling strength, the pattern formed by the pattern is uniform as a whole. preferable. Moreover, as an occupation area of the adhesive bond layer with respect to a microporous film, the range of 20 to 70% is preferable, and 30 to 50% is more preferable.
そして、接着剤層の厚みとしては、一般に５〜１００μｍが好ましく、１０〜７０μｍがより好ましく、２０〜５０μｍが特に好ましい。厚みが５μｍ未満になると、透湿防水性布帛の剥離強力が乏しくなる傾向にあり、一方、１００μｍを超えると、透湿性能が低下したり、風合いが硬化したりすることがあるので、いずれも好ましくない。 And as thickness of an adhesive bond layer, generally 5-100 micrometers is preferable, 10-70 micrometers is more preferable, and 20-50 micrometers is especially preferable. If the thickness is less than 5 μm, the peel strength of the moisture-permeable and waterproof fabric tends to be poor. On the other hand, if it exceeds 100 μm, the moisture-permeable performance may be lowered or the texture may be cured. It is not preferable.
以上のように、本発明の透湿防水性布帛は、布帛、ポリウレタン微多孔質膜、接着剤層及び布帛の順に積層貼合されてなるものであって、優れた透湿防水性能を発揮するものである。かかる透湿防水性能を具体的に数値化すると、防水性能の指標たる耐水圧としては２５０〜５００ｋＰａが好ましく、透湿性能の指標たる透湿度としては７０００〜１１０００ｇ／ｍ２・２４ｈｒｓが好ましい。なお、耐水圧は、ＪＩＳ Ｌ１０９２（高水圧法）に、透湿度は、ＪＩＳ Ｌ１０９９（Ａ−１法）にそれぞれ準じて測定されるものである。 As described above, the moisture-permeable and waterproof fabric of the present invention is formed by laminating and bonding a fabric, a polyurethane microporous membrane, an adhesive layer and a fabric in this order, and exhibits excellent moisture-permeable and waterproof performance. Is. When this moisture-permeable waterproof performance is specifically quantified, the water pressure resistance as an index of waterproof performance is preferably 250 to 500 kPa, and the moisture permeability as an index of moisture-permeable performance is preferably 7000 to 11000 g / m 2 · 24 hrs. The water pressure resistance is measured according to JIS L1092 (high water pressure method), and the moisture permeability is measured according to JIS L1099 (A-1 method).
次に、本発明の透湿防水性布帛の製法について説明する。なお、以下に記載する製法は、単なる代表例に過ぎないと理解されるべきである。 Next, the manufacturing method of the moisture-permeable waterproof fabric of this invention is demonstrated. It should be understood that the manufacturing methods described below are merely representative examples.
まず、布帛を用意する。本発明では、例えば布帛として製織編しただけのもの（生機）や染色上がりの布帛などをそのまま用いてもよいが、布帛に樹脂溶液を塗布する際に樹脂溶液が布帛内部へ深く浸透するのを防ぐ観点から、撥水加工やカレンダー加工された布帛を用いるのがよい。 First, a fabric is prepared. In the present invention, for example, a woven or knitted fabric (raw machine) or a dyed fabric may be used as it is, but when the resin solution is applied to the fabric, the resin solution penetrates deeply into the fabric. From the viewpoint of prevention, it is preferable to use a water repellent or calendered fabric.
上記撥水加工に用いる撥水剤としては、例えば、パラフィン系撥水剤、ポリシロキサン系撥水剤、フッ素系撥水剤などがあげられ、加工方法としては、例えば、パディング法、コーティング法、スプレー法などがあげられる。 Examples of the water repellent used for the water repellent processing include paraffinic water repellent, polysiloxane water repellent, fluorine water repellent, and the processing methods include, for example, padding, coating, The spray method etc. are mention | raise | lifted.
また、上記カレンダー加工としては、温度制御機能を有する鏡面ロールと、コットンロール又はプラスチックロールとの間に布帛を走行させ、鏡面ロールでもって布帛表面を目潰しすればよい。なお、後述する樹脂溶液の塗布は、布帛のカレンダー加工された面に対し行うのが一般的である。 Moreover, as said calendar process, a cloth should just run between the mirror roll which has a temperature control function, and a cotton roll or a plastic roll, and the cloth surface should just be crushed with a mirror roll. In general, application of a resin solution described later is performed on a calendered surface of a fabric.
布帛を準備した後、ポリウレタン樹脂を含む所定の樹脂溶液を準備する。かかる樹脂溶液中に含まれる固形分濃度（固形分とは、揮発、蒸発などしない成分の総称であり、具体的には、樹脂成分、微粉末、添加剤成分、機能剤成分の他、各種助剤成分などが該当する）としては、１５〜３５％が好ましい。また、粘度としては、５０００〜３００００ｍＰａ・ｓ（２５℃）が好ましい。粘度が５０００ｍＰａ・ｓ（２５℃）未満では、樹脂溶液が布帛内部へ深く浸透する傾向が強く、一方、３００００ｍＰａ・ｓ（２５℃）を超えると、樹脂溶液のレベリング性に問題が生じやすくなる傾向にあり、いずれも好ましくない。 After preparing the fabric, a predetermined resin solution containing a polyurethane resin is prepared. Concentration of solid content contained in the resin solution (solid content is a general term for components that do not volatilize or evaporate. Specifically, in addition to resin components, fine powders, additive components, functional agent components, various assistants are included. 15 to 35% is preferable as the agent component. Moreover, as a viscosity, 5000-30000 mPa * s (25 degreeC) is preferable. If the viscosity is less than 5000 mPa · s (25 ° C.), the resin solution has a strong tendency to penetrate deeply into the fabric. On the other hand, if the viscosity exceeds 30000 mPa · s (25 ° C.), problems tend to occur in the leveling properties of the resin solution. Both are not preferred.
そして、かかる樹脂溶液中には、既述したフュームドシリカ系微粉末が含まれており、含有量は全固形分に対し１５〜４５質量％含まれる。 And in this resin solution, the fumed silica type fine powder mentioned above is contained, and content is 15-45 mass% with respect to the total solid.
フュームドシリカ系微粉末は、均一構造の微多孔質膜を形成する観点から、溶液中に均一に含有されていることが好ましく、このため、溶液中に当該微粉末を含有させる際は、その目的に沿う手段を採用する。具体的には、３本ロールミル機、ニーダー機、サンドミル機などの混練機を用いて、所定の含有率に均一分散する、又は同混練機で高含有率に混練した後、所定の含有率に均一撹拌するなどの手段が好ましく採用される。 From the viewpoint of forming a microporous film having a uniform structure, the fumed silica-based fine powder is preferably contained uniformly in the solution. Therefore, when the fine powder is contained in the solution, Adopt means that meet your objectives. Specifically, using a kneader such as a three roll mill, a kneader, or a sand mill, uniformly disperse to a predetermined content, or after kneading to a high content with the same kneader, to a predetermined content Means such as uniform stirring are preferably employed.
また、ポリウレタン樹脂を溶解させる溶媒としては、前述のようにＮ，Ｎ−ジメチルホルムアミドが好ましいが、本発明の効果を損なわない範囲で、Ｎ，Ｎ−ジメチルホルムアミド以外のものを併用してもよい。 Further, as described above, N, N-dimethylformamide is preferable as a solvent for dissolving the polyurethane resin, but other than N, N-dimethylformamide may be used in combination as long as the effects of the present invention are not impaired. .
本発明では、布帛、樹脂溶液を準備した後、布帛の片面に樹脂溶液を塗布する。塗布は、布帛の片面全面に行い、必要に応じ所々厚みに差を設けてもよい。 In the present invention, after preparing a fabric and a resin solution, the resin solution is applied to one side of the fabric. Application may be performed on the entire surface of one side of the fabric, and if necessary, a difference in thickness may be provided in some places.
塗布手段としては、例えば、コンマコータ、ナイフコータなどを用いて塗布する手段があげられる。そして、塗布量としては、最終的に得られる微多孔質膜の厚みを１０〜５０μｍとする点を十分考慮して適宜決定する。 Examples of the application means include means for applying using a comma coater, a knife coater or the like. The coating amount is appropriately determined in consideration of the point that the thickness of the finally obtained microporous film is 10 to 50 μm.
樹脂溶液を塗布した後は、樹脂溶液中に含まれる固形分を湿式法により凝固させる。 After applying the resin solution, the solid content contained in the resin solution is solidified by a wet method.
湿式凝固に用いる凝固液としては、前述のように、水又はＮ，Ｎ−ジメチルホルムアミドを少量含有する水混合液を使用する。水混合液の場合、濃度としては、操業性や環境面を考慮し、５〜３０％程度が好ましい。また、凝固液の温度としては５〜３５℃が好ましく、凝固時間としては３０秒間〜５分間が好ましい。 As the coagulation liquid used for wet coagulation, as described above, water or a water mixed solution containing a small amount of N, N-dimethylformamide is used. In the case of a water mixture, the concentration is preferably about 5 to 30% in consideration of operability and environmental aspects. The temperature of the coagulation liquid is preferably 5 to 35 ° C., and the coagulation time is preferably 30 seconds to 5 minutes.
固形分を凝固させた後は、Ｎ，Ｎ−ジメチルホルムアミドの除去を促進する目的で、３５〜８０℃の温度下で１〜１０分間湯洗する。そして、湯洗後は、５０〜１５０℃の温度下で１〜１０分間乾燥する。以上のようにしてポリウレタン微多孔質膜を形成できるが、次工程後たる接着剤層の形成に移る前に、防水耐久性や撥水耐久性などを付与する目的で、得られた布帛を撥水加工してもよい。ここで行う撥水加工としては、撥水剤、加工方法共に既述の撥水加工を準用すればよい。 After solidifying the solid content, it is washed with hot water at a temperature of 35 to 80 ° C. for 1 to 10 minutes for the purpose of promoting the removal of N, N-dimethylformamide. And after hot water washing, it dries for 1 to 10 minutes at the temperature of 50-150 degreeC. Although the polyurethane microporous membrane can be formed as described above, the resulting fabric is repelled for the purpose of imparting waterproof durability, water repellency durability, etc. before proceeding to the formation of the adhesive layer after the next step. Water processing may be performed. As the water-repellent processing performed here, the above-described water-repellent processing may be applied to both the water-repellent agent and the processing method.
ポリウレタン微多孔質膜を形成した後は、この膜上に接着剤層を形成する。接着剤層を形成するには、例えば、樹脂のタイプがエマルジョン型や溶剤型であれば、コンマコータ、グラビアコータ、スクリーンなどを用いて、微多孔質膜上に樹脂溶液を任意の形状で塗布し、５０〜１５０℃で１〜５分間乾燥すれば容易に形成することができる。また、樹脂がホットメルト型であれば、Ｔダイ、グラビアロールなどを用いて、微多孔質膜上に樹脂溶液を任意の形状で押し出し、２０〜１５０℃で圧着貼合すれば容易に形成できる。 After forming the polyurethane microporous membrane, an adhesive layer is formed on the membrane. In order to form the adhesive layer, for example, if the resin type is an emulsion type or a solvent type, a resin solution is applied on the microporous film in an arbitrary shape using a comma coater, gravure coater, screen or the like. It can be easily formed by drying at 50 to 150 ° C. for 1 to 5 minutes. Further, if the resin is a hot melt type, it can be easily formed by extruding a resin solution in an arbitrary shape onto a microporous film using a T die, a gravure roll or the like and pressure bonding at 20 to 150 ° C. .
そして、接着剤層の形成後、予め準備しておいたもう一枚の布帛を接着剤層表面に圧着もしくは熱圧着して、本発明の透湿防水性布帛を得ることができる。なお、本発明では、防水性能や洗濯耐久性などの向上のため、もう一枚の布帛を貼り付けた後、前述した撥水加工を準用するなどして撥水加工してもよい。 Then, after the formation of the adhesive layer, another fabric prepared in advance can be pressure-bonded or thermo-compressed to the surface of the adhesive layer to obtain the moisture-permeable and waterproof fabric of the present invention. In the present invention, in order to improve waterproof performance, washing durability, etc., after applying another piece of fabric, the above-described water-repellent treatment may be applied mutatis mutandis.
以下、実施例により本発明をさらに具体的に説明する。なお、実施例、比較例における布帛の性能の測定、評価は、次の方法で行った。 Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the measurement of the performance of the fabric in an Example and a comparative example and evaluation were performed with the following method.
（１）耐水圧
ＪＩＳ Ｌ１０９２（高水圧法）に準じて測定した。
(1) Water pressure resistance Measured according to JIS L1092 (high water pressure method).
（２）洗濯耐久性
同一の布帛について、洗濯前の耐水圧と、ＪＩＳ Ｌ０２１７（１０３法）に準じた洗濯を２０回繰り返した後（２０洗後）の耐水圧とを測定した後、洗濯前の耐水圧（Ａ）に対する２０洗後耐水圧（Ｂ）の保持率（Ａ／Ｂ×１００（％））を算出し、布帛の洗濯耐久性とした。
(2) Washing durability After measuring the water pressure resistance before washing and the water pressure resistance after washing 20 times (after 20 washing) in accordance with JIS L0217 (103 method) for the same fabric, before washing The retention rate (A / B × 100 (%)) of the water pressure resistance after washing 20 (A / B × 100 (%)) relative to the water pressure resistance (A) of the fabric was calculated as the washing durability of the fabric.
（３）透湿度
ＪＩＳ Ｌ１０９９（Ａ?１法）塩化カルシウム法に準じて測定した。
(3) Moisture permeability Measured according to JIS L1099 (A-1 method) calcium chloride method.
（４）剥離強度
ＪＩＳ Ｌ１０８９に準じて裏地（もう一枚の布帛）経方向の接着強度を測定することで布帛の剥離強度を評価した。
(4) Peel strength The peel strength of the fabric was evaluated by measuring the adhesive strength in the warp direction of the backing (another fabric) according to JIS L1089.
（５）風合い
下記３水準で官能評価した。
○：ソフト
△：普通
×：ペーパーライクで粗硬
(5) Texture The sensory evaluation was performed according to the following three levels.
○: Soft △: Normal ×: Paper-like and coarse
（６）樹脂膜の厚み及び断面形態の観察
オリンパス光学工業（株）製、「ＯＬＹＭＰＵＳ ＢＨ−２型（商品名）」を用いて、倍率６６０倍の光学写真を撮影し、樹脂膜の厚み及び断面形態を観察した。
(6) Observation of thickness and cross-sectional shape of resin film Using Olympus Optical Co., Ltd., “OLYMPUS BH-2 type (trade name)”, an optical photograph at a magnification of 660 times was taken, and the thickness of the resin film and The cross-sectional form was observed.
（参考例１）
経緯糸にナイロン６フィラメント糸７８ｄｔｅｘ／６８ｆを用い、経糸密度１１５本／２．５４ｃｍ、緯糸密度９５本／２．５４ｃｍの平組織の布帛たるタフタを製織した。得られた布帛を精練した後、酸性染料（日本化薬（株）製、「ＫａｙａｎｏｌＭｉｌｌｉｎｇ Ｂｌｕｅ ＧＷ（商品名）」）１．０％ｏｍｆを用いて染色した。その後、フッ素系撥水剤エマルジョン（旭硝子（株）製、「アサヒガードＧＳ１０（商品名）」の５％水分散液を用いて、布帛をパディングし（絞り率４０％）、乾燥後、１７０℃で４０秒間熱処理した。続いて、鏡面ロールを有するカレンダー加工機を用いて、温度１７０℃、圧力３００ｋＰａ、速度３０ｍ／分の条件で布帛をカレンダー加工した。
( Reference Example 1)
Nylon 6 filament yarn 78 dtex / 68f was used for the warp and weave taffeta as a plain fabric with a warp density of 115 / 2.54 cm and a weft density of 95 / 2.54 cm. The obtained fabric was scoured and then dyed with 1.0% omf of an acid dye (manufactured by Nippon Kayaku Co., Ltd., “Kayanol Milling Blue GW (trade name)”). Thereafter, the fabric was padded with a 5% aqueous dispersion of a fluorine-based water repellent emulsion (Asahi Glass GS10 (trade name), manufactured by Asahi Glass Co., Ltd.) (squeezing rate 40%), dried, and 170 ° C. Then, the fabric was calendered using a calendering machine having a mirror roll at a temperature of 170 ° C., a pressure of 300 kPa, and a speed of 30 m / min.
一方で、ナイロン６フィラメント糸２２ｄｔｅｘ／７ｆを用い、針密度２８本／２．５４ｃｍのトリコット経編機にて経編地を編成し、これを通常の方法で精練し、裏地に供する布帛（もう一枚の布帛）とした。 On the other hand, using a nylon 6 filament yarn 22dtex / 7f, a warp knitted fabric is knitted with a tricot warp knitting machine having a needle density of 28 / 2.54 cm, and this is scoured by a normal method and used for a lining (another fabric) A piece of fabric).
また、Ｎ，Ｎ−ジメチルホルムアミドを溶媒とするエステル型ポリウレタン樹脂溶液であって固形分濃度が２８％である、セイコー化成（株）製、「ラックスキン１７４０−２９Ｂ（商品名）」と、一次粒子径が１６ｎｍの疎水性フュームドシリカ系微粉末であってＮ，Ｎ−ジメチルホルムアミドの吸着量が２６０ｍＬ／１００ｇである、日本アエロジル（株）製、「ＡＥＲＯＳＩＬ Ｒ９７２（商品名）」と、Ｎ，Ｎ−ジメチルホルムアミドとを順に３：１：１の割合で粗練りした後、３本ロールミル機を用いて均一に混練し、無色透明の樹脂溶液（樹脂溶液Ａ）を得た。 Further, an ester type polyurethane resin solution containing N, N-dimethylformamide as a solvent and having a solid content of 28%, “Lack Skin 1740-29B (trade name)” manufactured by Seiko Chemical Co., Ltd. “AEROSIL R972 (trade name)” manufactured by Nippon Aerosil Co., Ltd., which is a hydrophobic fumed silica fine powder having a particle size of 16 nm and has an adsorption amount of N, N-dimethylformamide of 260 mL / 100 g; , N-dimethylformamide in the order of 3: 1: 1, and then kneaded uniformly using a three-roll mill to obtain a colorless and transparent resin solution (resin solution A).
次いで、上記樹脂溶液Ａを含有する、下記処方１に示す組成のポリウレタン樹脂溶液を準備した。なお、この樹脂溶液は、粘度が２５℃下において１００００ｍＰａ・ｓであり、固形分濃度は２４％、全固形分中に占める疎水性フュームドシリカ系微粉末の割合は３０質量％であった。 Subsequently, the polyurethane resin solution of the composition shown in the following prescription 1 containing the resin solution A was prepared. This resin solution had a viscosity of 10,000 mPa · s at 25 ° C., a solid content concentration of 24%, and a proportion of hydrophobic fumed silica-based fine powder in the total solid content was 30% by mass.
《処方１》
エステル型ポリウレタン樹脂溶液（セイコー化成（株）製、「ラックスキン１７４０−２９Ｂ（商品名）」） ５０質量部
樹脂溶液Ａ ５０質量部
イソシアネート化合物（大日精化工業（株）製、架橋剤「レザミンＸ（商品名）」固形分１００％） １質量部
Ｎ，Ｎ−ジメチルホルムアミド ３８質量部
<< Prescription 1 >>
Ester-type polyurethane resin solution (manufactured by Seiko Kasei Co., Ltd., “Rack Skin 1740-29B (trade name)”) 50 parts by mass
Resin solution A 50 parts by mass Isocyanate compound (manufactured by Dainichi Seika Kogyo Co., Ltd., cross-linking agent “Rezamine X (trade name)” 100% solid content) 1 part by mass N, N-dimethylformamide 38 parts by mass
そして、コンマコータを用いて、布帛（タフタ）のカレンダー加工された面の全面に、上記処方１にかかる樹脂溶液を１００ｇ／ｍ２塗布した。塗布後直ちに、かかる布帛をＮ，Ｎ−ジメチルホルムアミドを濃度１５％含有する水混合液（２０℃）に２分間浸漬した。続いて、布帛を５０℃の温度下で５分間湯洗し、マングルで絞った後、１３０℃で２分間乾燥し、ポリウレタン微多孔質膜を形成した。 And using the comma coater, 100 g / m < 2 > of the resin solution concerning the said prescription 1 was apply | coated to the whole surface by which the calendar process of the fabric (taffeta) was carried out. Immediately after application, the fabric was immersed in an aqueous mixture (20 ° C.) containing N, N-dimethylformamide at a concentration of 15% for 2 minutes. Subsequently, the fabric was washed with hot water at a temperature of 50 ° C. for 5 minutes, squeezed with a mangle, and then dried at 130 ° C. for 2 minutes to form a polyurethane microporous membrane.
その後、フッ素系溶剤型撥水剤（旭硝子（株）製「アサヒガードＡＧ５８５０（商品名）」の３％ミネラルターペン溶液を用いて、得られた布帛をパディングし（絞り率３０％）、乾燥後、１７０℃で４０秒熱処理した。 Thereafter, the resulting fabric was padded with a 3% mineral turpentine solution of “Asahi Guard AG5850 (trade name)” manufactured by Asahi Glass Co., Ltd. And heat treatment at 170 ° C. for 40 seconds.
次に、下記処方２に示す組成のポリウレタン樹脂溶液を準備した。この樹脂溶液は２液タイプであり、接着剤層を形成するためのものである。粘度は２５℃下において１０００ｍＰａ・ｓであり、固形分濃度は３５％であった。 Next, a polyurethane resin solution having the composition shown in Formula 2 below was prepared. This resin solution is a two-component type for forming an adhesive layer. The viscosity was 1000 mPa · s at 25 ° C., and the solid content concentration was 35%.
《処方２》
非膨潤型ポリウレタン樹脂溶液（セイコー化成（株）製、「ラックスキンＵＤ−１０８（商品名）」） ５０質量部
膨潤型ポリウレタン樹脂溶液（セイコー化成（株）製、「ラックスキンＵＤ−４０４８（商品名）」） ５０質量部
イソシアネート化合物（日本ポリウレタン工業（株）製、架橋剤「コロネートＨＬ（商品名）」固形分１００％） ８質量部
メチルエチルケトン ３５質量部
トルエン １５質量部
<< Prescription 2 >>
Non-swelling polyurethane resin solution (manufactured by Seiko Kasei Co., Ltd., “Lackskin UD-108 (trade name)”) 50 parts by mass swelling polyurethane resin solution (manufactured by Seiko Kasei Co., Ltd., “Rackskin UD-4048 (product) Name) ") 50 parts by mass isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd., cross-linking agent" Coronate HL (trade name) "solid content 100%) 8 parts by mass methyl ethyl ketone 35 parts by mass toluene 15 parts by mass
そして、ドッド状に彫刻したグラビアロール（０．４ｍｍ／４０メッシュ、深度１００μｍ）を用いて、微多孔質膜上の全面にこの樹脂溶液を３５ｇ／ｍ２塗布した。塗布後、１３０℃で２分間乾燥し、接着剤層を形成した。 Then, 35 g / m 2 of this resin solution was applied to the entire surface of the microporous film using a gravure roll (0.4 mm / 40 mesh, depth 100 μm) engraved in a dod shape. After application, the film was dried at 130 ° C. for 2 minutes to form an adhesive layer.
接着剤層の形成後、前述の裏地（もう一枚の布帛）を、接着剤層表面に３００ｋＰａなるゲージ圧力にて圧着し、５０℃下で５日間エージングし、透湿防水性布帛を得た。 After formation of the adhesive layer, the above-mentioned lining (another piece of fabric), and pressed at a gauge pressure comprised 300kPa the adhesive layer surface, and aging for 5 days under 50 ° C., to obtain a moisture-permeable waterproof fabric .
透湿防水性布帛を得た後、微多孔質膜の態様につき、検証した。まず、光学写真から厚みは２５μｍと測定され、従来の透湿防水性布帛に比べ、厚みが薄いことが確認できた。また、同写真からは、膜中にハニカムスキンコア構造を発見できなかった。さらに進んで検証すべく、電界放射形走査電子顕微鏡（（株）日立製作所製、「Ｓ−４０００（商品名）」）を用いて、３０００倍、１００００倍の写真を撮影したところ、膜中には孔径１μｍ以下の孔が多数存在し、それらは膜全体に渡って略均等に分布していることが確認できた。 After obtaining a moisture-permeable and waterproof fabric, the aspect of the microporous membrane was verified. First, from an optical photograph, the thickness was measured to be 25 μm, and it was confirmed that the thickness was thinner than a conventional moisture-permeable and waterproof fabric. Further, from the same photograph, a honeycomb skin core structure could not be found in the film. For further verification, when a field-emission scanning electron microscope (manufactured by Hitachi, Ltd., “S-4000 (trade name)”) was photographed 3000 times and 10,000 times, It was confirmed that there were a large number of pores having a pore diameter of 1 μm or less, and these were distributed substantially evenly throughout the membrane.
他方、接着剤層についても、同じく光学写真から厚みを測定したところ、５〜２０μｍであった。 On the other hand, when the thickness of the adhesive layer was also measured from the optical photograph, it was 5 to 20 μm.
（実施例２）
ドッド状に彫刻したグラビアロールとして、０．４ｍｍ／４０メッシュ、深度１００μｍなるものに代えて、０．７ｍｍ／２５メッシュ、深度２００μｍなるものを用い、上記処方２にかかる樹脂溶液に代えて、下記処方３に示す組成のポリウレタン樹脂溶液をドット占有率４０％のドットパターンに塗布する以外は、参考例１と同様にして本発明の透湿防水性布帛を得た。なお、この樹脂溶液（処方３）も２液タイプであり、粘度は２５℃下において３０００ｍＰａ・ｓであり、固形分濃度は３９％であった。
(Example 2)
As a gravure roll engraved in a dod shape, instead of a 0.4 mm / 40 mesh and a depth of 100 μm, a 0.7 mm / 25 mesh and a depth of 200 μm are used. A moisture-permeable waterproof fabric of the present invention was obtained in the same manner as in Reference Example 1 except that a polyurethane resin solution having the composition shown in Formula 3 was applied to a dot pattern having a dot occupancy of 40%. In addition, this resin solution (prescription 3) was also a two-component type, the viscosity was 3000 mPa · s at 25 ° C., and the solid content concentration was 39%.
《処方３》
非膨潤型ポリウレタン樹脂溶液（セイコー化成（株）製、「ラックスキンＵＤ−１０８（商品名）」） １００質量部
イソシアネート化合物（日本ポリウレタン工業（株）製、架橋剤「コロネートＨＬ（商品名）」固形分１００％） ８質量部
メチルエチルケトン ２５質量部
トルエン １０質量部
<< Prescription 3 >>
Non-swelling polyurethane resin solution (Seiko Kasei Co., Ltd., “Lackskin UD-108 (trade name)”) 100 parts by mass isocyanate compound (Nihon Polyurethane Industry Co., Ltd., cross-linking agent “Coronate HL (trade name)” (Solid content 100%) 8 parts by mass methyl ethyl ketone 25 parts by mass toluene 10 parts by mass
透湿防水性布帛を得た後、参考例１の場合と同様の手段で微多孔質膜の態様を検証したところ、厚みは２５μｍと測定された。また、膜の構造としては、ハニカムスキンコア構造は発見されず、ナノオーダーレベルにある多数の微細孔を略均等に内在した構造であることが確認できた。さらに、接着剤層の厚みも同様に測定したところ、ドット中央部の最大厚みが約５０μｍであった。 After obtaining the moisture-permeable and waterproof fabric, the aspect of the microporous membrane was verified by the same means as in Reference Example 1, and the thickness was measured to be 25 μm. In addition, as a film structure, a honeycomb skin core structure was not found, and it was confirmed that the structure had a large number of micropores at the nano-order level substantially uniformly. Furthermore, when the thickness of the adhesive layer was measured in the same manner, the maximum thickness at the center of the dot was about 50 μm.
（実施例３）
ナイロン６フィラメント糸からなる布帛（タフタ）に代えて、下記の布帛を用いる以外は、参考例１と同様にして本発明の透湿防水性布帛を得た。すなわち、経緯糸にポリエステルフィラメント糸８３ｄｔｅｘ／６８ｆを用い、経糸密度１２０本／２．５４ｃｍ、緯糸密度９５本／２．５４ｃｍの平組織の布帛たるタフタを製織した。得られた布帛を精練した後、分散染料（ダイスター（株）製、「ＤｉａｎｉｘＹｅｌｌｏｗ ＳＥ−５Ｇ（商品名）」）０．３％ｏｍｆを用いて染色し、以降は参考例１と同様にして透湿防水性布帛を得た。
(Example 3)
A moisture-permeable waterproof fabric of the present invention was obtained in the same manner as in Reference Example 1 except that the following fabric was used instead of the fabric (taffeta) made of nylon 6 filament yarn. That is, polyester filament yarn 83dtex / 68f was used for the warp and weaved taffeta as a plain fabric with a warp density of 120 yarns / 2.54 cm and a weft density of 95 yarns / 2.54 cm. After scouring the resulting fabric, disperse dyes (DyStar Co., Ltd., "DianixYellow SE-5G (trade name)") were stained with 0.3% omf, and later permeability in the same manner as in Reference Example 1 A wet waterproof fabric was obtained.
透湿防水性布帛を得た後、参考例１の場合と同様の手段で微多孔質膜の態様を検証したところ、ハニカムスキンコア構造は発見されず、ナノオーダーレベルにある多数の微細孔を略均等に内在した構造であることが確認できた。 After obtaining the moisture-permeable and waterproof fabric, the aspect of the microporous membrane was verified by the same means as in Reference Example 1. As a result, a honeycomb skin core structure was not found, and a large number of micropores at the nano-order level were formed. It was confirmed that the structure was substantially uniform.
（参考例４、実施例５）
処方１にかかる樹脂溶液の塗布量を１００ｇ／ｍ２に代えて６０ｇ／ｍ２（参考例４）、１７０ｇ／ｍ２（実施例５）とする以外は、実施例２と同様にして透湿防水布帛を得た。
( Reference Example 4, Example 5)
Except that the coating amount of the prescription 1 resin solution in place of 100g / m 2 60g / m 2 ( Example 4), 170 g / m 2 (Example 5), moisture permeable in the same manner as in Example 2 A waterproof fabric was obtained.
透湿防水性布帛を得た後、参考例１の場合と同様の手段で微多孔質膜の態様を検証したところ、厚みが１５μｍ（参考例４）、厚みが４５μｍ（実施例５）であり、構造はいずれの膜においても、多数の微細孔を内在する略均一な構造であることが確認できた。 After obtaining the moisture-permeable and waterproof fabric, the aspect of the microporous membrane was verified by the same means as in Reference Example 1. The thickness was 15 μm ( Reference Example 4) and the thickness was 45 μm (Example 5). In any film, it was confirmed that the structure was a substantially uniform structure containing a large number of micropores.
（比較例１、２）
処方１にかかるポリウレタン樹脂溶液に代えて、下記処方４に示す組成のポリウレタン樹脂溶液を用いる以外は、参考例１と同様にして（比較例１）、また、実施例２と同様にして（比較例２）、それぞれ透湿防水性布帛を得た。なお、処方４にかかる樹脂溶液は、粘度が２５℃下において１３０００ｍＰａ・ｓであり、固形分濃度は２２％、全固形分中に占める疎水性フュームドシリカ系微粉末の割合は１０質量％であった。
(Comparative Examples 1 and 2)
In the same manner as in Reference Example 1 (Comparative Example 1) and in the same manner as in Example 2 except that a polyurethane resin solution having the composition shown in Formula 4 below is used instead of the polyurethane resin solution according to Formula 1 (Comparison) Example 2), moisture permeable waterproof fabrics were obtained. The resin solution according to Formula 4 has a viscosity of 13000 mPa · s at 25 ° C., a solid content concentration of 22%, and the proportion of the hydrophobic fumed silica fine powder in the total solid content is 10% by mass. there were.
《処方４》
エステル型ポリウレタン樹脂溶液（セイコー化成（株）製、「ラックスキン１７４０−２９Ｂ（商品名）」） ８５質量部
樹脂溶液Ａ １５質量部
イソシアネート化合物（大日精化工業（株）製、架橋剤「レザミンＸ（商品名）」固形分１００％） １質量部
Ｎ，Ｎ−ジメチルホルムアミド ３０質量部
<< Prescription 4 >>
Ester-type polyurethane resin solution (Seiko Kasei Co., Ltd., “Lackskin 1740-29B (trade name)”) 85 parts by mass Resin solution A 15 parts by mass Isocyanate compound (Daiichi Seika Kogyo Co., Ltd., crosslinker “Rezamin” X (trade name) "solid content 100%) 1 part by mass N, N-dimethylformamide 30 parts by mass
透湿防水性布帛を得た後、参考例１の場合と同様の手段で微多孔質膜の態様を検証したところ、共に厚みが６０μｍと測定され、従来の透湿防水性布帛と略同様のものであることが確認できた。また、構造としても、共に孔径１０〜４０μｍの縦長楕円状の孔が多数認められ、いわゆるハニカムスキンコア構造であるのが確認できた。 After obtaining the moisture-permeable and waterproof fabric, the aspect of the microporous membrane was verified by the same means as in Reference Example 1. Both thicknesses were measured to be 60 μm, which was almost the same as the conventional moisture-permeable and waterproof fabric. It was confirmed that it was. As for the structure, a large number of oblong holes having a hole diameter of 10 to 40 μm were recognized, confirming the so-called honeycomb skin core structure.
（比較例３）
処方１にかかるポリウレタン樹脂溶液に代えて、下記処方５に示す組成のポリウレタン樹脂溶液を用いる以外は、実施例２と同様にして透湿防水性布帛を得た。なお、処方５にかかる樹脂溶液は、粘度が２５℃下において１１０００ｍＰａ・ｓであり、固形分濃度は２７％、全固形分中に占める疎水性フュームドシリカ系微粉末の割合は５４質量％であった。
(Comparative Example 3)
A moisture-permeable waterproof fabric was obtained in the same manner as in Example 2 except that a polyurethane resin solution having the composition shown in the following formulation 5 was used instead of the polyurethane resin solution according to the formulation 1. The resin solution according to Formula 5 has a viscosity of 11000 mPa · s at 25 ° C., a solid content concentration of 27%, and a proportion of hydrophobic fumed silica fine powder in the total solid content is 54% by mass. there were.
《処方５》
樹脂溶液Ａ １００質量部
イソシアネート化合物（大日精化工業（株）製、架橋剤「レザミンＸ（商品名）」固形分１００％） １質量部
Ｎ，Ｎ−ジメチルホルムアミド ４０質量部
<< Prescription 5 >>
Resin solution A 100 parts by mass Isocyanate compound (manufactured by Dainichi Seika Kogyo Co., Ltd., cross-linking agent “Rezamine X (trade name)” solid content 100%) 1 part by mass N, N-dimethylformamide 40 parts by mass
透湿防水性布帛を得た後、参考例１の場合と同様の手段で微多孔質膜の態様を検証したところ、厚みが３０μｍと測定され、ハニカムスキンコア構造は発見されなかったものの、微粉末の含有量が多過ぎたため、微多孔質膜は脆いものとなった。その結果、得られた透湿防水性布帛は、下記表１に示すように洗濯耐久性に乏しく、硬い風合いのものとなった。 After obtaining the moisture-permeable and waterproof fabric, the aspect of the microporous membrane was verified by the same means as in Reference Example 1. As a result, the thickness was measured to be 30 μm, and the honeycomb skin core structure was not found. Since the powder content was too high, the microporous membrane became brittle. As a result, the obtained moisture-permeable and waterproof fabric was poor in washing durability and had a hard texture as shown in Table 1 below.
（比較例４、５）
処方１にかかる樹脂溶液の塗布量を１００ｇ／ｍ２に代えて３０ｇ／ｍ２（比較例４）、２５０ｇ／ｍ２（比較例５）とする以外は、実施例２と同様にして透湿防水布帛を得た。
(Comparative Examples 4 and 5)
Moisture permeability in the same manner as in Example 2, except that the coating amount of the resin solution according to Formula 1 was changed to 30 g / m 2 (Comparative Example 4) and 250 g / m 2 (Comparative Example 5) instead of 100 g / m 2. A waterproof fabric was obtained.
透湿防水性布帛を得た後、参考例１の場合と同様の手段で微多孔質膜の態様を検証したところ、厚みが６〜８μｍ（比較例４）、６０μｍ（比較例５）と測定された。膜の構造としては、前者（比較例４）ではハニカムスキンコア構造は発見されなかったものの、膜の厚みが薄すぎたため、透湿防水性布帛は防水性能に劣るものとなった。一方、後者（比較例５）では、膜の厚みが所定の範囲を超えており、膜がハニカムスキンコア構造を呈しているのが確認できた。 After obtaining the moisture-permeable and waterproof fabric, the aspect of the microporous membrane was verified by the same means as in Reference Example 1, and the thickness was measured as 6 to 8 μm (Comparative Example 4) and 60 μm (Comparative Example 5). It was done. As the membrane structure, although the honeycomb skin core structure was not found in the former (Comparative Example 4), the thickness of the membrane was too thin, so that the moisture-permeable waterproof fabric was inferior in waterproof performance. On the other hand, in the latter (Comparative Example 5), the thickness of the film exceeded a predetermined range, and it was confirmed that the film had a honeycomb skin core structure.
上記実施例及び比較例で得られた各布帛の性能を下記表１に示す。 The performance of each fabric obtained in the above examples and comparative examples is shown in Table 1 below.
表１の結果から明らかなように、本発明の透湿防水性布帛は、透湿性能、防水性能共に優れるだけでなく、良好な洗濯耐久性、さらにはソフト感に富む風合いも併せもつものであった。
As is apparent from the results in Table 1, the moisture-permeable and waterproof fabric of the present invention has not only excellent moisture permeability and waterproof performance, but also has good washing durability and a soft texture. there were.
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