JP2015530234A - Improved barrier cloth - Google Patents

Improved barrier cloth Download PDF

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JP2015530234A
JP2015530234A JP2015526636A JP2015526636A JP2015530234A JP 2015530234 A JP2015530234 A JP 2015530234A JP 2015526636 A JP2015526636 A JP 2015526636A JP 2015526636 A JP2015526636 A JP 2015526636A JP 2015530234 A JP2015530234 A JP 2015530234A
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barrier
layer
composition
fabric
primer composition
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ミェチスワフ ミシェル スタシュニック
ミェチスワフ ミシェル スタシュニック
エリック アントワーヌ ヒュブシュ
エリック アントワーヌ ヒュブシュ
ノエル ステファン ブラッブス
ノエル ステファン ブラッブス
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/724—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged forming webs during fibre formation, e.g. flash-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • D04H3/166—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion the filaments being flash-spun
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
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    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
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    • D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
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    • D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
    • D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
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    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
    • D06M14/06—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of animal origin, e.g. wool or silk
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    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
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    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
    • D06M14/10—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
    • D06M14/12—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
    • D06M14/12—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M14/14—Polyesters
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    • D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
    • D06M14/12—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
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    • D06M14/28—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
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    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2041—Two or more non-extruded coatings or impregnations
    • Y10T442/2049—Each major face of the fabric has at least one coating or impregnation
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    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2041—Two or more non-extruded coatings or impregnations
    • Y10T442/2098—At least two coatings or impregnations of different chemical composition

Abstract

第１の面と反対側の第２の面とを有する不織障壁布の製造方法であって、蒸着またはエアロゾル沈着法により、布の第１の面に、フッ素化化合物を実質的に含まないプライマー組成物を塗付して、プライマー組成物の層を形成する工程と、少なくとも１種の不飽和フッ素化化合物を含む障壁組成物を、蒸着またはエアロゾル沈着法により、プライマー組成物層に塗布して、プライマー組成物層上に、少なくとも一層の、好ましくは一（１）〜四（４）層の、より好ましくは二（２）または三（２）層の障壁組成物の層を形成する工程とを含む方法、およびこの方法により得られる布。A method for producing a nonwoven barrier fabric having a first side and a second side opposite the first side, wherein the first side of the fabric is substantially free of fluorinated compounds by vapor deposition or aerosol deposition. Applying the primer composition to form a layer of the primer composition and applying the barrier composition containing at least one unsaturated fluorinated compound to the primer composition layer by vapor deposition or aerosol deposition. Forming at least one, preferably one (1) to four (4) layers, more preferably two (2) or three (2) layers of the barrier composition layer on the primer composition layer. And a fabric obtained by this method.

Description

本発明は、障壁布およびその製造方法の分野に関する。   The present invention relates to the field of barrier fabrics and methods of manufacturing the same.

不織布は、例えば、衣服の用途、医療用途、個人防護の用途、濾過の用途など、多くの用途で使用し得る汎用性の高い材料である。   Nonwoven fabrics are highly versatile materials that can be used in many applications, such as clothing applications, medical applications, personal protection applications, and filtration applications.

そのようなものとして、不織布に求められる機能的要件は、意図する使用または用途によってかなり異なり得る。   As such, the functional requirements required of nonwovens can vary considerably depending on the intended use or application.

例えば、不織布で作られた衣服は、例えば、帯電防止性および撥アルコール性などの多様な特性を有することが要求され、他の種類の衣服では、殺菌性を備えている必要があるかもしれない。多様な特性を付与するために、不織布は、一般に、帯電防止剤、撥液剤などの１種以上の適切な化学物質で処理される。   For example, garments made of non-woven fabric are required to have various properties such as antistatic and alcohol repellency, and other types of garments may need to be bactericidal . In order to impart a variety of properties, nonwoven fabrics are generally treated with one or more suitable chemicals such as antistatic agents, liquid repellents and the like.

しかしながら、異なる特性を与える化学物質の殆どは、互いに相溶せず、併用すれば互いに負の影響を及ぼし得ることから、不織布に対して多様な特性を組み合わせることは、厄介な問題を引き起こし得る。   However, combining most of the various properties with the nonwoven fabric can cause complications because most chemicals that give different properties are not compatible with each other and can have negative effects on each other when used together.

したがって、互いに悪影響を及ぼす薬剤を、たとえ布の反対側に塗付したとしても、薬剤は布を通って移動し、最悪の場合、互いの特性を打ち消し合うおそれがある。この問題は、布が非常に薄く、坪量が小さく、かつ／または非常に多孔質の場合に、一層悪化する。   Therefore, even if drugs that adversely affect each other are applied to the opposite side of the cloth, the drugs move through the cloth and in the worst case, they can cancel each other's properties. This problem is exacerbated when the fabric is very thin, has a low basis weight, and / or is very porous.

この理由により、不織布の技術分野においては、相いれない薬剤を不織布に併用し得る様々な方法が提案されている。   For this reason, in the technical field of nonwoven fabrics, various methods have been proposed in which incompatible drugs can be used in combination with the nonwoven fabric.

国際公開第０９／０７７８８９号パンフレットには、帯電防止性および撥アルコール性を向上させた不織布ウェブが記載されており、そこでは不織布ウェブは、帯電防止剤および熱可塑性ポリマーの混合物を用いて製造されている。すなわち、帯電防止剤を紡いで不織布ウェブとしている。帯電防止剤を紡いで不織布ウェブとすることにより、後で蒸着法により塗付できる撥アルコール剤に対するその悪影響が打ち消される。しかしながら、帯電防止剤を紡いで不織布ウェブにすることは、製造工程に対して、時間のかかる多くの調節を必要とする。   WO 09/077889 describes a nonwoven web having improved antistatic and alcohol repellency, wherein the nonwoven web is produced using a mixture of an antistatic agent and a thermoplastic polymer. ing. That is, an antistatic agent is spun into a nonwoven web. By spinning the antistatic agent into a nonwoven web, its adverse effect on the alcohol repellent that can be applied later by vapor deposition is counteracted. However, spinning antistatic agents into a nonwoven web requires many time-consuming adjustments to the manufacturing process.

国際公開第０６／０５５８４２号パンフレットには、表面張力の小さい溶媒とフルオロケミカルからなる非水性溶液を塗布し、溶媒を除去し、そして障壁布表面へ水性の帯電防止剤を塗布することによる、障壁布の仕上げ方法が記載されている。   WO 06/055842 discloses a barrier by applying a non-aqueous solution consisting of a low surface tension solvent and a fluorochemical, removing the solvent, and applying an aqueous antistatic agent to the surface of the barrier fabric. A method for finishing the fabric is described.

さらに、大部分の不織障壁布に塗付される障壁組成物は、高価なフッ素化化合物を大量に含んでおり、製造コストのかなりの部分を占めている。一般に、布の障壁効果は、それに塗付されたフッ素化化合物の量と共に増大するが、そのような高価な化合物の含有量を低減し、それでもなお、十分な障壁特性が維持されるようにする要望が常に存在する。   In addition, barrier compositions applied to most nonwoven barrier fabrics contain large amounts of expensive fluorinated compounds and represent a significant portion of manufacturing costs. In general, the barrier effect of a fabric increases with the amount of fluorinated compound applied to it, but reduces the content of such expensive compounds so that sufficient barrier properties are still maintained. There is always a desire.

したがって、潜在的に互いに悪影響を及ぼす化学薬剤により与えられる多くの特性が、好ましくは低濃度で、たとえ薄く、かつ多孔質な布であっても、容易に組み合わせることができる布（薄く多孔質の布でも）、およびそのような布を製造する方法を提供することが強く望まれている。   Thus, many properties conferred by chemical agents that potentially adversely affect each other are preferably fabrics that are easily combined, even at low concentrations, even thin and porous fabrics (thin and porous It is highly desirable to provide a fabric) and a method for producing such a fabric.

本発明は、第１の面と反対側の第２の面とを有する不織障壁布の製造方法であって、
（ａ）蒸着またはエアロゾル沈着法により、布の第１の面に、フッ素化化合物を実質的に含まないプライマー組成物を塗付して、布の第１の面上に、前記プライマー組成物の層を形成する工程と、
（ｂ）少なくとも１種の不飽和フッ素化化合物を含む障壁組成物を、蒸着またはエアロゾル沈着法により、プライマー組成物層に塗布して、プライマー組成物層上に、少なくとも一層の、好ましくは一（１）〜四（４）層の、より好ましくは二（２）または三（２）層の前記障壁組成物の層を形成する工程と
を含む方法を提供する。 The present invention is a method of manufacturing a nonwoven barrier fabric having a first side and a second side opposite to the first side,
(A) A primer composition substantially free of a fluorinated compound is applied to the first surface of the cloth by vapor deposition or aerosol deposition, and the primer composition is coated on the first surface of the cloth. Forming a layer;
(B) A barrier composition containing at least one unsaturated fluorinated compound is applied to the primer composition layer by vapor deposition or aerosol deposition, and at least one layer, preferably one ( 1) to 4 (4) layers, more preferably two (2) or three (2) layers of the barrier composition.

さらに、本発明は上記方法により得られる布を提供する。   Furthermore, the present invention provides a fabric obtained by the above method.

本開示の特徴および利点は、以下の詳細な説明を読めば、当業者であればより容易に理解されるであろう。   The features and advantages of the present disclosure will be more readily understood by those of ordinary skill in the art upon reading the following detailed description.

明確にするために、上で説明し、また以下の個々の実施形態の文脈の中で説明する本開示のいくつかの特徴が、また、単一の実施形態で組み合わせて提供され得ることは、認識されるべきである。   For clarity, some features of the present disclosure described above and in the context of the individual embodiments below may also be provided in combination in a single embodiment, Should be recognized.

逆に言えば、簡潔さのために単一の実施形態の文脈の中で説明している本開示の各種特徴はまた、別々に、または任意の下位の組み合わせで提供することができる。さらに、文脈中で特に断らない限り、単数形での言及はまた、複数形を含み得る（例えば、「ａ」および「ａｎ」は、１つ、または１つ以上を意味し得る）。   Conversely, the various features of the disclosure that are described in the context of a single embodiment for the sake of brevity can also be provided separately or in any subcombination. Further, unless otherwise specified in context, references to the singular can also include the plural (eg, “a” and “an” can mean one, or more than one).

本明細書では、用語「繊維」は、共に天然および／または合成の、ステープルファイバー、牽切繊維および連続フィラメントをいう。   As used herein, the term “fiber” refers to staple fibers, checkout fibers and continuous filaments, both natural and / or synthetic.

本明細書では、用語「不織布」は、不規則に配置されて、編地または織布とは異なり、同定できるパターンを有さない平面材料を形成する、個々の繊維からなる構造を有するあらゆる布をいう。不織布の例としては、メルトブロー布、スパンボンド不織ウェブ、カードおよびエアレイド布などの単繊維ベースの布、スパンレース布、ＤＥのＷｉｌｍｉｎｇｔｏｎのＥ．Ｉ．ｄｕ Ｐｏｎｔ ｄｅ Ｎｅｍｏｕｒｓ ａｎｄ Ｃｏｍｐａｎｙ（ＤｕＰｏｎｔ）からＴｙｖｅｃ（登録商標）の商標で商業的に入手可能な布などのフラッシュスパン布、ならびにこれらの任意の組み合わせが挙げられるが、これらに限定されない。   As used herein, the term “nonwoven” refers to any fabric having a structure of individual fibers that is randomly arranged to form a planar material that, unlike a knitted or woven fabric, does not have an identifiable pattern. Say. Examples of nonwovens include meltblown fabrics, spunbond nonwoven webs, monofilament based fabrics such as card and airlaid fabrics, spunlace fabrics, DE, Wilmington E.I. I. Examples include, but are not limited to, flashspun fabrics such as those commercially available under the trademark Tyvec® from du Pont de Nemours and Company (DuPont), as well as any combination thereof.

本明細書では、用語「織布」は、周期的に配置されて、不織布とは反対に同定可能なパターンを有する平面材料を形成する、少なくとも１本の緯糸および少なくとも１本の経糸を有する布をいう。   As used herein, the term “woven fabric” refers to a fabric having at least one weft and at least one warp that are periodically arranged to form a planar material having an identifiable pattern as opposed to a nonwoven. Say.

本明細書では、用語「（メタ）アクリル」は、アクリルおよびメタクリルの双方をいう。   As used herein, the term “(meth) acryl” refers to both acrylic and methacrylic.

本明細書では、用語「フルオロ（ジ）アクリレート」は、フルオロアクリレートおよびフルオロジアクリレートの双方をいう。   As used herein, the term “fluoro (di) acrylate” refers to both fluoroacrylate and fluorodiacrylate.

本明細書では、用語「静水頭」は、ＥＮ ２０８１１規格により測定される、センチメートル単位の透水抵抗をいう。   As used herein, the term “hydrostatic head” refers to hydraulic resistance in centimeters as measured by the EN 20811 standard.

用語「ＭＶＴＲ］は、ＥＮ ＩＳＯ １２５７２（ウェットカップ法を用いるｃｌｉｍａｔｅ Ｃ）により測定される水蒸気透過率をいう。   The term “MVTR” refers to water vapor transmission rate as measured by EN ISO 12572 (Climate C using wet cup method).

用語「微量」は１０００ｐｐｍ未満をいう。   The term “trace” refers to less than 1000 ppm.

用語「面密度」および「面重量」は同義語として使用され、本明細書では単位面積当たりの布の重さをいう。   The terms “area density” and “area weight” are used as synonyms and refer herein to the weight of the fabric per unit area.

本発明は、第１の面と反対側の第２の面とを有する不織障壁布の製造方法であって、蒸着またはエアロゾル沈着法により、布の第１の面に、フッ素化化合物を実質的に含まないプライマー組成物を塗付して、布の第１の面上に、前記プライマー組成物の層を形成する工程と、
少なくとも１種の不飽和フッ素化化合物を含む障壁組成物を、蒸着またはエアロゾル沈着法により、プライマー組成物層に塗布して、プライマー組成物層上に、少なくとも一層の、好ましくは一（１）〜四（４）層の、より好ましくは二（２）または三（２）層の前記障壁組成物の層を形成する工程と
を含む方法を提供する。 The present invention is a method for producing a nonwoven barrier fabric having a first side and a second side opposite the first side, wherein the fluorinated compound is substantially applied to the first side of the fabric by vapor deposition or aerosol deposition. Applying a primer composition that does not contain the primer composition to form a layer of the primer composition on the first side of the fabric;
A barrier composition comprising at least one unsaturated fluorinated compound is applied to the primer composition layer by vapor deposition or aerosol deposition, and on the primer composition layer, at least one layer, preferably one (1) to Forming a layer of said barrier composition of four (4) layers, more preferably two (2) or three (2) layers.

プライマー層は蒸着またはエアロゾル沈着法により設けられることから、プライマー層のプライマー組成物は、不織障壁布の第１の面上にのみ実質的に存在し、他の適切でない沈着法が使用された場合のように、布の細孔または内部の隙間に広がることはない。別の言い方をすれば、不織障壁布の内部は、プライマーおよび障壁組成物を実質的に含まない。   Since the primer layer is provided by vapor deposition or aerosol deposition, the primer composition of the primer layer is substantially present only on the first side of the nonwoven barrier fabric and other unsuitable deposition methods were used. As is the case, it does not spread into the pores or internal gaps of the fabric. In other words, the interior of the nonwoven barrier fabric is substantially free of primer and barrier composition.

本発明の方法でプライマー組成物および障壁組成物を塗布するのに適していない例示的な沈着法は、ナイフコーティング、ロールコーティング、スクリーン印刷、キスロールコーティング、ディッピング、ソーキングなどが挙げられる。   Exemplary deposition methods that are not suitable for applying primer and barrier compositions with the methods of the present invention include knife coating, roll coating, screen printing, kiss roll coating, dipping, soaking, and the like.

本発明の方法においては、適切な不織障壁布は、１種以上の天然または合成（人工）の繊維またはフィラメントを含むものから選択できる。   In the process of the present invention, suitable nonwoven barrier fabrics can be selected from those comprising one or more natural or synthetic (artificial) fibers or filaments.

不織障壁布が１種以上の天然の繊維またはフィラメントを含む場合、これらは、セルロース、綿、ウール、絹、サイザル麻、リンネル、亜麻、ジュート、ケナフ、麻、ココナツ、コムギ、米、および／またはこれらの混合物から選択できる。   If the nonwoven barrier fabric comprises one or more natural fibers or filaments, these are cellulose, cotton, wool, silk, sisal, linen, flax, jute, kenaf, hemp, coconut, wheat, rice, and / or Or it can choose from these mixtures.

不織障壁布が１種以上の合成（人工）の繊維またはフィラメントを含む場合、これらは、ポリアミド、ポリエステル、ポリイミド、ポリオレフィン、および／またはこれらの混合物から選択できる。   If the nonwoven barrier fabric comprises one or more synthetic (artificial) fibers or filaments, these can be selected from polyamides, polyesters, polyimides, polyolefins, and / or mixtures thereof.

不織障壁布は、ポリオレフィンもしくはポリエステル不織布、またはポリオレフィン／ポリエステル混合不織布から選択できることが好ましい。   The non-woven barrier fabric is preferably selected from polyolefin or polyester non-woven fabrics or polyolefin / polyester mixed non-woven fabrics.

ポリオレフィン不織布は、ポリエチレン不織布、ポリプロピレン不織布、またはポリエチレン／ポリプロピレン混合不織布から選択できることが好ましい。   The polyolefin nonwoven fabric is preferably selected from a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, or a polyethylene / polypropylene mixed nonwoven fabric.

ポリエステル不織布は、ポリエチレンテレフタレート（ＰＥＴ）不織布、例えばポリ乳酸（ＰＬＡ）などのポリヒドロキシルアルカノエート不織布（ＰＨＡ）、またはＰＥＴ／ＰＨＡ混合不織布から選択できることが好ましい。   The polyester nonwoven fabric can preferably be selected from a polyethylene terephthalate (PET) nonwoven fabric, for example, a polyhydroxyl alkanoate nonwoven fabric (PHA) such as polylactic acid (PLA), or a PET / PHA mixed nonwoven fabric.

本発明の方法の不織障壁布は、ポリエチレンフラッシュスパン布であることが最も好ましい。   Most preferably, the nonwoven barrier fabric of the method of the present invention is a polyethylene flash spun fabric.

本発明の方法の不織障壁布は、５ｇ／ｍ2〜５００ｇ／ｍ2、１０ｇ／ｍ2〜２５０ｇ／ｍ2、または３０ｇ／ｍ2〜９０ｇ／ｍ2の面密度を有する。 Nonwoven barrier fabric of the method of the present invention has a surface density of 5g / m 2 ~500g / m 2 , 10g / m 2 ~250g / m 2 or 30g / m 2 ~90g / m 2 ,.

本発明の方法の不織障壁布は、不織布の２層以上の個別層の組み合わせであってもよい。それは、例えば、少なくとも１枚のポリエチレン不織布と少なくとも１枚のポリプロピレン不織布からなる積層体などの、２種以上の異なる種類の織布または不織布を組み合わせた積層体であってもよい。当該技術分野で知られている、２種以上の異なる種類の不織布からなる積層体は、スパンボンド−メルトブロー−スパンボンド積層体とも呼ばれているＳＭＳ積層体である。   The nonwoven barrier fabric of the method of the present invention may be a combination of two or more individual layers of nonwoven fabric. The laminate may be a combination of two or more different types of woven fabrics or nonwoven fabrics, such as a laminate composed of at least one polyethylene nonwoven fabric and at least one polypropylene nonwoven fabric. A laminate made up of two or more different types of nonwovens known in the art is an SMS laminate, also called a spunbond-meltblown-spunbond laminate.

本発明の方法は、好ましくは蒸着またはエアロゾル沈着法により、不織障壁布の第１の面に、フッ素化化合物を実質的に含まないプライマー組成物を塗付して、布の第１の面上に、前記プライマー組成物の層を形成する工程を含む。別の言い方をすれば、プライマー組成物は、フッ素化化合物を極微量に含む。   The method of the present invention comprises applying a primer composition substantially free of fluorinated compounds to the first side of the nonwoven barrier fabric, preferably by vapor deposition or aerosol deposition, to provide the first side of the fabric. And forming a layer of the primer composition. In other words, the primer composition contains a trace amount of the fluorinated compound.

布の第１の面上のプライマー組成物は、下塗り機能、および任意選択によりさらに１つ以上の機能を付与するのに適した組成物であってよく、１平方メートル当たり０．２〜２グラム、好ましくは１平方メートル当たり０．４〜０．８グラムの量で塗付し得る。   The primer composition on the first side of the fabric may be a composition suitable for imparting a primer function, and optionally one or more functions, 0.2-2 grams per square meter, Preferably it can be applied in an amount of 0.4 to 0.8 grams per square meter.

プライマー組成物は、フッ素化化合物を実質的に含まず、好ましくは、ケイ素化合物も実質的に含まず、好ましくは、少なくとも１種のオレフィン性不飽和基を有する、少なくとも１種の架橋性モノマー化合物、例えば、（メタ）アクリル酸、または１，３−ブチレングリコールジメタクリレートのような（メタ）アクリル酸エステル；１，４−ブタンジオールジメタクリレート；１，６ヘキサンジオールジアクリレート（ＨＤＤＡ）；１，６ヘキサンジオールジメタクリレート（ＨＤＤＭＡ）、アルコキシル化ジアクリレート；ジエチレングリコールジメタクリレート；ジプロピレングリコールジアクリレート；ジプロピレングリコールジアクリレート；エトキシル化（１０）ビスフェノールＡジアクリレート；エトキシル化（２）ビスフェノールＡジメタクリレート；エトキシル化（３）ビスフェノールＡジアクリレート、エトキシル化（３）ビスフェノールＡジメタクリレート；エトキシル化（４）ビスフェノールＡジアクリレート、エトキシル化（４）ビスフェノールＡジメタクリレート；エトキシル化ビスフェノールＡジメタクリレート；エトキシル化ビスフェノールＡジメタクリレート；エトキシル化（１０）ビスフェノールＡジメタクリレート；エチレングリコールジメタクリレート；エチレングリコールジメタクリレート；ポリエチレングリコール（２００）ジアクリレート；ポリエチレングリコール（４００）ジアクリレート；ポリエチレングリコール（４００）ジメタクリレート；ポリエチレングリコール（６００）ジアクリレート；ポリエチレングリコール（６００）ジメタクリレート；１．１０−ビス（アクリロイルオキシ）デカン；ポリエチレングリコール（４００）ジアクリレート；ポリエチレングリコールジメタクリレート；プロポキシル化（２）ネオペンチルグリコールジアクリレート；プロポキシル化ネオペンチルグリコールジアクリレート；テトラエチレングリコールジアクリレート；テトラエチレングリコールジメタクリレート；トリシクロデカンジメタノールジアクリレート；トリシクロデカンジメタノールジメタクリレート；トリエチレングリコールジアクリレート；トリエチレングリコールジメタクリレート；トリプロピレングリコールジアクリレート；１．１０−ビス（アクリロイルオキシ）デカン、および／またはこれらの組み合わせなどを含む。   The primer composition is substantially free of fluorinated compounds, preferably substantially free of silicon compounds, and preferably has at least one crosslinkable monomer compound having at least one olefinically unsaturated group. (Meth) acrylic acid or (meth) acrylic acid esters such as 1,3-butylene glycol dimethacrylate; 1,4-butanediol dimethacrylate; 1,6 hexanediol diacrylate (HDDA); 6 hexanediol dimethacrylate (HDDMA), alkoxylated diacrylate; diethylene glycol dimethacrylate; dipropylene glycol diacrylate; dipropylene glycol diacrylate; ethoxylated (10) bisphenol A diacrylate; ethoxylated (2) bisphenol Ethanolated (3) Bisphenol A diacrylate, Ethoxylated (3) Bisphenol A dimethacrylate; Ethoxylated (4) Bisphenol A diacrylate, Ethoxylated (4) Bisphenol A dimethacrylate; Ethoxylated bisphenol A di Methacrylate; ethoxylated bisphenol A dimethacrylate; ethoxylated (10) bisphenol A dimethacrylate; ethylene glycol dimethacrylate; ethylene glycol dimethacrylate; polyethylene glycol (200) diacrylate; polyethylene glycol (400) diacrylate; polyethylene glycol (400) Dimethacrylate; Polyethylene glycol (600) diacrylate; Polyethylene glycol 600) dimethacrylate; 1.10-bis (acryloyloxy) decane; polyethylene glycol (400) diacrylate; polyethylene glycol dimethacrylate; propoxylated (2) neopentyl glycol diacrylate; propoxylated neopentyl glycol diacrylate; Tetraethylene glycol diacrylate; tetraethylene glycol dimethacrylate; tricyclodecane dimethanol diacrylate; tricyclodecane dimethanol dimethacrylate; triethylene glycol diacrylate; triethylene glycol dimethacrylate; tripropylene glycol diacrylate; 1.10- Bis (acryloyloxy) decane, and / or combinations thereof.

最も好ましくは、少なくとも１種のオレフィン性不飽和基を有する、少なくとも１種の架橋性モノマー化合物は、プロポキシル化ネオペンチルグリコールジアクリレート、１．１０−ビス（アクリロイルオキシ）デカンなどの１．１０−ビス（アクリロイルオキシ）アルカン、またはこれらの混合物であり得る。   Most preferably, the at least one crosslinkable monomer compound having at least one olefinically unsaturated group is 1.10 such as propoxylated neopentyl glycol diacrylate, 1.10-bis (acryloyloxy) decane. It can be a bis (acryloyloxy) alkane, or a mixture thereof.

本発明の方法は、少なくとも１種の不飽和フッ素化化合物を含む障壁組成物を、蒸着またはエアロゾル沈着法により、プライマー組成物層に塗布して、プライマー組成物層上に、少なくとも１層の、好ましくは１〜４層の、より好ましくは２または３層の前記障壁組成物の層を形成する工程をさらに含む。   The method of the present invention comprises applying a barrier composition comprising at least one unsaturated fluorinated compound to a primer composition layer by vapor deposition or aerosol deposition, and at least one layer on the primer composition layer. Preferably, the method further comprises the step of forming 1-4 layers of the barrier composition, more preferably 2 or 3 layers.

障壁組成物は、少なくとも１種の不飽和フッ素化化合物を含み、かつ障壁機能を付与するのに適した任意の組成物であってよい。   The barrier composition may be any composition comprising at least one unsaturated fluorinated compound and suitable for providing a barrier function.

障壁組成物１層当たりの障壁組成物の量は、１平方メートル当たり０．１〜１グラムであってよく、より好ましくは１平方メートル当たり０．４〜０．８グラムであってよい。例えば、障壁組成物からなる２層が設けられる場合、塗付される障壁組成物の全体量は上記の量の２倍、すなわち１平方メートル当たり０．２〜２グラム、より好ましくは０．８〜１．６グラムである。   The amount of barrier composition per layer of barrier composition may be from 0.1 to 1 gram per square meter, more preferably from 0.4 to 0.8 gram per square meter. For example, if two layers of barrier composition are provided, the total amount of barrier composition applied is twice the above amount, ie 0.2-2 grams per square meter, more preferably 0.8- 1.6 grams.

布に一定量の障壁組成物を塗布することにより得ることができる前記布の障壁特性は、前記障壁組成物を１層より多くの層に塗布することにより、驚くほど高め得ることがわかった。例えば、１平方メートル当たり１．２グラムの量の障壁組成物からなる１層をコーティングした布の障壁特性または撥液性評価は、同じ絶対量の障壁組成物がコーティングされているが、障壁組成物の量を２層に分割して１平方メートル当たりそれぞれ０．６グラムとした同一の布と比べて驚くほど低い。別の言い方をすれば、所与のコーティング量に対しては、層の数を増すことが、撥液性の向上のためには好ましい。   It has been found that the barrier properties of the fabric that can be obtained by applying a certain amount of the barrier composition to the fabric can be surprisingly enhanced by applying the barrier composition to more than one layer. For example, the barrier properties or liquid repellency rating of a layer coated fabric comprising a barrier composition in an amount of 1.2 grams per square meter is the same absolute amount of barrier composition coated, but the barrier composition Is surprisingly low compared to the same fabric divided into two layers, each 0.6 grams per square meter. In other words, for a given coating amount, increasing the number of layers is preferred for improving liquid repellency.

障壁組成物は、プライマー組成物について上で定義したような少なくとも１種の架橋性モノマー化合物を、障壁組成物の全重量に対して、１０〜５０重量パーセント、または１０〜３５重量パーセント、さらに含むことが好ましい。障壁層に含まれる少なくとも１種の架橋性モノマー化合物は、プロポキシル化ネオペンチルグリコールジアクリレート、１．１０−ビス（アクリロイルオキシ）デカンなどの１．１０−ビス（アクリロイルオキシ）アルカン、またはこれらの混合物から選択することがより好ましい。   The barrier composition further comprises 10-50 weight percent, or 10-35 weight percent, based on the total weight of the barrier composition, at least one crosslinkable monomer compound as defined above for the primer composition. It is preferable. At least one crosslinkable monomer compound contained in the barrier layer is propoxylated neopentyl glycol diacrylate, 1.10-bis (acryloyloxy) alkane such as 1.10-bis (acryloyloxy) decane, or these More preferably, it is selected from a mixture.

好ましい実施形態では、本発明の方法は、第１の面と反対側の第２の面とを有する不織障壁布の製造であって、好ましくは蒸着またはエアロゾル沈着法により、布の第１の面に、フッ素化化合物を実質的に含まないプライマー組成物を塗付して、布の第１の面上に、前記プライマー組成物の層を形成する工程と、少なくとも１種の不飽和フッ素化化合物を含む障壁組成物を、蒸着またはエアロゾル沈着法により、プライマー組成物層に塗布して、プライマー組成物層上に、一（１）〜四（４）層の、より好ましくは二（２）または三（２）層の前記障壁組成物の層を形成する工程とを含む製造を提供する。   In a preferred embodiment, the method of the present invention is the manufacture of a nonwoven barrier fabric having a first side and a second side opposite the first side, preferably by vapor deposition or aerosol deposition methods. Applying a primer composition substantially free of a fluorinated compound to the surface to form a layer of said primer composition on the first surface of the fabric; and at least one unsaturated fluorination The barrier composition containing the compound is applied to the primer composition layer by vapor deposition or aerosol deposition, and one (1) to four (4) layers, more preferably two (2), on the primer composition layer. Or forming a layer of the barrier composition of three (2) layers.

本発明に有用な不飽和フッ素化化合物は、少なくとも１種の不飽和フッ素化モノマー、例えば、
（ＣＨ2＝ＣＨ2）z（ＣｎＦ2n+2-z）
（式中、ｚは１（不飽和フッ素化モノマーがペルフルオロアルケンのとき）から２（不飽和フッ素化モノマーがペルフルオロアルカジエンのとき）の範囲の整数、ｎは１〜１４の範囲の整数である）で示される一般構造を有するペルフルオロアルカ（ジ）エン、具体例としては、３，３，４，４，５，５，６，６，７，７−デカフルオロ−ノナ−１，８−ジエン；３，３，４，４，５，５，６，６，６−ノナフルオロ−ヘクス−１−エンなど；または、例えば、
［ＣＨ2＝ＣＲＣＯＯ（ＣＨ2）x（Ｓｕ）y］z（ＣnＦ2n+2-z）
（式中、ｎは１〜１４の範囲の整数、ｘは独立して１〜８の範囲の整数、Ｒは独立して水素原子、または鎖長が炭素数１〜１６個の範囲のアルキル基、好ましくはメチルまたはエチル基、Ｓｕはスルホンアミド基、ｙは独立して０〜１の範囲の整数、およびｚは１〜２の範囲の整数である）で示される一般構造を有するフルオロ（ジ）アクリレートモノマーなどを含む化合物から選択することができる。多くの場合、不飽和フッ素化化合物は、ｎ、ｙ、ｚおよびｘが独立して異なる値であるフルオロ（ジ）アクリレートモノマー同族体の混合物を含み得る。 Unsaturated fluorinated compounds useful in the present invention include at least one unsaturated fluorinated monomer, such as
(CH 2 = CH 2 ) z (CnF 2n + 2-z )
Wherein z is an integer ranging from 1 (when the unsaturated fluorinated monomer is a perfluoroalkene) to 2 (when the unsaturated fluorinated monomer is a perfluoroalkadiene), and n is an integer ranging from 1 to 14. Perfluoroalka (di) ene having a general structure represented by the following formula: 3,3,4,4,5,5,6,6,7,7-decafluoro-nona-1,8-diene 3,3,4,4,5,5,6,6,6-nonafluoro-hex-1-ene and the like; or, for example,
[CH 2 = CRCOO (CH 2 ) x (Su) y] z (C n F 2n + 2-z)
Wherein n is an integer in the range of 1 to 14, x is independently an integer in the range of 1 to 8, R is independently a hydrogen atom, or an alkyl group having a chain length of 1 to 16 carbons. , Preferably a methyl or ethyl group, Su is a sulfonamide group, y is independently an integer in the range of 0 to 1, and z is an integer in the range of 1 to 2). ) It can be selected from compounds containing acrylate monomers and the like. In many cases, the unsaturated fluorinated compound may comprise a mixture of fluoro (di) acrylate monomer homologues where n, y, z and x are independently different values.

そのようなフルオロ（ジ）アクリレートモノマーの具体例としては、アクリル酸２，２，３，３，４，４，５，５，６，６，７，７，８，８，８−ペンタデカフルオロオクチルエステル；アクリル酸２−メチル−２，２，３，３，４，４，５，５，６，６，７，７，８，８，８−ペンタデカフルオロオクチルエステル；アクリル酸ペンタフルオロエチルエステル；アクリル酸２−メチル−ペンタフルオロフェニルエステル；２，３，４，５，６−ペンタフルオロスチレン；アクリル酸２，２，２−トリフルオロエチルエステル；アクリル酸２−メチル−２，２，２−トリフルオロエチルエステル；２，２，３，３，４，４，５，５−オクタフルオロ−１，６，ヘキサンジオールジアクリレート、および１，１，５，５−テトラヒドロペルフルオロ−１，５−ペンタンジオールジメタクリレートがある。   Specific examples of such fluoro (di) acrylate monomers include acrylic acid 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro. Octyl ester; 2-methyl-2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl ester; pentafluoroethyl acrylate Esters; acrylic acid 2-methyl-pentafluorophenyl ester; 2,3,4,5,6-pentafluorostyrene; acrylic acid 2,2,2-trifluoroethyl ester; 2-methyl-2,2, acrylic acid 2-trifluoroethyl ester; 2,2,3,3,4,4,5,5-octafluoro-1,6, hexanediol diacrylate, and 1,1,5,5-tetrahydroperfur There is b-1,5-pentanediol dimethacrylate.

前述した種類のフルオロ（ジ）アクリレートモノマーは、ＺＯＮＹＬ（登録商標）またはＣＡＰＳＴＯＮＥの商標でＤｕｐｏｎｔから商業的に入手することができる。   Fluoro (di) acrylate monomers of the type described above are commercially available from Dupont under the trademark ZONYL® or CAPSTONE.

不飽和シリコーン化合物は、
［ＣＨ2＝ＣＲＣＯＯ（ＣＨ2）x］z（ＳｉＲ2［ＳｉＲ2Ｏ］nＯＳｉＲ4-z）
（式中、ｎは独立して１〜５０の範囲の整数、ｘは独立して１〜８の範囲の整数、Ｒは独立して水素原子、または鎖長が炭素数１〜１６個の範囲のアルキル基、好ましくはメチルまたはエチル基、ｚは１（シリコーン化合物がアクリレートのとき）から２（シリコーン化合物がジアクリレートのとき）の範囲の整数である）の一般構造を有する、少なくとも１種のシリコーン（ジ）アクリレートモノマーを含み得る。多くの場合、シリコーン化合物は、ｎ、ｚおよびｘの異なる値であるシリコーン（ジ）アクリレートモノマー同族体の混合物を含み得る。 Unsaturated silicone compounds
[CH 2 = CRCOO (CH 2 ) x ] z (SiR 2 [SiR 2 O] n OSiR 4-z )
Wherein n is independently an integer in the range of 1-50, x is independently an integer in the range of 1-8, R is independently a hydrogen atom, or a chain length of 1-16 carbons. An alkyl group, preferably a methyl or ethyl group, wherein z is an integer ranging from 1 (when the silicone compound is an acrylate) to 2 (when the silicone compound is a diacrylate), at least one kind Silicone (di) acrylate monomers may be included. In many cases, the silicone compound may comprise a mixture of silicone (di) acrylate monomer homologues with different values of n, z and x.

疎水性薬剤は、不飽和フッ素化化合物から選択することが好ましく、フルオロ（ジ）アクリレートモノマーから選択することがより好ましい。   The hydrophobic agent is preferably selected from unsaturated fluorinated compounds, more preferably selected from fluoro (di) acrylate monomers.

プライマー層および障壁層をそれぞれ形成するプライマー組成物および障壁組成物は、抗菌組成物、熱反射組成物、難燃組成物、インク受容組成物、染色組成物、増粘組成物、接着促進組成物、ＵＶ吸収組成物、蛍光増白組成物、および／またはこれらの組み合わせを含有してもよい。   The primer composition and the barrier composition for forming the primer layer and the barrier layer are antibacterial composition, heat reflection composition, flame retardant composition, ink receiving composition, dyeing composition, thickening composition, adhesion promoting composition, respectively. , UV absorbing compositions, fluorescent whitening compositions, and / or combinations thereof.

本発明の方法では、不織障壁布の第１の面上にプライマー組成物層を形成するプライマー組成物は、蒸着またはエアロゾル沈着法により塗布することができる。   In the method of the present invention, the primer composition that forms the primer composition layer on the first side of the nonwoven barrier fabric can be applied by vapor deposition or aerosol deposition.

蒸着法によるプライマー組成物の塗布は、真空中でプライマー組成物を蒸発させ、布の第１の面上で凝縮させてプライマー組成物層を形成させ、その後、形成されたプライマー組成物層を硬化させることにより達成することができる。例示的な蒸着法は、Ｓｉｇｍａ Ｌａｂｏｒａｔｏｒｉｅｓ ｏｆ Ａｒｉｚｏｎａ，Ｉｎｃ．の欧州特許第１６１８２２５号明細書に記載されている。代替法として、エアロゾル沈着法によるプライマー組成物の塗付は、「大気圧プラズマ液体沈着法」（ＡＰＰＬＤ）として知られている方法により、大気圧でプロセスガス中にプライマー組成物のエアロゾルを発生させ、エアロゾルを適切な電離プラズマ放電に曝露し、エアロゾルを布に向けて誘導することにより達成することができる。   The application of the primer composition by vapor deposition involves evaporating the primer composition in a vacuum and condensing on the first side of the fabric to form a primer composition layer, and then curing the formed primer composition layer. This can be achieved. Exemplary deposition methods are available from Sigma Laboratories of Arizona, Inc. European Patent No. 1618225. As an alternative, the application of the primer composition by the aerosol deposition method generates an aerosol of the primer composition in the process gas at atmospheric pressure by a method known as the “atmospheric pressure plasma liquid deposition method” (APPLD). This can be accomplished by exposing the aerosol to a suitable ionized plasma discharge and inducing the aerosol towards the fabric.

蒸着法でもエアロゾル沈着法でも、不織障壁布の第１の面の表面繊維またはフィラメントのみがプライマー組成物でコーティングされるため、布の通気性は悪影響を受けない、すなわち通気性が維持される。   In both vapor deposition and aerosol deposition methods, only the surface fibers or filaments on the first side of the nonwoven barrier fabric are coated with the primer composition so that the breathability of the fabric is not adversely affected, i.e., the breathability is maintained. .

プライマー組成物を蒸着法で塗付する場合、そのようにして形成されたプライマー組成物層は、布の第１の面上に凝縮後、直ちに、例えば、可視光、赤外線（熱）、紫外線、および／またはガンマ線、Ｘ線もしくは電子ビームなどの電離放射線などの高エネルギー放射線に曝露させることにより硬化させる。   When the primer composition is applied by a vapor deposition method, the primer composition layer thus formed is immediately condensed after being condensed on the first surface of the cloth, for example, visible light, infrared (heat), ultraviolet, And / or cured by exposure to high energy radiation such as ionizing radiation such as gamma rays, X-rays or electron beams.

プライマー組成物をエアロゾル沈着法、特に大気圧プラズマ液体沈着法（ＡＰＰＬＤ）で塗付する場合、硬化工程は、プライマー組成物エアロゾルを適当なプラズマ放電に曝露させる（ここで、電離したプロセスガスの分子によりエアロゾル液滴表面にフリーラジカルが発生する）工程、および、布に向けてエアロゾルを誘導する（ここで、エアロゾル液滴表面が布と相互接触して反応する）工程を含む。そのようなプラズマ放電を発生させるために使用される装置の代表的な例としては、国際公開第０１／５９８０９号パンフレット、同第０２／２８５４８号パンフレット、同第０５／１１０６２６号パンフレット、米国特許出願公開第２００５／０１７８３３０号明細書に記載されているものが挙げられる。   When the primer composition is applied by aerosol deposition, particularly atmospheric pressure plasma liquid deposition (APPLD), the curing step exposes the primer composition aerosol to an appropriate plasma discharge (where ionized process gas molecules To generate free radicals on the surface of the aerosol droplet), and to induce the aerosol toward the cloth (where the aerosol droplet surface reacts in contact with the cloth). Representative examples of the apparatus used to generate such plasma discharge include WO 01/59809, 02/28548, 05/110626, US patent application. What is described in the specification of the publication 2005/0178330 is mentioned.

プライマー組成物を布の第１の面に塗布する前に、例えば、プラズマエッチング、プラズマ処理、コロナ放電処理、または静電放電処理などの高エネルギー処理を布の第１の面に施し得ることが好ましい。   Before applying the primer composition to the first side of the fabric, it may be possible to subject the first side of the fabric to a high energy treatment such as, for example, plasma etching, plasma treatment, corona discharge treatment, or electrostatic discharge treatment. preferable.

本発明の方法では、不織障壁布のプライマー組成物層の上に１〜４層の障壁組成物層を形成する障壁組成物は、蒸着またはエアロゾル沈着法により塗布される。   In the method of the present invention, the barrier composition that forms one to four barrier composition layers on the primer composition layer of the nonwoven barrier fabric is applied by vapor deposition or aerosol deposition.

蒸着法による障壁組成物の塗布は、真空中で障壁組成物を蒸発させ、布のプライマー組成物層上で凝縮させて１〜４層の障壁組成物層を形成させ、その後、形成された障壁組成物層を硬化させることにより達成することができる。例示的な蒸着法は、Ｓｉｇｍａ Ｌａｂｏｒａｔｏｒｉｅｓ ｏｆ Ａｒｉｚｏｎａ，Ｉｎｃ．の欧州特許第１６１８２２５号明細書に記載されている。   Application of the barrier composition by vapor deposition involves evaporating the barrier composition in a vacuum and condensing on the primer composition layer of the fabric to form one to four barrier composition layers, after which the barrier formed This can be achieved by curing the composition layer. Exemplary deposition methods are available from Sigma Laboratories of Arizona, Inc. European Patent No. 1618225.

代替として、エアロゾル沈着法による障壁組成物の塗布は、「大気圧プラズマ液体沈着法（ＡＰＰＬＤ）」として知られている方法により、障壁組成物のエアロゾルを大気圧でプロセスガス中に発生させ、エアロゾルを適切な電離プラズマ放電に曝露させ、エアロゾルを布のプライマー組成物層に向けて誘導することにより達成することができる。   Alternatively, the application of the barrier composition by aerosol deposition may be accomplished by generating an aerosol of the barrier composition in the process gas at atmospheric pressure by a method known as “atmospheric pressure plasma liquid deposition (APPLD)” Can be achieved by exposing the aerosol to a suitable ionized plasma discharge and directing the aerosol towards the primer composition layer of the fabric.

蒸着法でもエアロゾル沈着法でも、不織障壁布の第１の面の表面繊維またはフィラメントのみがプライマー組成物でコーティングされるため、追加の障壁組成物層がプライマー組成物層の上面に塗布されても、布の通気性は悪影響を受けない。   In both vapor deposition and aerosol deposition methods, since only the surface fibers or filaments of the first side of the nonwoven barrier fabric are coated with the primer composition, an additional barrier composition layer is applied to the top surface of the primer composition layer. However, the breathability of the fabric is not adversely affected.

障壁組成物を蒸着法で塗付する場合、そのようにして形成された障壁組成物層は、布のプライマー組成物層上に凝縮後、直ちに、例えば、可視光、赤外線（熱）、紫外線、および／またはガンマ線、Ｘ線もしくは電子ビームなどの電離放射線などの高エネルギー放射に曝露させることにより硬化させる。   When the barrier composition is applied by vapor deposition, the barrier composition layer thus formed, for example, immediately after condensation on the primer composition layer of the fabric, for example, visible light, infrared (heat), ultraviolet, And / or cured by exposure to high energy radiation such as ionizing radiation such as gamma rays, X-rays or electron beams.

障壁組成物をエアロゾル沈着法、特に大気圧プラズマ液体沈着法（ＡＰＰＬＤ）で塗付する場合、硬化工程は、障壁組成物エアロゾルを適当なプラズマ放電に曝露させる（ここで、電離したプロセスガスによりエアロゾル液滴表面にフリーラジカルが発生する）工程、および、下塗りした布に向けてエアロゾルを誘導する（ここで、エアロゾル液滴表面がプライマー組成物層と相互接触して反応する）工程を含む。そのようなプラズマ放電を発生させるために使用される装置の代表的な例としては、国際公開第０１／５９８０９号パンフレット、同第０２／２８５４８号パンフレット、同第０５／１１０６２６号パンフレット、米国特許出願公開第２００５／０１７８３３０号明細書に記載されているものが挙げられる。   When the barrier composition is applied by aerosol deposition, particularly atmospheric pressure plasma liquid deposition (APPLD), the curing step exposes the barrier composition aerosol to a suitable plasma discharge (where the aerosol is ionized by the process gas). A step of generating free radicals on the droplet surface) and a step of inducing an aerosol toward the primed cloth (where the aerosol droplet surface reacts in contact with the primer composition layer). Representative examples of the apparatus used to generate such plasma discharge include WO 01/59809, 02/28548, 05/110626, US patent application. What is described in the specification of the publication 2005/0178330 is mentioned.

障壁組成物を布のプライマー組成物層に塗布する前に、例えば、プラズマエッチング、プラズマ処理、コロナまたは静電放電処理などの高エネルギー処理を布のプライマー組成物層に施し得ることが好ましい。   Prior to applying the barrier composition to the primer composition layer of the fabric, it is preferred that a high energy treatment such as plasma etching, plasma treatment, corona or electrostatic discharge treatment can be applied to the primer composition layer of the fabric.

本発明の方法は、プライマー組成物層、および／または１〜４層の障壁組成物層を、好ましくは個別に、すなわち組成物を塗布して対応する層を形成した後で、その度に硬化させる工程を含んでもよい。   The method of the present invention involves curing the primer composition layer and / or 1-4 barrier composition layers, preferably each time after applying the composition to form the corresponding layer. You may include the process to make.

プライマーおよび／または障壁組成物層を硬化させる場合、得られる層の耐摩耗性および機械的安定性は高められるであろう。   When the primer and / or barrier composition layer is cured, the wear resistance and mechanical stability of the resulting layer will be increased.

本発明の方法は、布の反対側の第２の面に帯電防止組成物を塗布し、布の反対側の第２の面上に前記帯電防止組成物層を形成する工程をさらに含んでもよい。   The method of the present invention may further include the step of applying an antistatic composition to the second surface on the opposite side of the fabric and forming the antistatic composition layer on the second surface on the opposite side of the fabric. .

帯電防止組成物層は、限定はされないが、有機リン酸エステル、アルカリ金属、アルカリ土類金属もしくは遷移金属のリン酸塩、例えば、ポリメタリン酸カリウムなど；アルケニルホスホン酸もしくはそれらのエステル；アルキルスルホン酸塩；脂肪酸塩；第４級アミン；塩化ナトリウム；ポリエチレングリコールなどのポリオール；および／またはこれらの組み合わせを含む群から選択される、少なくとも１種の適切な帯電防止剤を含む。少なくとも１種の帯電防止剤は有機リン酸エステルであることが好ましい。   Antistatic composition layers include, but are not limited to, organophosphates, alkali metal, alkaline earth metal or transition metal phosphates such as potassium polymetaphosphate; alkenyl phosphonic acids or esters thereof; alkyl sulfonic acids A fatty acid salt; a quaternary amine; sodium chloride; a polyol such as polyethylene glycol; and / or at least one suitable antistatic agent selected from the group comprising combinations thereof. The at least one antistatic agent is preferably an organophosphate.

有機リン酸エステルは、アルキルリン酸エステル、例えば、一または二置換ｎ−プロピルリン酸カリウム、一または二置換ｉ−ブチルリン酸カリウム、および／またはこれらの組み合わせなどを含む群から選択し得る。有機リン酸エステルは、Ｓｔｅｐａｎ Ｃｈｅｍｉｃａｌ（Ｎｏｒｔｈｆｉｅｌｄ ＩＬ，ＵＳ）からＺＥＬＥＣ（登録商標）の商標で商業的に入手することができる。   The organophosphate ester may be selected from the group comprising alkyl phosphate esters, such as mono or disubstituted potassium n-propyl phosphate, mono or disubstituted potassium i-butyl phosphate, and / or combinations thereof. Organophosphates are commercially available from Stepan Chemical (Northfield IL, US) under the ZELEC® trademark.

プライマーおよび／または障壁組成物は、平均粒径が０．５マイクロメートル〜５０マイクロメートル、または０．５マイクロメートル〜１５マイクロメートルの粒状物質の少なくとも１種をさらに含んでもよい。プライマーおよび障壁組成物がいずれも少なくとも１種の粒状物質を含む場合、プライマー層に含まれる粒状物質の平均粒径が、障壁層に含まれる粒状物質の平均粒径より大きいことが好ましい。   The primer and / or barrier composition may further comprise at least one particulate material having an average particle size of 0.5 micrometers to 50 micrometers, or 0.5 micrometers to 15 micrometers. When both the primer and the barrier composition contain at least one particulate material, the average particle size of the particulate material contained in the primer layer is preferably larger than the average particle size of the particulate material contained in the barrier layer.

好ましい実施形態では、プライマー組成物は、平均粒径が０．５マイクロメートル〜１５マイクロメートル、好ましくは２マイクロメートル〜１０マイクロメートルの粒状物質を含み、障壁組成物は、平均粒径が０．５〜１５マイクロメートル、好ましくは０．５〜２マイクロメートルの粒状物質を含む。   In a preferred embodiment, the primer composition comprises a particulate material having an average particle size of 0.5 micrometers to 15 micrometers, preferably 2 micrometers to 10 micrometers, and the barrier composition has an average particle diameter of 0.00. 5 to 15 micrometers, preferably 0.5 to 2 micrometers of particulate material.

他の好ましい実施形態では、障壁組成物は粒状物質を実質的に含まず、一方、プライマー組成物は平均粒径が０．５マイクロメートル〜５０マイクロメートル、または０．５マイクロメートル〜１５マイクロメートル、好ましくは２マイクロメートル〜１０マイクロメートルの粒状物質を含む。   In other preferred embodiments, the barrier composition is substantially free of particulate material, while the primer composition has an average particle size of 0.5 micrometers to 50 micrometers, or 0.5 micrometers to 15 micrometers. , Preferably 2 to 10 micrometers of particulate material.

粒状物質は、例えば、二酸化チタン、シリカ、架橋ポリメチルメタクリレート、架橋ベンゾグアナミンホルムアルデヒド樹脂、架橋ベンゾグアナミンメラミンホルムアルデヒド樹脂、架橋シロキサン、およびこれらの混合物などの、無機または有機材料から選択し得る。粒状物質は、例えば、ポリメチルシルセスキオキサンなどの架橋シロキサンであることが好ましい。粒状物質は、障壁またはプライマー組成物中に、障壁またはプライマー組成物の全重量に対して１重量パーセント〜１０重量パーセント、より好ましくは１重量パーセント〜５重量パーセントの範囲の量で含まれ得る。   The particulate material may be selected from inorganic or organic materials such as, for example, titanium dioxide, silica, crosslinked polymethylmethacrylate, crosslinked benzoguanamine formaldehyde resin, crosslinked benzoguanamine melamine formaldehyde resin, crosslinked siloxane, and mixtures thereof. The particulate material is preferably a crosslinked siloxane such as polymethylsilsesquioxane, for example. The particulate material may be included in the barrier or primer composition in an amount ranging from 1 weight percent to 10 weight percent, more preferably from 1 weight percent to 5 weight percent, relative to the total weight of the barrier or primer composition.

本発明はまた、第１の面と反対側の第２の面とを有し、前記第１の面上にプライマー組成物層を含み、プライマー組成物層上に少なくとも１層の、好ましくは１〜４層の、より好ましくは２または３層の障壁組成物層を含む、上記方法により得られる障壁布であって、障壁布の内部（表面に対立するものとして）にプライマーおよび障壁組成物を実質的に含まない障壁布を提供する。   The present invention also includes a first surface and a second surface opposite the first surface, including a primer composition layer on the first surface, and at least one layer, preferably 1 on the primer composition layer. A barrier fabric obtained by the above method comprising -4 layers, more preferably 2 or 3 barrier composition layers, wherein the primer and the barrier composition are placed inside the barrier fabric (as opposed to the surface). Provide a substantially free barrier fabric.

さらに他の実施形態では、本発明は、第１の面と反対側の第２の面とを有し、前記第１の面上にプライマー組成物層を含み、プライマー組成物層上に１〜４層の障壁組成物層を含み、前記反対側の第２の面上に帯電防止組成物層をさらに含む、上記方法により得られる障壁布を提供する。   In yet another embodiment, the present invention comprises a first surface and a second surface opposite the first surface, comprising a primer composition layer on the first surface, Provided is a barrier fabric obtained by the above method comprising four barrier composition layers and further comprising an antistatic composition layer on the opposite second side.

公称坪量が１平方メートル当たり５８グラムの、ＤｕｐｏｎｔからＴＹＶＥＣ（登録商標）１５６０Ｂの商標で商業的に入手可能な、ポリエチレンフラッシュスパン布を蒸着装置に挿入し、後で説明するように、組成物を組み合わせた異なる層でコーティングした。ウェブ速度を毎分１００メートルとし、布のウェブにコーティングする化合物を、１８０℃、圧力１．５×１０-2ｍｂａｒで蒸発させた。沈着後、１０．３ｋＶ、１Ａにセットした電子ビームにより、アルゴンガス中、圧力１．７×１０-2ｍｂａｒでコーティング層を硬化させた。組成物を表１に記載する。 A polyethylene flash spun fabric, commercially available under the trademark TYVEC® 1560B from Dupont, with a nominal basis weight of 58 grams per square meter, is inserted into the vapor deposition apparatus and the composition as described below. Coated with different layers combined. The compound that coats the web of fabric at a web speed of 100 meters per minute was evaporated at 180 ° C. and a pressure of 1.5 × 10 −2 mbar. After deposition, the coating layer was cured at a pressure of 1.7 × 10 −2 mbar in argon gas by an electron beam set at 10.3 kV, 1A. The compositions are listed in Table 1.

Figure 2015530234
Figure 2015530234

フッ素化化合物は、ＤｕｐｏｎｔからＺＯＮＹＬ（登録商標）ＴＭ−Ｎの商標で商業的に入手可能なペルフルオロアルキルエチルメタクリレートを約９５重量パーセント含む混合物とした。
架橋性モノマー化合物は、Ｓａｒｔｏｍｅｒ Ｃｏｍｐａｎｙ（Ｅｘｔｏｎ，ＵＳ）からＳＡＲＴＯＭＥＲ（登録商標）ＳＲ９００３の商標で商業的に入手可能な、純プロポキシル化ネオペンチルグリコールジアクリレートとした。
増白剤化合物は、Ｃｉｂａ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ（Ｂａｓｌｅ、ＣＨ）からＵＶＩＴＥＸ（登録商標）ＯＢの商標で商業的に入手可能な、２，５−チオフェンジイルビス（５−ｔｅｒｔ−ブチル−１，３−ベンゾオキサゾール）とした。 The fluorinated compound was a mixture containing about 95 weight percent of perfluoroalkylethyl methacrylate commercially available from Dupont under the trademark ZONYL® TM-N.
The crosslinkable monomer compound was pure propoxylated neopentyl glycol diacrylate, commercially available from Sartomer Company (Exton, US) under the trademark SARTOMER® SR9003.
The brightener compound is 2,5-thiophenediylbis (5-tert-butyl-1,3-benzoate, commercially available from Ciba Specialty Chemicals (Basle, CH) under the trademark UVITEX® OB. Oxazole).

蒸着装置は、ポリエチレンフラッシュスパン布に、１度に１層のコーティングができるだけであるため、１層より多くの層を塗布するときは、塗布する追加層毎に、コーティングしたポリエチレンフラッシュスパン布を蒸着装置に再度挿入した。その後、炭化水素に対する試料布の撥液性を試験した。撥液性の評価はＡＡＴＣＣ Ｔｅｓｔ Ｍｅｔｈｏｄ １１８（２００７）に拠った。撥液性評価が高いほど、炭化水素などの疎水性物質に対する撥液性が良好である。結果を表２にまとめる。   The vapor deposition equipment can only coat one layer of polyethylene flash spun cloth at a time, so when applying more than one layer, deposit the coated polyethylene flash spun cloth for each additional layer to be applied. Reinserted into the device. Thereafter, the liquid repellency of the sample fabric against hydrocarbons was tested. Evaluation of liquid repellency was based on AATCC Test Method 118 (2007). The higher the liquid repellency evaluation, the better the liquid repellency for hydrophobic substances such as hydrocarbons. The results are summarized in Table 2.

Figure 2015530234
Figure 2015530234

表２から分かるように、撥液性評価は、例えば、試料２（０．６ｇ／ｍ2の１障壁層、評価：１）と試料３（０．６ｇ／ｍ2の２障壁層、評価：３）との間のように、障壁組成物の総量が増すとともに高くなる。また、例えば、試料３（０．６ｇ／ｍ2の２障壁層、評価：３）と試料６（０．４ｇ／ｍ2の３障壁層、評価：４）との間のように、障壁組成物の総量がより多くの層に存在するとき、撥液性評価が高くなることも分かる。さらに、試料２（０．６ｇ／ｍ2の１障壁層、評価：１）と試料４（０．６ｇ／ｍ2の１プライマー層、０．６ｇ／ｍ2の１障壁層、評価：３）を比較すれば分かるように、プライマー層の存在は、炭化水素に対する撥液性に影響する。プライマー層と多障壁層の利点の組み合わせ、すなわち多障壁層と１プライマー層は、試料５（０．６ｇ／ｍ2の１プライマー層、０．６ｇ／ｍ2の２障壁層、評価：５）のように、非常に高い撥液性評価をもたらす。 As can be seen from Table 2, the liquid repellency is evaluated by, for example, Sample 2 (0.6 g / m 2 1 barrier layer, evaluation: 1) and Sample 3 (0.6 g / m 2 2 barrier layer, evaluation: As in 3), the total amount of the barrier composition increases as it increases. Also, for example, between the sample 3 (0.6 g / m 2 two-barrier layer, evaluation: 3) and the sample 6 (0.4 g / m 2 three-barrier layer, evaluation: 4), the barrier composition It can also be seen that the liquid repellency evaluation is higher when the total amount of objects is present in more layers. Furthermore, (1 barrier layer of 0.6 g / m 2, Rating: 1) Sample 2 and Sample 4 (1 primer layer of 0.6 g / m 2, 1 barrier layer of 0.6 g / m 2, rating: 3) As can be seen from the comparison, the presence of the primer layer affects the liquid repellency of hydrocarbons. The combination of the advantages of the primer layer and the multi-barrier layer, i.e. a multi-barrier layer and a primer layer, Sample 5 (1 primer layer of 0.6 g / m 2, 2 barrier layer of 0.6 g / m 2, Rating: 5) As a result, the liquid repellency evaluation is very high.

Claims (14)

第１の面と反対側の第２の面とを有する不織障壁布の製造方法であって、
（ａ）前記布の前記第１の面に、フッ素化化合物を実質的に含まないプライマー組成物を塗付して、前記布の前記第１の面上に、前記プライマー組成物の層を形成する工程と、
（ｂ）少なくとも１種の不飽和フッ素化化合物を含む障壁組成物を、蒸着またはエアロゾル沈着法により、前記プライマー組成物層に塗布して、前記プライマー組成物層上に、１〜４層の前記障壁組成物の層を形成する工程と
を含む方法。 A method for producing a nonwoven barrier fabric having a first side and a second side opposite to the first side,
(A) A primer composition substantially free of a fluorinated compound is applied to the first surface of the fabric to form a layer of the primer composition on the first surface of the fabric. And a process of
(B) A barrier composition containing at least one unsaturated fluorinated compound is applied to the primer composition layer by vapor deposition or aerosol deposition, and 1 to 4 layers of the primer composition layer are formed on the primer composition layer. Forming a layer of the barrier composition. 第１の面と反対側の第２の面とを有する不織障壁布の製造方法であって、
（ａ）蒸着またはエアロゾル沈着法により、前記布の前記第１の面に、フッ素化化合物を実質的に含まないプライマー組成物を塗付して、前記布の前記第１の面上に、前記プライマー組成物の層を形成する工程と、
（ｂ）少なくとも１種の不飽和フッ素化化合物を含む障壁組成物を、蒸着またはエアロゾル沈着法により、前記プライマー組成物層に塗布して、前記プライマー組成物層上に、少なくとも１層の前記障壁組成物の層を形成する工程と
を含む方法。 A method for producing a nonwoven barrier fabric having a first side and a second side opposite to the first side,
(A) applying a primer composition substantially free of a fluorinated compound to the first surface of the fabric by vapor deposition or aerosol deposition, and then applying the primer composition to the first surface of the fabric; Forming a layer of the primer composition;
(B) A barrier composition containing at least one unsaturated fluorinated compound is applied to the primer composition layer by vapor deposition or aerosol deposition, and at least one barrier layer is formed on the primer composition layer. Forming a layer of the composition. 前記少なくとも１種の不飽和フッ素化化合物が、
［ＣＨ2＝ＣＲＣＯＯ（ＣＨ2）x（Ｓｕ）y］z（ＣnＦ2n+2-z）
（式中、ｎは１〜１４の範囲の整数、ｘは独立して１〜８の範囲の整数、Ｒは独立して水素原子、または鎖長が炭素数１〜１６個の範囲のアルキル基、Ｓｕはスルホンアミド基、ｙは独立して０〜１の範囲の整数、およびｚは１〜２の範囲の整数である）で示される一般構造を有するフルオロ（ジ）アクリレートモノマーの少なくとも１種を含む請求項１または２に記載の方法。 The at least one unsaturated fluorinated compound is
[CH 2 = CRCOO (CH 2 ) x (Su) y] z (C n F 2n + 2-z)
Wherein n is an integer in the range of 1 to 14, x is independently an integer in the range of 1 to 8, R is independently a hydrogen atom, or an alkyl group having a chain length of 1 to 16 carbons. , Su is a sulfonamide group, y is independently an integer in the range of 0 to 1, and z is an integer in the range of 1 to 2, and at least one fluoro (di) acrylate monomer having a general structure The method according to claim 1 or 2, comprising: Ｒが、好ましくはメチルまたはエチル基である請求項３に記載の方法。   4. A process according to claim 3, wherein R is preferably a methyl or ethyl group. 前記障壁組成物が、さらに、少なくとも１種の架橋性モノマー化合物を、前記障壁組成物の全重量に対して、１０〜５０重量パーセント含む請求項１〜４のいずれか一項に記載の方法。   The method according to claim 1, wherein the barrier composition further comprises 10 to 50 weight percent of at least one crosslinkable monomer compound, based on the total weight of the barrier composition. （ｃ）前記プライマー組成物層、および前記少なくとも１層の障壁組成物層を硬化させる工程
をさらに含む請求項１〜５のいずれか一項に記載の方法。 (C) The method of any one of claims 1 to 5, further comprising the step of curing the primer composition layer and the at least one barrier composition layer. （ｄ）前記布の前記反対側の第２の面に帯電防止組成物を塗布して、前記布の前記反対側の第２の面上に前記帯電防止組成物の層を形成する工程をさらに含む請求項１〜６のいずれか一項に記載の方法。   (D) applying an antistatic composition to the second surface on the opposite side of the fabric to further form a layer of the antistatic composition on the second surface on the opposite side of the fabric; The method according to claim 1, comprising: 前記プライマー組成物が、前記布に、１平方メートル当たり０．２〜２グラムの量で塗付される請求項１〜７のいずれか一項に記載の方法。   8. The method according to any one of claims 1 to 7, wherein the primer composition is applied to the fabric in an amount of 0.2 to 2 grams per square meter. 障壁組成物１層当たりの障壁組成物の量が、１平方メートル当たり０．１〜１グラムである請求項１〜８のいずれか一項に記載の方法。   9. A method according to any one of the preceding claims, wherein the amount of barrier composition per layer of barrier composition is 0.1 to 1 gram per square meter. 前記プライマー組成物および前記障壁は、少なくとも１種の、平均粒径が０．５〜５０マイクロメートルの粒状物質をさらに含む請求項１〜９のいずれか一項に記載の方法。   The method according to any one of claims 1 to 9, wherein the primer composition and the barrier further comprise at least one particulate material having an average particle size of 0.5 to 50 micrometers. 前記プライマー層に含まれる前記粒状物質の平均粒径が、前記障壁層に含まれる前記粒状物質の平均粒径より大きい請求項１０に記載の方法。   The method according to claim 10, wherein an average particle size of the particulate material included in the primer layer is larger than an average particle size of the granular material included in the barrier layer. 前記粒状物質が、架橋シロキサン粒子を含む請求項１０または１１に記載の方法。   12. A method according to claim 10 or 11, wherein the particulate material comprises crosslinked siloxane particles. 第１の面と反対側の第２の面とを有し、前記第１の面上にプライマー組成物層を含み、前記プライマー組成物層上に少なくとも１層の障壁組成物層を含む請求項１〜１２のいずれか一項により得られる障壁布。   A first surface and a second surface opposite the first surface, comprising a primer composition layer on the first surface, and comprising at least one barrier composition layer on the primer composition layer. The barrier cloth obtained by any one of 1-12. 前記布の前記反対側の第２の面上に帯電防止組成物層を有する請求項１３に記載の障壁布。   14. The barrier fabric according to claim 13, comprising an antistatic composition layer on the opposite second surface of the fabric.
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