JP6480335B2 - Antibacterial non-woven sheet, liquid-containing sheet, and face mask - Google Patents

Antibacterial non-woven sheet, liquid-containing sheet, and face mask Download PDF

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JP6480335B2
JP6480335B2 JP2015539137A JP2015539137A JP6480335B2 JP 6480335 B2 JP6480335 B2 JP 6480335B2 JP 2015539137 A JP2015539137 A JP 2015539137A JP 2015539137 A JP2015539137 A JP 2015539137A JP 6480335 B2 JP6480335 B2 JP 6480335B2
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antibacterial
fiber
sheet
weight
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JPWO2015045982A1 (en
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大前　好信
好信 大前
宗訓 熊谷
宗訓 熊谷
純人 清岡
純人 清岡
和之 中山
和之 中山
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Kuraray Co Ltd
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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
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43835—Mixed fibres, e.g. at least two chemically different fibres or fibre blends
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0208—Tissues; Wipes; Patches
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212—Face masks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8129—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • 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
    • D04H1/425—Cellulose series
    • D04H1/4258—Regenerated cellulose 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
    • D04H1/40—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
    • D04H1/4309—Polyvinyl alcohol
    • 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
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • 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
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/43828—Composite fibres sheath-core
    • 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
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/4383—Composite fibres sea-island
    • 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
    • D04H1/44—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling
    • D04H1/46—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
    • D04H1/492—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres by fluid jet
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns

Description

本発明は、***物、皮脂、化粧品などの肌の清拭、拭き取りや、保湿、美容などの機能を有する化粧料組成物を含む流動性組成物の肌への吸着、吸収に有効な基材となる抗菌性不織布シートに関する。また、本発明は、美容成分、薬効成分などを含む流動性組成物を含浸させ、抗菌性不織布シートと一体化させた含液シート、特に、皮膚に貼付して使用する、抗菌性を有するフェイスマスクに関する。   The present invention provides a substrate effective for adsorbing and absorbing a fluid composition containing a cosmetic composition having functions such as cleansing, wiping, moisturizing, and beauty of skin such as excrement, sebum and cosmetics. Relates to an antimicrobial non-woven sheet. Further, the present invention is a liquid-impregnated sheet integrated with an antibacterial non-woven sheet by impregnating a flowable composition containing a cosmetic component, a pharmaceutically active component and the like, and in particular, an antibacterial face About the mask.

従来から、水や水性の流動性組成物を不織布シートと一体としたウェットティッシュ、使い捨ておしぼり、肌を被覆するシート状化粧料などの含水シートには、レーヨンなどの親水性繊維、または親水性繊維と熱接着性複合繊維の混綿からなる繊維ウェブに高圧水流処理を施した不織布、あるいは前記不織布を機能的な改善を施した様々な不織布が提案されている。しかしながら、レーヨンなどの親水性繊維は湿潤時に、繊維のコシの低下や繊維の収縮などによりシワの発生が起きて、作業性や保液性を損う形態安定性の低下につながるなどの問題や、繊維内に水分が取り込まれて、水分の効果を有効に利用できないなどの問題があった。上記問題を改善すべく、疎水性合成短繊維を５０重量％以上含有し、構成繊維同士が部分的熱圧着部により接合された熱接着不織布の両面に、親水性短繊維を４０重量％以上含有してなる繊維ウェブが積層され、絡合されてなる複合湿潤シートが提案されている（たとえば、特開２００１−３３６０５３号公報（特許文献１）を参照）。   Conventionally, a water-containing sheet such as a wet tissue, a disposable towel, or a sheet-like cosmetic for covering the skin, in which water or an aqueous fluid composition is integrated with a non-woven sheet, hydrophilic fibers such as rayon or hydrophilic fibers A non-woven fabric obtained by high-pressure water flow treatment on a fiber web composed of a blend of heat-adhesive composite fibers and various non-woven fabrics obtained by functionally improving the non-woven fabric has been proposed. However, when hydrophilic fibers such as rayon are wet, wrinkles are generated due to a decrease in the stiffness of the fibers or shrinkage of the fibers, which causes problems such as deterioration in workability and liquid retention, and deterioration in form stability. There is a problem that moisture is taken into the fiber and the effect of the moisture can not be effectively used. In order to ameliorate the above problems, hydrophilic short fibers are contained at 40% by weight or more on both surfaces of a heat-bonded non-woven fabric containing 50% by weight or more of hydrophobic synthetic short fibers and having constituent fibers joined together by partial thermocompression bonding A composite wet sheet in which the resulting fibrous web is laminated and entangled is proposed (see, for example, Japanese Patent Application Laid-Open No. 2001-336053 (Patent Document 1)).

しかしながら、特許文献１のように熱接着性成分を融着することで作製されたシートは、湿潤時の収縮は改善されるがシート全体が硬くなってしまい肌への沿い性が低下する。さらに、シート表面は親水性繊維を主体繊維としているため繊維内に含浸した薬液を取り込んでしまい、充分に拭き取り対象物に放出することができなくなる。また、社会ニーズの広がりによってさらに種々の流動性組成物を取り込む機能を求められることになった。   However, in the sheet produced by fusing the heat-adhesive component as in Patent Document 1, the shrinkage when wet is improved but the entire sheet becomes hard and the running property to the skin decreases. Furthermore, since the sheet surface is mainly composed of hydrophilic fibers, the chemical solution impregnated in the fibers can be taken in and can not be sufficiently wiped off and released to the object. In addition, the spread of social needs has made it necessary to have a function to further incorporate various fluid compositions.

これらを解決するため、たとえば特開２００８−２６１０６７号公報（特許文献２）には、肌触りが良く、水の保液性及び放出性、形態安定性に優れる含水シートとして、３０〜６０ｍｍの繊維長を有する溶剤紡糸セルロース系繊維と鞘芯型複合繊維とが、互いに交絡してなる不織布シートであって、前記鞘芯型複合繊維は鞘部と芯部とからなり、前記鞘部がエチレン−ビニルアルコール系共重合体であるとともに、前記芯部が疎水性樹脂からなりその径が５〜１５μｍである不織布シートが提案されている。   In order to solve these, for example, JP-A 2008-261067 (patent document 2) has a fiber length of 30 to 60 mm as a water-containing sheet which is good in touch, excellent in water retention and release, and shape stability. A solvent-spun cellulosic fiber having a core and a sheath-core type composite fiber are entangled with each other, wherein the sheath-core type composite fiber comprises a sheath part and a core part, and the sheath part is ethylene-vinyl A non-woven sheet which is an alcohol-based copolymer and in which the core portion is made of a hydrophobic resin and the diameter of which is 5 to 15 μm has been proposed.

近年では、これらの不織布シートに抗菌性を求められるようになり、特にパラベンなどの防腐剤・抗菌剤が多く使用されるようになった。ところが、ブチルパラベンにおける内分泌物攪乱作用を有する疑い、パラベン全体における一過性の刺激発現可能性の高さなど、パラベンの使用に制限すべき状況が存在するほか、皮膚に付着すると肌荒れ、かぶれなどの肌トラブルをもたらす虞があることから、パラベンフリー（パラベン不使用）で防腐・抗菌を図ることが望まれているのが現状である。   In recent years, these nonwoven sheets have been required to have antibacterial properties, and in particular, preservatives and antibacterial agents such as parabens have been widely used. However, there is a condition that should be restricted to the use of paraben such as suspicion of endocrine disrupting action in butyl paraben, high possibility of transient irritation expression in the whole paraben, etc. If it adheres to the skin, it may cause rough skin, rash etc. Because there is a risk of causing skin problems, it is currently desirable to aim for antiseptic and antifungal use with paraben free (non use of paraben).

特開２００１−３３６０５３号公報JP 2001-336053 A 特開２００８−２６１０６７号公報JP, 2008-261067, A

すなわち本発明が解決しようとする課題は、パラベンなどを含有しなくても優れた防腐・抗菌性を有し、柔らかく肌触りがよく、種々の流動性組成物を含浸したときに良好な含浸性と保液性を持ち、さらに圧力などによって該流動性組成物を効率良く放出でき、流動性組成物の含浸によるコシの低下や収縮が少ないことで形態安定性に優れる抗菌性不織布シートを提供することにある。また、本発明は、肌触りが良く、水などを含めた流動性組成物の保液性、放出性、形態安定性に優れる含液シートを提供することである。   That is, the problem to be solved by the present invention is that it has excellent antiseptic and antibacterial properties without containing parabens, etc., is soft and has a good touch, and has good impregnatability when impregnated with various fluid compositions. It is possible to provide an antibacterial non-woven fabric sheet which has a liquid retention property, can efficiently release the flowable composition by pressure, etc., and is excellent in form stability by reducing shrinkage and shrinkage due to impregnation of the flowable composition. It is in. Another object of the present invention is to provide a liquid-containing sheet which has a good touch and is excellent in the liquid retaining property, releasing property and form stability of the flowable composition including water and the like.

我々は以上の課題を鑑みて鋭意検討し、本発明に至った。
すなわち、第１の発明は、無機系抗菌微粒子を内部に分散した状態で含有する抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在し、該無機系抗菌微粒子の平均粒径が０．０１〜２０μｍであって、且つ該抗菌性エチレン−ビニルアルコール系共重合体のエチレン含有率が１０〜７０モル％である抗菌性繊維と、溶剤紡糸セルロース系繊維とが、互いに交絡してなることを特徴とする抗菌性不織布シートである。In view of the above problems, we have studied intensively and arrived at the present invention.
That is, in the first invention, the antibacterial ethylene-vinyl alcohol copolymer containing the inorganic antibacterial particles dispersed in the inside is present in at least a part of the fiber surface, and the average particles of the inorganic antibacterial particles are contained. An antibacterial fiber having a diameter of 0.01 to 20 μm and having an ethylene content of 10 to 70 mol% of the antibacterial ethylene-vinyl alcohol copolymer, and a solvent-spun cellulose-based fiber are mutually entangled. It is an antibacterial nonwoven fabric sheet characterized by becoming.

第２の発明は、第１の発明の抗菌性繊維、及び溶剤紡糸セルロース系繊維の繊維長が５〜６０ｍｍであり、これらが互いに交絡してなることを特徴とする抗菌性不織布シートである。   A second invention is an antibacterial nonwoven sheet according to the first invention, wherein the fiber length of the solvent-spun cellulose-based fiber is 5 to 60 mm, and these fibers are entangled with each other.

第３の発明は、第１の発明、及び／または第２の発明の抗菌性繊維が鞘芯型複合繊維であって、該鞘部が、平均粒径が０．０１〜２０μｍの無機系抗菌微粒子を内部に分散した状態で含有する抗菌性エチレン−ビニルアルコール系共重合体であるとともに、該芯部が疎水性樹脂からなりその径が５〜１５μｍであることを特徴とする抗菌性不織布シートである。   In a third invention, the antibacterial fiber of the first invention and / or the second invention is a sheath-core type composite fiber, and the sheath is an inorganic antibacterial having an average particle diameter of 0.01 to 20 μm. An antimicrobial non-woven sheet characterized in that it is an antimicrobial ethylene-vinyl alcohol copolymer containing fine particles dispersed therein, and the core is made of a hydrophobic resin and its diameter is 5 to 15 μm. It is.

第４の発明は、第１〜３の発明の抗菌性不織布シートであって、前記抗菌性不織布シートの表面が凹凸を有することを特徴とする抗菌性不織布シートである。   4th invention is an antibacterial nonwoven fabric sheet of the 1st-3rd invention, Comprising: The surface of the said antibacterial nonwoven fabric sheet has an unevenness | corrugation, It is an antibacterial nonwoven fabric sheet characterized by the above-mentioned.

第５の発明は、第１〜４の発明の抗菌性不織布シートであって、前記抗菌性繊維を３０〜９０重量％含むことを特徴とする抗菌性不織布シートである。   5th invention is an antibacterial nonwoven fabric sheet of the 1st-4th invention, Comprising: The antibacterial nonwoven fabric sheet characterized by including 30-90 weight% of said antibacterial fibers.

第６の発明は、第５の発明の抗菌性不織布シートであって、前記抗菌性繊維を４０〜９０重量％含み、前記抗菌性繊維のヤング率が２５ｃＮ／ｄｔｅｘ以上であることを特徴とする抗菌性不織布シートである。   A sixth invention is the antibacterial nonwoven sheet of the fifth invention, characterized in that it contains 40 to 90% by weight of the antibacterial fiber, and the Young's modulus of the antibacterial fiber is 25 cN / dtex or more. It is an antibacterial non-woven sheet.

第７の発明は、第１〜６の発明の抗菌性不織布シートと流動性組成物とが一体となった含液シートである。   A seventh invention is a liquid-containing sheet in which the antibacterial nonwoven fabric sheet of the first to sixth invention and the flowable composition are integrated.

第８の発明は、第７の発明の含液シートであって、前記流動性組成物が水を含む、含液シートである。   The eighth invention is the liquid-containing sheet of the seventh invention, wherein the flowable composition contains water.

第９の発明は、第７の発明の含液シートであって、前記流動性組成物が、化粧料を含む、含液シートである。   A ninth invention is the liquid-containing sheet of the seventh invention, wherein the flowable composition includes a cosmetic.

第１０の発明は、第９の発明の含液シートであって、スキンケアシートである、含液シートである。   A tenth invention is a liquid-containing sheet according to the ninth invention, which is a liquid-care sheet which is a skin care sheet.

第１１の発明は、第９または１０の発明の含液シートであって、流動性組成物を自重に対して９００重量％含浸させて、２６０ｇ／ｃｍ2の荷重を１分間負荷して取り除いたとき、厚み方向の圧縮に対する復位が５分間で３５％以上であることを特徴とする、含液シートである。The eleventh invention is a liquid-containing sheet according to the ninth or tenth invention, wherein 900% by weight of the flowable composition is impregnated with respect to its own weight and removed by applying a load of 260 g / cm 2 for 1 minute. When it is a liquid-containing sheet characterized in that reversion to compression in the thickness direction is 35% or more in 5 minutes.

第１２の発明は、第９〜１１の発明の含液シートを用いたフェイスマスクである。   A twelfth invention is a face mask using the liquid-containing sheet of the ninth to eleventh inventions.

以上述べた手段によって、本発明は、***物、皮脂、化粧品などの肌の清拭、拭き取りや、保湿、美容などの機能を有する化粧料を含む流動性組成物の肌への吸着、吸収に有効な基材となる抗菌性不織布シートを提供するとともに、該抗菌性不織布シートを含む含液シート、フェイスマスクを提供するものである。   By the above-described means, the present invention relates to absorption and absorption to the skin of a fluid composition containing a cosmetic having functions such as cleansing, wiping, moisturizing, and beauty of the skin such as excrement, sebum, and cosmetics. While providing the antimicrobial nonwoven fabric sheet used as an effective base material, the liquid containing sheet containing this antibacterial nonwoven fabric sheet, and a face mask are provided.

第１の発明は、無機系抗菌微粒子を内部に分散した状態で含有する抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在する繊維と、溶剤紡糸セルロース系繊維が共に親水性を有するだけでなく、２つの繊維が互いに交絡することによって不織布シートを構成するので柔らかく肌触りが良い。また、抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在する繊維と、溶剤紡糸セルロース系繊維は共に流動性組成物の含浸性が高く、すみやかに水などの流動性組成物を含浸できる。   In the first invention, both the fiber in which the antibacterial ethylene-vinyl alcohol copolymer containing the inorganic antibacterial fine particles dispersed therein is present in at least a part of the fiber surface and the solvent-spun cellulose fiber are both hydrophilic. As well as having a property, the two fibers form a non-woven sheet by being entangled with each other, so that they have a soft touch. In addition, the fiber in which the antibacterial ethylene-vinyl alcohol copolymer is present in at least a part of the fiber surface and the solvent-spun cellulose-based fiber both have high impregnatability of the flowable composition, and the flowability composition such as water quickly Can be impregnated.

また、抗菌性エチレン−ビニルアルコール系共重合体が疎水性部分を有し、そのエチレン含有率を調整することや、抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在する繊維と、溶剤紡糸セルロース系繊維の含有率などを調節することで種々の流動性組成物を含浸できる。   In addition, the antibacterial ethylene-vinyl alcohol copolymer has a hydrophobic portion, and the ethylene content is adjusted, and the antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface. Various flowable compositions can be impregnated by adjusting the content of fibers and solvent-spun cellulosic fibers.

さらに、溶剤紡糸セルロース系繊維は水や水溶液、極性溶媒、これらのエマルジョンなどの親水性の流動性組成物の保液性が高い。一方、抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在する繊維は保液性が低い。このため圧力などで容易に抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在する繊維付近の流動性組成物が外に染み出す。さらに、流動性組成物を放出した抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在する繊維は高い含浸性で溶剤紡糸セルロース系繊維からさらに流動性組成物を奪うので、適当な速度で連続的に流動性組成物が外に染み出す。本発明の抗菌性不織布シートは、抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在する繊維と、溶剤紡糸セルロース系繊維とが互いに交絡してなることで、流動性組成物の移動を速やかに行うことができる。これらによって含浸した流動性組成物の放出性が高くなるので有効に流動性組成物を使用できることとなる。   Furthermore, the solvent-spun cellulose-based fiber has high liquid retention of a hydrophilic fluid composition such as water, an aqueous solution, a polar solvent, and an emulsion thereof. On the other hand, the fiber in which the antimicrobial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface has low liquid retention. For this reason, the flowable composition in the vicinity of the fiber in which the antibacterial ethylene-vinyl alcohol copolymer is present in at least a part of the fiber surface is easily exuded to the outside by pressure or the like. Furthermore, the fiber in which the antibacterial ethylene-vinyl alcohol copolymer released the flowable composition is present in at least a part of the surface of the fiber is highly impregnated and further depletes the flowable composition from the solvent-spun cellulose-based fiber, The flowable composition oozes out continuously at an appropriate rate. The antibacterial non-woven fabric sheet of the present invention is a fluid composition in which the fiber in which the antibacterial ethylene-vinyl alcohol copolymer is present in at least a part of the fiber surface and the solvent-spun cellulose-based fiber are mutually entangled. You can move things quickly. Since the releasability of the flowable composition impregnated by these becomes high, the flowable composition can be effectively used.

抗菌性エチレン−ビニルアルコール系共重合体については、特定の粒子径を有する無機系抗菌微粒子を内部に分散した状態で存在させることで、磨耗などによる物理的外因によって、繊維、及び／または不織布シートから無機系抗菌微粒子の脱落を防ぐことができ、持続的に抗菌性能を発現させることができる。   With respect to the antibacterial ethylene-vinyl alcohol copolymer, fibers and / or non-woven sheets are obtained by physical extrinsic factors such as abrasion by causing inorganic antibacterial fine particles having a specific particle size to be present dispersed in the inside. It is possible to prevent the falling off of the inorganic antibacterial fine particles from the above, and to continuously exhibit the antibacterial performance.

第２の発明は、抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在する繊維と、溶剤紡糸セルロース系繊維の繊維長が５〜６０ｍｍであることで、不織布の剛性と適度な柔軟性と伸縮性を確保でき、且つ柔らかい肌触りと肌へのフィット感が実現できる。また、特に乾式条件での繊維交絡による製造においては、流動性組成物の含浸に優れるとともにクッション性にも優れた、嵩高い不織布シートが得られる。   The second invention is a fiber having an antibacterial ethylene-vinyl alcohol copolymer present in at least a part of the fiber surface, and a fiber length of the solvent-spun cellulose-based fiber being 5 to 60 mm. Appropriate flexibility and elasticity can be secured, and a soft touch and a feeling of fit to the skin can be realized. Moreover, in manufacture by the fiber entanglement in dry condition especially, while being excellent in the impregnation of a fluid composition, a bulky nonwoven fabric sheet excellent also in cushioning properties is obtained.

第３の発明は、抗菌性エチレン−ビニルアルコール系共重合体を鞘部、疎水性樹脂を芯部とする鞘芯型複合繊維とし、さらにその芯部の径が５〜１５μｍとすることによって、水分の含浸による収縮が少なく、シワになりにくく、保液性や作業性を損なうこともない抗菌性不織布シートとすることができる。また、使用時に芯のコシを肌に感じることができるので、柔らかい感触となるとともに、たとえば皮膚に密着させることが重要な化粧料の基材などの用途では肌への沿い性が高くなる。   The third invention is a sheath-core type composite fiber having an antibacterial ethylene-vinyl alcohol copolymer as a sheath and a hydrophobic resin as a core, and the diameter of the core is 5 to 15 μm. The antibacterial non-woven sheet can be made to be resistant to shrinkage due to the impregnation of water, to be less prone to wrinkles, and to not impair the liquid retention property and the workability. In addition, since the core of the skin can be felt at the time of use, the skin feels soft and, for example, in applications such as a base material for cosmetics in which close contact with the skin is important, the smoothness to the skin becomes high.

第４の発明は、抗菌性不織布シートの表面が凹凸を有することで、肌と密着したときに肌との間に空気層ができるので蒸れにくい。また、抗菌性不織布シートの表面が凹凸を有することで、表面積が高まるので肌との密着性が高まる。流動性組成物を含浸させ圧力によって放出させる、ウェットティッシュ、使い捨ておしぼり、化粧料を含む流動性組成物を用いた含液シートなどの用途では凹部に流動性組成物が保持されることで、肌に触れやすい凸部がさらっとしていながら良好な流動性組成物の放出が得られるので肌触りがさらに良い。また凹部により流動性組成物の保液効果が高まり、抗菌性エチレン−ビニルアルコール系共重合体の共重合比などによって、全体の極性を調節することなく広範な極性の流動性組成物を保持できる。   In the fourth invention, the surface of the antibacterial non-woven fabric sheet is uneven, so that an air layer is formed between the skin and the skin when it is in close contact with the skin, so it is hard to be stuffed. In addition, since the surface of the antibacterial nonwoven fabric sheet is uneven, the surface area is increased, and the adhesion to the skin is enhanced. In applications such as wet tissues, disposable towels, liquid containing sheets using a flowable composition containing a cosmetic, and the like, the flowable composition is retained in the recess to allow the flowable composition to be retained in the recess. Since the release of a good flowable composition can be obtained while the easily accessible convex portion is being scratched, the touch is even better. In addition, the liquid storage effect of the flowable composition is enhanced by the recess, and the flowability composition of wide polarity can be maintained without adjusting the overall polarity by the copolymerization ratio of the antibacterial ethylene-vinyl alcohol copolymer and the like. .

第５の発明は、本発明の抗菌性不織布シートにおいて、前記抗菌性繊維を３０〜９０重量％含み、且つ、溶剤紡糸セルロース系繊維を７０〜１０重量％含むことによって、肌触りが良く、流動性組成物を含浸して用いた場合には、含浸性、放出性、親水性の流動性組成物の保液性が良く、且つ含浸時の繊維の収縮やコシの低下がないことによる形態安定性などのバランスに非常に優れた抗菌性不織布シートとすることができる。   The fifth invention is the antibacterial nonwoven fabric sheet of the present invention, containing 30 to 90% by weight of the antibacterial fiber and 70 to 10% by weight of solvent-spun cellulose-based fiber, so that the skin feels good and fluidity When the composition is impregnated and used, the impregnating, releasing, and hydrophilic flowable composition has good retention of liquid, and the shape stability due to the absence of shrinkage and stiffness reduction of the fiber upon impregnation. It is possible to make an antibacterial non-woven sheet very excellent in balance such as.

第６の発明は、本発明の抗菌性不織布シートにおいて、抗菌性繊維を４０〜９０重量％含み、前記抗菌性繊維のヤング率が２５ｃＮ／ｄｔｅｘ以上であることによって、抗菌性を有しながら、且つ柔らかく、肌触りが良く、さらに美容液などの化粧料を含む流動性組成物を速やかに含浸することができ、適度なコシ、及び弾性が付加された抗菌性不織布シートとすることができる。   A sixth invention is the antibacterial nonwoven fabric sheet of the present invention, containing 40 to 90% by weight of antibacterial fiber, and having a Young's modulus of 25 cN / dtex or more of the antibacterial fiber while having antibacterial properties. And it can be soft, has a good touch, can be rapidly impregnated with a flowable composition containing a cosmetic such as a cosmetic solution, and can be made into an antibacterial non-woven sheet to which adequate stiffness and elasticity are added.

第７の発明は、本発明の抗菌性不織布シートと流動性組成物とが一体となった含液シートであるので、肌触りが良く、流動性組成物の保液性、放出性、形態安定性に優れ、ウェットティッシュ、使い捨ておしぼり、スキンケアシート、フェイスマスクなどの用途に好適である。   The seventh invention is a liquid-containing sheet in which the antibacterial nonwoven fabric sheet of the present invention and the flowable composition are integrated, so that the touch is good, and the liquid retention property, the release property, and the form stability of the flowable composition. It is suitable for applications such as wet tissues, disposable towels, skin care sheets and face masks.

第８の発明は、流動性組成物が水を含む含液シート（含水シート）であり、肌触りが良く、水の保液性、放出性、形態安定性に優れ、上述した用途に好適である。   The eighth invention is a liquid-containing sheet (water-containing sheet) in which the flowable composition contains water, which has a good touch, is excellent in water retention property, release property, and form stability, and is suitable for the above-mentioned applications .

第９の発明は、流動性組成物が化粧料を含む含液シートであり、肌触りが良く、化粧料の放出性が良く、形態安定性に優れるので皮膚に容易かつきれいに貼り付けることができる。   The ninth invention is a liquid-containing sheet containing a cosmetic, the flowable composition having a good touch, a good cosmetic releasability, and an excellent form stability, so that it can be easily and cleanly attached to the skin.

第１０の発明は、上述した含液シートを用いることで、化粧料を含む流動性組成物の含浸性、保液性に優れたスキンケアシートとすることができる。   In the tenth invention, by using the liquid-containing sheet described above, it is possible to make a skin care sheet excellent in the impregnation property and the liquid retention property of the flowable composition containing the cosmetic.

第１１の発明は、美容液（化粧料）を自重に対して９００重量％含浸させて、２６０ｇ／ｃｍ2の荷重を１分間負荷して取り除いたとき、厚み方向の圧縮に対する復位が５分間で３５％以上であることによって、押圧部の美容液の戻りを十分に保つことが可能な含液シートとすることができる。In the eleventh invention, when a cosmetic liquid (cosmetic agent) is impregnated in 900% by weight with respect to its own weight and removed by applying a load of 260 g / cm 2 for 1 minute, reciprocation for compression in the thickness direction is 5 minutes By being 35% or more, it can be set as the liquid-containing sheet which can fully maintain the return of the cosmetics of a press part.

第１２の発明は、上述した含液シートを用いることで、美容液（化粧料）を肌に十分に浸透可能なフェイスマスクとすることができる。   According to a twelfth aspect of the present invention, by using the liquid containing sheet described above, the cosmetic liquid (cosmetic) can be made into a face mask which can sufficiently penetrate the skin.

実施例における原反復位の測定方法を説明するための概略図である。It is the schematic for demonstrating the measuring method of the original repetition position in an Example. 実施例における原反への液戻りの測定方法を説明するための概略図である。It is the schematic for demonstrating the measuring method of the liquid return to the original fabric in an Example.

＜抗菌性不織布シート＞
本発明の抗菌性不織布シートは、抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在する繊維（以下、「抗菌性ＥＶＯＨ含有繊維」、あるいは単に「抗菌性繊維」と略称することがある）と、溶剤紡糸セルロース系繊維とが、互いに交絡してなるシートであって、均一に混合した上記の繊維を水流絡合法などにより不織布化することで、柔らかく且つ嵩高な繊維交絡体を実現したものである。<Antibacterial non-woven sheet>
The antibacterial nonwoven fabric sheet of the present invention is a fiber having an antibacterial ethylene-vinyl alcohol copolymer at least partially present on the surface of the fiber (hereinafter, referred to as "antibacterial EVOH-containing fiber" or simply "antibacterial fiber" And the solvent-spun cellulose-based fibers are entangled with each other, and the above-mentioned uniformly mixed fibers are made into a non-woven fabric by a hydroentanglement method or the like, so that soft and bulky fiber entanglement is caused. It is a realization of the body.

本発明に用いる抗菌性繊維は、無機系抗菌微粒子を内部に分散した状態で含有するエチレン−ビニルアルコール系共重合体が繊維の表面の少なくとも一部に存在している。   In the antibacterial fiber used in the present invention, an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles dispersed in the inside is present on at least a part of the surface of the fiber.

本発明に用いられる抗菌性エチレン−ビニルアルコール系共重合体は、エチレン単位の割合（共重合割合）が、１０〜７０モル％であり、残余がビニルアルコール単位単独、またはビニルアルコールとその他のビニル系モノマーの繰り返し単位からなるものである。エチレン単位の割合は、好ましくは２０〜５５モル％、さらに好ましくは３０〜５０モル％である。なお、ビニルアルコール単位とその他のビニル系モノマー単位が併用される場合、ビニルアルコール単位の割合は、特に制限されるものではないが、その他のビニル系モノマー単位よりも通常多く、モル比で、好ましくは（ビニルアルコール単位）：（その他のビニル系モノマー単位）＝５５：４５〜９９．９：０．１、より好ましくは７０：３０〜９９．９：０．１、特に好ましくは８０：２０〜９９．９：０．１である。   The antibacterial ethylene-vinyl alcohol copolymer used in the present invention has a ratio of ethylene units (copolymerization ratio) of 10 to 70 mol%, and the balance is vinyl alcohol units alone, or vinyl alcohol and other vinyls. It consists of a repeating unit of a system monomer. The proportion of ethylene units is preferably 20 to 55 mol%, more preferably 30 to 50 mol%. When a vinyl alcohol unit and another vinyl monomer unit are used in combination, the proportion of the vinyl alcohol unit is not particularly limited, but is usually larger than that of other vinyl monomer units, preferably in molar ratio. (Vinyl alcohol unit): (other vinyl monomer unit) = 55: 45 to 99.9: 0.1, more preferably 70:30 to 99.9: 0.1, particularly preferably 80: 20 It is 99.9: 0.1.

該エチレン−ビニルアルコール系共重合体におけるエチレン単位の割合が１０モル％よりも少ないと、繊維化する際の曳糸性が不良となって紡糸時の単糸切れ、断糸切れが多くなり、しかも柔軟性の欠けたものとなる。さらに、低温（２０〜６０℃）の水で膨潤化し形態が変化してしまうという問題も発生する。   When the proportion of ethylene units in the ethylene-vinyl alcohol copolymer is less than 10 mol%, the spinnability at the time of fiberization becomes poor, and single yarn breakage at the time of spinning and breakage breakage increase. Moreover, it is not flexible. Furthermore, the problem of swelling with water at low temperature (20 to 60 ° C.) to change the form also occurs.

一方、エチレン単位の割合が７０モル％を超えると、ビニルアルコール単位、すなわち水酸基の割合が必然的に少なくなるため、吸湿性が低下し、共重合体内部に保持された無機系抗菌微粒子の効果が十分に得られなくなるため好ましくない。   On the other hand, when the proportion of ethylene units exceeds 70 mol%, the proportion of vinyl alcohol units, that is, hydroxyl groups inevitably decreases, so the hygroscopicity decreases and the effect of the inorganic antibacterial fine particles retained inside the copolymer Is not preferable because it can not be obtained sufficiently.

該エチレン−ビニルアルコール系共重合体は、エチレン／酢酸ビニル系共重合体の酢酸ビニル部分をケン化することにより得ることができ、該エチレン−ビニルアルコール系共重合体におけるビニルアルコール単位のケン化度は、特に制限されるものではないが、好ましくは９０〜９９．９９モル％であり、より好ましくは９５〜９９．９８モル％、特に好ましくは９６〜９９．９７モル％である。ケン化度が小さすぎると、強度などの物性が低下するだけでなく、熱安定性が低下し、熱分解やゲル化によって安定性が低下する。一方、ケン化度が大きすぎると、繊維自体の製造が困難となる。   The ethylene-vinyl alcohol copolymer can be obtained by saponifying a vinyl acetate moiety of an ethylene / vinyl acetate copolymer, and the saponification of vinyl alcohol units in the ethylene-vinyl alcohol copolymer The degree is not particularly limited, but is preferably 90 to 99.99 mol%, more preferably 95 to 99.98 mol%, and particularly preferably 96 to 99.97 mol%. When the degree of saponification is too small, not only the physical properties such as strength are lowered, but also the thermal stability is lowered, and the stability is lowered by thermal decomposition and gelation. On the other hand, if the degree of saponification is too large, production of the fiber itself becomes difficult.

また、該エチレン−ビニルアルコール系共重合体の数平均分子量は、特に制限されるものではないが、好ましくは５０００〜２５０００、より好ましくは８０００〜２００００である。ここでいう数平均分子量とは、ＧＰＣ法により測定した値である。   The number average molecular weight of the ethylene-vinyl alcohol copolymer is not particularly limited, but is preferably 5,000 to 25,000, and more preferably 8,000 to 20,000. The number average molecular weight as referred to herein is a value measured by the GPC method.

該エチレン−ビニルアルコール系共重合体は、例えば（株）クラレより“エバール”の商品名で、また日本合成化学工業（株）より“ソアノール”の商品名で市販されており、容易に入手可能である。また、市販されているエチレンと酢酸ビニルからラジカル重合などによってエチレン／酢酸ビニル共重合体を製造し、それをケン化して使用してもよい。   The ethylene-vinyl alcohol copolymer is commercially available, for example, from Kuraray Co., Ltd. under the trade name of "EVAL" and from Nippon Synthetic Chemical Industry Co., Ltd. under the trade name of "SOANOL". It is. Alternatively, ethylene / vinyl acetate copolymer may be produced from ethylene and vinyl acetate commercially available by radical polymerization or the like, and it may be saponified and used.

本発明で用いる無機系抗菌微粒子の種類は特に制限されず、繊維の溶融紡糸時の加熱などにより揮発、分解、変質などを生じず、且つ短期間で抗菌作用が低下しない無機系抗菌微粒子のいずれもが使用できる。   The type of the inorganic antibacterial fine particles used in the present invention is not particularly limited, and any of the inorganic antibacterial fine particles which do not cause volatilization, decomposition, deterioration, etc. by heating at melt spinning of fibers, etc. You can use it.

該無機系抗菌微粒子の例としては、銀イオン、銅イオン、亜鉛イオン、錫イオンなどの抗菌作用を有する金属イオンを無機担体に内包させた無機系抗菌微粒子、酸化チタン系無機系抗菌微粒子などを挙げることができ、これらの１種または２種以上を用いることができる。   Examples of the inorganic antibacterial fine particles include inorganic antibacterial fine particles in which metal ions having an antibacterial activity such as silver ions, copper ions, zinc ions and tin ions are contained in an inorganic carrier, titanium oxide inorganic fine particles, etc. These can be mentioned, and one or more of these can be used.

本発明に用いる無機担体は、抗菌性を有する金属イオンを内包し、繊維の劣化作用を抑制できる限り、その種類は特に制限されないが、例えば、このような無機担体としては、包接格子を有する無機担体が好ましく用いられる。包接格子とは、原子や分子が入り込む程度の隙間で、この包接格子を有する無機粉体は微小な層状やかご状空洞を有する構造の部分に分子をとじ込める性質を持っている。   The type of the inorganic carrier used in the present invention is not particularly limited as long as it can contain metal ions having antibacterial properties and can suppress the deterioration of the fiber. For example, as such an inorganic carrier, it has a clathrate lattice An inorganic carrier is preferably used. The inclusion lattice is a gap that allows atoms and molecules to enter, and the inorganic powder having this inclusion lattice has the property of being able to repel molecules into a portion of a structure having a minute layer or cage-like cavity.

包接格子を有する無機担体としては、ゼオライト、層状リン酸塩（リン酸ジルコニウム、リン酸チタン、リン酸カルシウムなど）、層状粘土鉱物、遷移金属カルコゲン化物、黒鉛、遷移金属酸化物、層状酸素酸塩などが挙げられる。これらの無機担体は、単独で、または二種以上を組み合わせて用いてもよい。   As an inorganic support having an inclusion lattice, zeolite, layered phosphate (zirconium phosphate, titanium phosphate, calcium phosphate etc.), layered clay mineral, transition metal chalcogenide, graphite, transition metal oxide, layered oxygenate etc. Can be mentioned. These inorganic carriers may be used alone or in combination of two or more.

その中でも高いイオン交換能を有するゼオライト、リン酸ジルコニウムが特に好ましい。上記した無機系抗菌微粒子のうちでも、本発明では、銀イオンを前記した無機担体に保持させた無機系抗菌微粒子が特に好ましく用いられる。   Among them, zeolite having high ion exchange ability and zirconium phosphate are particularly preferable. Among the above-mentioned inorganic antibacterial fine particles, in the present invention, inorganic antibacterial fine particles in which silver ions are held on the above-mentioned inorganic carrier are particularly preferably used.

本発明に用いられるエチレン−ビニルアルコール系共重合体に含有させる無機系抗菌微粒子の平均粒径は、０．０１〜２０μｍであり、０．１〜１０μｍであることが好ましく、０．３〜６μｍであることがより好ましい。無機系抗菌微粒子の平均粒径が２０μｍよりも大きいと、紡糸する際に断糸、フィルター詰りが発生しやすく、また、繊維からの無機系抗菌微粒子の脱落などが起き易くなるため好ましくないほか、より細い繊維を得ようとした際には、繊維径より無機系抗菌微粒子の方が小さくなければならず、無機系抗菌微粒子径／繊維径の比は０．８以下であるのが望ましい。一方、無機系抗菌微粒子の平均粒径が０．０１μｍ未満の場合は、練り込みの際に無機系抗菌微粒子間の凝集などが生じやすく、エチレン−ビニルアルコール系共重合体中に均一に分散されにくくなるため好ましくない。   The average particle diameter of the inorganic antibacterial fine particles to be contained in the ethylene-vinyl alcohol copolymer used in the present invention is 0.01 to 20 μm, preferably 0.1 to 10 μm, and 0.3 to 6 μm. It is more preferable that If the average particle diameter of the inorganic antibacterial fine particles is larger than 20 μm, it is likely to cause thread breakage and filter clogging during spinning, and it is also not preferable because the falling of inorganic antibacterial fine particles from fibers is likely to occur. In order to obtain thinner fibers, the inorganic antibacterial fine particles must be smaller than the fiber diameter, and the ratio of the inorganic antibacterial fine particle diameter / fiber diameter is preferably 0.8 or less. On the other hand, when the average particle size of the inorganic antibacterial fine particles is less than 0.01 μm, aggregation between the inorganic antibacterial fine particles is likely to occur during kneading, and the particles are uniformly dispersed in the ethylene-vinyl alcohol copolymer. It is not preferable because it becomes difficult.

本発明に用いられる抗菌性エチレン−ビニルアルコール系共重合体に含有させる無機系抗菌微粒子の添加量は、該エチレン−ビニルアルコール系共重合体の重量に基づいて０．０１〜１０重量％にするのが好ましく、０．１〜５重量％がより好ましく、０．５〜１．５重量％が特に好ましい。無機微粒子における抗菌性金属イオンによるイオン交換容量、または吸着量にもよるが、イオン交換容量または金属イオン吸着能の９０％以上が抗菌性の金属イオンでイオン交換または吸着されている無機微粒子（抗菌性金属イオン保持無機微粒子）を使用する場合であっても、抗菌性金属イオン保持無機微粒子の添加量が０．０１重量％よりも少ないと繊維に充分な抗菌性能を付与しにくく、特に耐久性のある抗菌性能が得られにくくなる。一方、抗菌性金属イオン保持無機微粒子の添加量が１０重量％を超えると、抗菌性能は充分であるが、繊維化工程において無機系抗菌微粒子間の凝集が発生しやすくなりフィルターの目詰まりなどが生じる虞があるため好ましくない。   The addition amount of the inorganic antibacterial fine particle to be contained in the antibacterial ethylene-vinyl alcohol copolymer used in the present invention is 0.01 to 10% by weight based on the weight of the ethylene-vinyl alcohol copolymer. Is preferable, 0.1 to 5% by weight is more preferable, and 0.5 to 1.5% by weight is particularly preferable. Inorganic particles in which at least 90% of the ion exchange capacity or metal ion adsorption capacity is ion-exchanged or adsorbed by an antibacterial metal ion, depending on the ion exchange capacity or adsorption amount by the antibacterial metal ion in the inorganic particles Even in the case of using inorganic metal ion holding inorganic fine particles), when the addition amount of the antibacterial metal ion holding inorganic fine particles is less than 0.01% by weight, it is difficult to impart sufficient antibacterial performance to the fiber, and in particular the durability Antibacterial performance is difficult to obtain. On the other hand, when the addition amount of the antibacterial metal ion holding inorganic fine particles exceeds 10% by weight, although the antibacterial performance is sufficient, aggregation between the inorganic antibacterial fine particles is easily generated in the fiberization step, clogging of the filter, etc. It is not preferable because it may occur.

また、本発明に用いられるエチレン−ビニルアルコール系共重合体のエチレン含有率（Ｅ：モル％）と、該エチレン−ビニルアルコール系共重合体中の無機系抗菌微粒子の割合（Ｗ：重量％）とは、以下に示す式の関係を有してもよい。   In addition, the ethylene content (E: mol%) of the ethylene-vinyl alcohol copolymer used in the present invention and the ratio (W: wt%) of inorganic antibacterial fine particles in the ethylene-vinyl alcohol copolymer And may have the relationship of the formula shown below.

例えば、
１≦（１００−Ｅ）×Ｗ≦９０
であり、好ましくは、
５≦（１００−Ｅ）×Ｗ≦８０
である。For example,
1 ≦ (100−E) × W ≦ 90
And preferably
5 ≦ (100−E) × W ≦ 80
It is.

本発明の抗菌性ＥＶＯＨ含有繊維は、無機系抗菌微粒子を内部に分散した状態で含有する抗菌性エチレン−ビニルアルコール系共重合体を、少なくとも外表面に有している限り特に限定されず、該抗菌性エチレン−ビニルアルコール系共重合体単独からなる繊維であってもよいし、他の熱可塑性重合体との複合繊維であってもよい。   The antimicrobial EVOH-containing fiber of the present invention is not particularly limited as long as it has an antimicrobial ethylene-vinyl alcohol copolymer containing inorganic antimicrobial fine particles dispersed therein at least on the outer surface, It may be a fiber consisting of an antibacterial ethylene-vinyl alcohol copolymer alone or a composite fiber with another thermoplastic polymer.

本発明に用いる他の熱可塑性重合体は、抗菌性エチレン−ビニルアルコール系共重合体と複合可能である限り特に限定されず、繊維の目的に応じて幅広い種類を利用することが可能である。例えば、他の熱可塑性重合体としては、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、スチレン系樹脂、ポリ酢酸ビニル系樹脂、アクリル系樹脂、ポリ乳酸系樹脂、ポリカーボネート系樹脂、熱可塑性エラストマーなどの熱可塑性重合体を例示することができる。なお、抗菌性を有さないエチレン−ビニルアルコール系共重合体を他の熱可塑性重合体として用いても良い。   The other thermoplastic polymers used in the present invention are not particularly limited as long as they can be combined with the antibacterial ethylene-vinyl alcohol copolymer, and a wide variety of types can be used depending on the purpose of the fiber. For example, as other thermoplastic polymers, polyolefin resins, polyester resins, polyamide resins, polyvinyl chloride, polyvinylidene chloride, styrene resins, polyvinyl acetate resins, acrylic resins, polylactic resins, Thermoplastic polymers such as polycarbonate resins and thermoplastic elastomers can be exemplified. In addition, you may use the ethylene-vinyl alcohol-type copolymer which does not have antibacterial property as another thermoplastic polymer.

上記の中でも、特に耐熱性、繊維形成性及び寸法安定性の点から、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂を用いることが好ましく、さらにはポリオレフィン系樹脂、ポリエステル系樹脂といった疎水性樹脂が特に好ましい。この点については後述する。   Among the above, it is preferable to use polyolefin resins, polyester resins, and polyamide resins from the viewpoint of heat resistance, fiber formability and dimensional stability, and hydrophobic resins such as polyolefin resins and polyester resins are further preferable. Particularly preferred. This point will be described later.

ポリオレフィン系樹脂としては、ポリプロピレン、ポリエチレンなどが好ましく、これらのポリオレフィン系樹脂にも、共重合可能な他の単位が含まれていてもよい。   As a polyolefin resin, a polypropylene, polyethylene, etc. are preferable, and the other unit which can be copolymerized may be contained also in these polyolefin resin.

ポリエステル系樹脂としては、ポリＣ2-4アルキレンアリレート系樹脂などの芳香族ポリエステル系樹脂（ポリエチレンテレフタレート（ＰＥＴ）、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートなど）、特に、ＰＥＴなどのポリエチレンテレフタレート系樹脂が好ましい。ポリエチレンテレフタレート系樹脂は、エチレンテレフタレート単位の他に、他のジカルボン酸（例えば、イソフタル酸、ナフタレン−２，６−ジカルボン酸、フタル酸、４，４’−ジフェニルカルボン酸、ビス（カルボキシフェニル）エタン、５−ナトリウムスルホイソフタル酸など）やジオール（例えば、ジエチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール、シクロヘキサン−１，４−ジメタノール、ポリエチレングリコール、ポリテトラメチレングリコールなど）で構成された単位を２０モル％以下の割合で含んでいてもよい。Examples of polyester resins include aromatic polyester resins (polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate etc.) such as poly C 2-4 alkylene arylate resins, in particular polyethylene such as PET Terephthalate resins are preferred. The polyethylene terephthalate resin may contain, in addition to ethylene terephthalate units, other dicarboxylic acids (eg, isophthalic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid, 4,4'-diphenylcarboxylic acid, bis (carboxyphenyl) ethane) , 5-sodium sulfoisophthalic acid, etc. and diols (eg, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, A unit composed of polyethylene glycol, polytetramethylene glycol, etc.) may be contained in a proportion of 20 mol% or less.

ポリアミド系樹脂としては、ポリアミド６、ポリアミド６−６、ポリアミド６−１０、ポリアミド１０、ポリアミド１２、ポリアミド６−１２などの脂肪族ポリアミド、及びその共重合体、芳香族ジカルボン酸と脂肪族ジアミンとから合成された半芳香族ポリアミドなどが好ましい。これらのポリアミド系樹脂にも、共重合可能な他の単位が含まれていてもよい。   Examples of polyamide resins include aliphatic polyamides such as polyamide 6, polyamide 6-6, polyamide 6-10, polyamide 10, polyamide 12, polyamide 6-12, and copolymers thereof, aromatic dicarboxylic acids and aliphatic diamines. Preferred are semi-aromatic polyamides synthesized from These polyamide resins may also contain other copolymerizable units.

本発明の抗菌性ＥＶＯＨ含有繊維が複合繊維である場合には、エチレン−ビニルアルコール系共重合体：他の熱可塑性重合体の複合割合を、重量比率で、１０：９０〜９０：１０であることが望ましい。この範囲外であると、複合比率がアンバランスになるためノズル吐出後の放出糸が屈曲するなどの問題が生じ、紡糸性が不良になるため好ましくない。エチレン−ビニルアルコール系共重合体：他の熱可塑性重合体の複合割合は、より好ましくは、重量比率で、３０：７０〜７０：３０である。   When the antibacterial EVOH-containing fiber of the present invention is a composite fiber, the weight ratio of ethylene-vinyl alcohol copolymer: other thermoplastic polymer is 10:90 to 90:10. Is desirable. If the ratio is out of this range, the composite ratio becomes unbalanced, which causes problems such as bending of the discharged yarn after nozzle discharge, and the spinnability becomes poor, which is not preferable. The composite ratio of ethylene-vinyl alcohol copolymer: other thermoplastic polymer is more preferably 30:70 to 70:30 by weight.

前記複合繊維における複合形態としては、無機系抗菌微粒子を繊維内部に含有するエチレン−ビニルアルコール系共重合体を少なくとも外表面の一部に有している限り、鞘芯型、海島型、貼り合わせ型、それらの混在型などの任意の形態が挙げられる。鞘芯型の場合は、２層鞘芯型、及び３層以上の多層鞘芯型のいずれでもよい。また海島型の場合は、島の形状、数、分散状態を任意に選ぶことができ、島の一部が繊維表面に露出していてもよい。さらに貼り合わせ型の場合は、繊維の長さ方向に直角な繊維断面において、貼り合わせ面が直線状、円弧状またはその他、任意のランダムな曲線状のいずれの状態になっていてもよく、複数の貼り合わせ部分が平行になっていても、放射状になっていても、その他、任意の形状であっても何ら構わない。   As a composite form in the composite fiber, sheath-core type, sea-island type, bonding, as long as it has an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles in at least a part of the outer surface. It may be any form such as a type, a mixed type of them and the like. In the case of the sheath-core type, any of a two-layer sheath-core type and a multilayer sheath-core type having three or more layers may be used. In the case of the sea-island type, the shape, number, and dispersion state of the islands can be arbitrarily selected, and a part of the islands may be exposed on the fiber surface. Furthermore, in the case of the bonding type, in the fiber cross section perpendicular to the longitudinal direction of the fibers, the bonding surface may be linear, arc, or any other arbitrary arbitrary curved shape, and plural The bonded portions may be parallel, radial, or any other shape.

前記の複合形態の中でも、特に鞘芯型複合繊維は、繊維表面全体に無機系抗菌微粒子を含有するエチレン−ビニルアルコール系共重合体が配置されることから、抗菌性能の点で好適である。さらには、本発明の抗菌性不織布シートとした場合、無機系抗菌微粒子を含有するエチレン−ビニルアルコール系共重合体の単独繊維を用いると、吸液（流動性組成物の吸収）により剛性が低下して柔軟になりやすく、その製造、加工、包装などの工程、及びその使用時において、吸液やその時に加わる外力などの影響によって、圧縮されて繊維間の空間が維持でき難く、結果的に優れた保液性や作業性を確保することが困難になってしまう場合がある。これに対し、鞘芯型複合繊維とし、芯部に疎水性樹脂を用いることで、鞘部が吸液しても芯部は吸液せず、剛性の変化を生じないことから、これら加工工程においても所望の嵩高さ、すなわち空隙率を維持すると共に吸液性を確保することが可能となり、ウェット状態においても抗菌性不織布シートのコシを維持し、肌で抑えたときの感触も維持することが可能になる。   Among the above-mentioned composite forms, a sheath-core type composite fiber is particularly preferable in view of the antibacterial performance because an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles is disposed on the entire surface of the fiber. Furthermore, when it is set as the antibacterial nonwoven fabric sheet of this invention, rigidity will fall by liquid absorption (absorption of a fluid composition), using the single fiber of the ethylene-vinyl alcohol copolymer containing inorganic type antimicrobial fine particles. It is difficult to maintain the space between fibers due to the influence of liquid absorption and external force applied at the time of the process such as manufacturing, processing and packaging, and its use. It may be difficult to ensure excellent liquid retention and workability. On the other hand, by using a sheath-core type composite fiber and using a hydrophobic resin for the core, the core does not absorb liquid even if the liquid is absorbed in the sheath, and a change in rigidity does not occur. It is also possible to maintain the desired bulkiness, that is, the porosity, and to ensure the liquid absorption while maintaining the stiffness of the antibacterial non-woven sheet even in the wet state, and also to maintain the feel when suppressed by the skin. Becomes possible.

すなわち、本発明の抗菌性不織布シートで高い空隙率を確保するには、抗菌性不織布シートをヤング率（初期引張抵抗度）が高く、曲げ弾性が高い繊維で構成することが好ましい。そして特にこれらの加工工程の中で抗菌性不織布シートが吸液した状態になった場合においても高い繊維弾性を確保するために、構成する繊維が高弾性樹脂からなることが好ましい。ヤング率が高いほど不織布化された場合の空隙率を維持できるため、保液性を維持でき、作業性も向上可能となる。   That is, in order to ensure a high porosity in the antibacterial nonwoven sheet of the present invention, it is preferable to form the antibacterial nonwoven sheet from fibers having a high Young's modulus (initial tensile resistance) and high bending elasticity. In particular, in order to ensure high fiber elasticity even when the antibacterial non-woven fabric sheet is in a liquid-absorbed state in these processing steps, it is preferable that the constituent fibers be made of a highly elastic resin. As the Young's modulus is higher, the porosity in the case of being made into a non-woven fabric can be maintained, so the liquid retention can be maintained and the workability can be improved.

本発明の抗菌性不織布シートにおいて、後述する抗菌性ＥＶＯＨ含有繊維の含有率が４０〜９０重量％である場合、当該抗菌性ＥＶＯＨ含有繊維のヤング率は２５ｃＮ／ｄｔｅｘ以上が好ましい。特に、抗菌性ＥＶＯＨ含有繊維のヤング率は２５〜９０ｃＮ／ｄｔｅｘがより好ましく、さらに好ましくは３０〜７０ｃＮ／ｄｔｅｘ、特に好ましくは３５〜６０ｃＮ／ｄｔｅｘである。抗菌性ＥＶＯＨ含有繊維のヤング率が低すぎると、得られた抗菌性不織布シートのコシ及び弾性を向上できない。抗菌性ＥＶＯＨ含有繊維の構造は、前記ヤング率を有していれば、特に限定されず、無機系抗菌微粒子を含有するエチレン−ビニルアルコール系共重合体単独の繊維（単相の繊維）であってもよいが、弾性と保液性及び液放出性とを両立し易い点から、鞘芯型複合繊維が好ましい。   In the antibacterial nonwoven fabric sheet of the present invention, when the content of the antibacterial EVOH-containing fiber described later is 40 to 90% by weight, the Young's modulus of the antibacterial EVOH-containing fiber is preferably 25 cN / dtex or more. In particular, the Young's modulus of the antimicrobial EVOH-containing fiber is more preferably 25 to 90 cN / dtex, still more preferably 30 to 70 cN / dtex, and particularly preferably 35 to 60 cN / dtex. When the Young's modulus of the antimicrobial EVOH-containing fiber is too low, the stiffness and elasticity of the resulting antimicrobial nonwoven sheet can not be improved. The structure of the antibacterial EVOH-containing fiber is not particularly limited as long as it has the above-mentioned Young's modulus, and it is a fiber of an ethylene-vinyl alcohol copolymer alone containing inorganic antibacterial fine particles (fiber of a single phase). Although it may be used, a sheath-core type composite fiber is preferable because it is easy to make the elasticity, the liquid retaining property and the liquid releasing property compatible with each other.

本発明に用いる抗菌性ＥＶＯＨ含有繊維が鞘芯型複合繊維の場合において、鞘部は、濡れ性や保液性を確保するために、親水性樹脂で構成されているのが好ましい。親水性樹脂で構成された鞘部は、抗菌性不織布シートに化粧料（美容液）などを含む流動性組成物を付加した際に、流動性組成物を抗菌性不織布シートの内部まで取り込むために重要な役割を担うと共に、一度抗菌性不織布シート内に取り込んだ多量の化粧料を使用時に取り扱う際に液だれしないよう保持する役割を担う。   In the case where the antibacterial EVOH-containing fiber used in the present invention is a sheath-core type composite fiber, the sheath is preferably made of a hydrophilic resin in order to secure wettability and liquid retention. The sheath composed of a hydrophilic resin is for taking up the flowable composition up to the inside of the antibacterial non-woven sheet when the flowable composition containing a cosmetic (cosmetic fluid) etc. is added to the antibacterial non-woven sheet As well as playing an important role, it plays a role to keep the large amount of cosmetic that has been incorporated into the antibacterial non-woven sheet from dripping when handling at the time of use.

エチレン−ビニルアルコール系共重合体より高いヤング率の樹脂で、エチレン−ビニルアルコール系共重合体との組み合わせにおける紡糸性に優れた樹脂はポリオレフィン系樹脂、ポリエステル系樹脂が挙げられるが、よりヤング率が高く、抗菌性不織布シートの収縮が抑制でき、作業性も良好となる点においてポリエステル系樹脂が最適と言える。   Resins with a higher Young's modulus than ethylene-vinyl alcohol copolymers, and resins excellent in spinnability in combination with ethylene-vinyl alcohol copolymers, include polyolefin resins and polyester resins; Polyester resin is optimal in that the shrinkage of the antibacterial non-woven fabric sheet can be suppressed and the workability can be improved.

抗菌性不織布シートの空隙率が維持でき、保液量が高く、不織布にコシが出て、湿潤時の作業性を良好とするためには、鞘芯型複合繊維が好ましく、且つ芯部の径が５〜１５μｍであることが好ましい。さらに好適には芯部の径が８〜１２μｍである。芯部には上述の通り疎水性樹脂、特にポリエステル系樹脂を用いるのが好ましい。芯部の径が５μｍ未満になると、繊維のコシが低下し、結果的に不織布の密度が上がり、流動性組成物の含浸量が低下するといった問題が生じやすくなるため好ましくない。さらには、不織布のコシも低下し特に流動性組成物を含浸した状態での広げ性、装着性が低下することもある。一方で、芯部の径が１５μｍを超えると繊維のコシが強くなりすぎるため、特に顔面を覆うように用いられる、化粧料を含む流動性組成物を含浸させて使用する含液シート（後述）では顔面への沿い性が低下する場合があり、さらに繊維の強いコシにより不織布密度が低下するため不織布内繊維間距離が遠くなりすぎ化粧料を繊維間で保持出来なくなって不必要に液を放出しやすくなってしまう。   In order to maintain the porosity of the antibacterial non-woven fabric sheet, maintain a large amount of liquid retention, to give stiffness to the non-woven fabric, and to improve the workability when wet, sheath-core type composite fiber is preferable, and the diameter of the core part Is preferably 5 to 15 μm. More preferably, the diameter of the core portion is 8 to 12 μm. As described above, it is preferable to use a hydrophobic resin, particularly a polyester resin, for the core. If the diameter of the core portion is less than 5 μm, the stiffness of the fiber is reduced, and as a result, the density of the non-woven fabric is increased, which tends to cause a problem of decreasing the amount of impregnation of the flowable composition. Furthermore, the stiffness of the non-woven fabric may also be reduced, and in particular, the spreadability and the mountability in the state of being impregnated with the flowable composition may be reduced. On the other hand, when the diameter of the core exceeds 15 μm, the stiffness of the fiber becomes too strong, so a liquid containing sheet (described later) which is used to impregnate a flowable composition containing a cosmetic, which is used particularly to cover the face In this case, the lineage to the face may decrease, and the density of the non-woven fabric decreases due to the strength of the fibers, and the inter-non-fiber distance in the non-woven fabric becomes too long to hold the cosmetic between the fibers and unnecessarily discharge the liquid It becomes easy to do.

また、本発明の抗菌性ＥＶＯＨ含有繊維の断面形状はどのようなものであってもよく、円形、または異形の形状とすることができる。異形断面の場合は、例えば、偏平形、楕円形、三角形、四角形、五角形、六角形、七角形、八角形などの多角形、Ｔ字状、Ｈ字状、Ｖ字状、ドッグボーン（Ｉ字状）、３〜８葉形などの多葉形などの任意の形状とすることができ、それらの中空断面状などであってもよい。   In addition, the cross-sectional shape of the antimicrobial EVOH-containing fiber of the present invention may be any shape, and may be circular or irregular. In the case of a deformed cross section, for example, a flat shape, an oval, a triangle, a quadrangle, a pentagon, a hexagon, a heptagon, a polygon such as octagon, a T shape, an H shape, a V shape, a dog bone (I shape Shape, multi-leaf shape such as 3 to 8 leaf shape, and the like, and may have a hollow cross-section shape or the like.

本発明に用いる抗菌性ＥＶＯＨ含有繊維の繊度は、用途に応じて、例えば、０．０１〜１００ｄｔｅｘの範囲から選択でき、好ましくは０．５〜３０ｄｔｅｘ、さらに好ましくは１．０〜１０ｄｔｅｘである。抗菌性ＥＶＯＨ含有繊維の繊度が０．０１ｄｔｅｘ未満の場合、繊維からの無機系抗菌微粒子の脱落が起きやすくなり、また、抗菌性ＥＶＯＨ含有繊維の繊度が１００ｄｔｅｘを超える場合、樹脂内部に存在する抗菌剤の性能が十分に発揮されなくなるほか、繊維のコシが強くなりすぎるため、特に顔面を覆うように用いられる、化粧料を含む流動性組成物を含浸させて使用する含液シート、特にフェイスマスク（後述）では顔面への沿い性が低下する場合があり、さらに繊維の強いコシにより不織布密度が低下するため不織布内繊維間距離が遠くなりすぎ化粧料を繊維間で保持できなくなって不必要に液を放出しやすくなってしまうため好ましくない。   The fineness of the antibacterial EVOH-containing fiber used in the present invention can be selected, for example, from the range of 0.01 to 100 dtex, preferably 0.5 to 30 dtex, and more preferably 1.0 to 10 dtex. When the denier of the antibacterial EVOH-containing fiber is less than 0.01 dtex, falling of inorganic antibacterial fine particles from the fiber is likely to occur, and when the denier of the antibacterial EVOH-containing fiber exceeds 100 dtex, the antibacterial present inside the resin Liquid performance sheet impregnated with a flowable composition containing a cosmetic, especially used to cover the face, is used, in particular, a face mask, because the performance of the agent is not sufficiently exerted and the fiber becomes too strong. In the case of (described later), the lineability to the face may be reduced, and the density of the non-woven fabric is reduced due to the strong stiffness of the fibers, and the inter-non-woven fabric distance becomes too large to hold the cosmetic between the fibers. It is not preferable because it becomes easy to release the liquid.

本発明に用いる抗菌性ＥＶＯＨ含有繊維、または該繊維を用いた繊維製品は、さらに、慣用の添加剤、例えば、安定剤（銅化合物などの熱安定剤、紫外線吸収剤、光安定剤、酸化防止剤など）、微粒子、着色剤、蛍光増白剤、帯電防止剤、難燃剤、消臭剤、可塑剤、潤滑剤、結晶化速度遅延剤などを含有していてもよい。これらの添加剤は、単独でまたは二種以上組み合わせて使用できる。これらの添加剤は、繊維中に含まれていてもよく、繊維集合体表面に担持されていてもよい。   The antimicrobial EVOH-containing fiber to be used in the present invention, or a fiber product using the fiber is further added to a conventional additive, for example, a stabilizer (a heat stabilizer such as a copper compound, a UV absorber, a light stabilizer, an antioxidant And the like), fine particles, colorants, fluorescent whitening agents, antistatic agents, flame retardants, deodorants, plasticizers, lubricants, crystallization rate retarders and the like. These additives may be used alone or in combination of two or more. These additives may be contained in the fiber or may be carried on the surface of the fiber assembly.

本発明に用いる抗菌性ＥＶＯＨ含有繊維の製造方法については、特に制限はないが、例えば疎水性樹脂との二成分での複合繊維とする場合には、各々の樹脂をそれぞれ別の押出機で溶融混練し、引き続き前記両樹脂を紡糸ヘッドに導き、そして同一の紡糸ノズルから吐出させ、引き取りローラーにて引き取ることで得ることができる。   The method for producing the antimicrobial EVOH-containing fiber used in the present invention is not particularly limited. For example, in the case of forming a bicomponent fiber with a hydrophobic resin, each resin is melted in a separate extruder. It can be obtained by kneading and subsequently introducing the two resins to a spinning head and discharging from the same spinning nozzle and taking it off with a take-up roller.

また、本発明に用いる抗菌性ＥＶＯＨ含有繊維は、通常延伸して使用されるが、その延伸方法は紡糸時にノズルから吐出された繊維を引き取りローラーで引き取る際に、熱ロール間で延伸する１ステップ法でも良いし、一度引き取ってから水浴や熱風炉中にて低速で熱延伸する２ステップ法を採用しても構わない。   In addition, the antibacterial EVOH-containing fiber used in the present invention is usually stretched and used, but the stretching method is a 1-step stretching between hot rolls when the fiber discharged from the nozzle at the time of spinning is taken up by a take-off roller. A two-step method may be adopted, in which the film is drawn once and then heat drawn at low speed in a water bath or a hot air oven.

前述の抗菌性ＥＶＯＨ含有繊維は肌触りと親水性に優れている。しかしながら、例えば、抗菌性ＥＶＯＨ含有繊維を１００％用いて抗菌性不織布シートとした場合、水性の流動性組成物を含浸したときの含浸性は優れているが、該繊維自身は吸水性が低いために、吸液速度が遅く、また保液した水性流動性組成物をシート空間内に保液することが難しい。よって、水性流動性組成物を含浸して使用する場合に、吸液に時間を要し作業性効率が低下したり、また一部の水性流動性組成物がシート内部から不必要に放出され流れ落ちて無駄になったりするため、本発明の抗菌性不織布シートは、抗菌性ＥＶＯＨ含有繊維を１００％は用いず、抗菌性ＥＶＯＨ含有繊維に溶剤紡糸セルロース系繊維を併用し、互いに交絡してなることが重要である。   The aforementioned antimicrobial EVOH-containing fibers are excellent in touch and hydrophilicity. However, for example, when 100% of antimicrobial EVOH-containing fibers are used to make an antimicrobial nonwoven fabric sheet, the impregnating properties when impregnated with an aqueous flowable composition are excellent, but the fibers themselves have low water absorption. In addition, the liquid absorption speed is low, and it is difficult to retain the retained aqueous flowable composition in the sheet space. Therefore, when it is used by impregnating the aqueous flowable composition, it takes time to absorb the liquid and the efficiency of workability is lowered, and some of the aqueous flowable composition is unnecessarily released from the inside of the sheet and flowed off The antibacterial nonwoven fabric sheet of the present invention does not use 100% of the antibacterial EVOH-containing fiber, but uses the antibacterial EVOH-containing fiber in combination with the solvent-spun cellulose-based fiber and is entangled with each other. is important.

本発明の抗菌性不織布シートにおいて、抗菌性ＥＶＯＨ含有繊維が３０〜９０重量％含まれることが好ましく、より好ましくは４０〜９０重量％である。抗菌性ＥＶＯＨ含有繊維の含有率の下限値は、さらに好ましくは５０重量％以上、特に好ましくは６０重量％以上であり、抗菌性ＥＶＯＨ繊維の含有率の上限値は、さらに好ましくは８０重量％以下、またさらに好ましくは７５重量％以下、特に好ましくは７０重量％以下である。また、溶剤紡糸セルロース系繊維は１０〜７０重量％含まれることが好ましく、より好ましくは１０〜６０重量％である。溶剤紡糸セルロース系繊維の含有率の下限値は、さらに好ましくは２０重量％以上、またさらに好ましくは２５重量％以上、特に好ましくは３０重量％以上であり、溶剤紡糸セルロース系繊維の含有率の上限値は、さらに好ましくは５０重量％以下、特に好ましくは４０重量％以下である。   In the antibacterial nonwoven fabric sheet of the present invention, the content of the antibacterial EVOH-containing fiber is preferably 30 to 90% by weight, and more preferably 40 to 90% by weight. The lower limit of the content of the antimicrobial EVOH-containing fiber is more preferably 50% by weight or more, particularly preferably 60% by weight or more, and the upper limit of the content of the antimicrobial EVOH fiber is more preferably 80% by weight or less Also preferably, it is at most 75 wt%, particularly preferably at most 70 wt%. Moreover, it is preferable that 10 to 70 weight% of solvent spinning cellulose type fiber is contained, More preferably, it is 10 to 60 weight%. The lower limit of the content of the solvent-spun cellulose fiber is more preferably 20% by weight or more, still more preferably 25% by weight or more, particularly preferably 30% by weight or more, and the upper limit of the content of the solvent-spun cellulose fiber The value is more preferably at most 50% by weight, particularly preferably at most 40% by weight.

抗菌性ＥＶＯＨ含有繊維の含有率が３０重量％未満であると、特にウェット時においてセルロース系繊維の独特のきしみ感が強くなり、得られた抗菌性不織布シートの滑らかさが低減する。また、抗菌性ＥＶＯＨ含有繊維の含有率が３０重量％未満であると、流動性組成物を繊維内に取り込んでしまう比率が上がり、肌への有効利用が妨げられる。一方、抗菌性ＥＶＯＨ含有繊維の含有率が９０重量％を超えると含浸力、特に含浸速度が低下すると共に、流動性組成物保持力が低下し、流動性組成物がシート内部から不必要に放出され流れ落ちて無駄になるため好ましくない。   When the content of the antibacterial EVOH-containing fiber is less than 30% by weight, the unique squeakiness of the cellulose-based fiber becomes strong particularly when wet, and the smoothness of the obtained antibacterial non-woven sheet is reduced. In addition, when the content of the antimicrobial EVOH-containing fiber is less than 30% by weight, the ratio of incorporating the flowable composition into the fiber is increased, and the effective use to the skin is hindered. On the other hand, when the content of the antimicrobial EVOH-containing fiber exceeds 90% by weight, the impregnating power, in particular, the impregnation speed decreases, and the flowable composition retention ability decreases, and the flowable composition is unnecessarily released from the inside of the sheet It is not preferable because it will be washed away and be wasted.

本発明に用いる溶剤紡糸セルロース系繊維は、従来のビスコースレーヨン、銅アンモニアレーヨンなどのように、セルロースを一旦セルロース誘導体に化学的に変換させたのち再度セルロースに戻す、いわゆる再生セルロース系繊維と異なり、セルロースを化学的に変化させることなく、単に溶剤に溶解して得られる溶液からセルロースを析出させた繊維（精製セルロース系繊維）を意味する。   Unlike the conventional viscose rayon, copper ammonia rayon, etc., the solvent-spun cellulose fiber used in the present invention is different from a so-called regenerated cellulose fiber in which cellulose is once chemically converted to a cellulose derivative and then returned to cellulose again. Also, it means fibers (purified cellulose fibers) in which cellulose is precipitated from a solution obtained by simply dissolving cellulose in a solvent without chemically changing the cellulose.

本発明に用いる溶剤紡糸セルロース系繊維の好ましい例としては、セルロースをアミンオキサイドに溶解させた紡糸原液を水中に乾湿式紡糸してセルロースを析出させ得られた繊維をさらに延伸する方法で製造されたセルロース系繊維が挙げられる。このような繊維の代表例としてリヨセルが挙げられ、オーストリアのレンチング社より「テンセル」（登録商標）の商品名で販売されている。このような繊維は、汎用的に使用されている再生セルロース系繊維と異なり、丸あるいは楕円の断面形状を有しているため、対人に使用時に肌をいためる危険性が低いため非常に好ましい。さらに、ビスコースレーヨン繊維はウェット条件下で繊維強力が低下するため、この繊維を混合して得られたシートでは薬液などを含む流動性組成物を含浸したウェットな状態では、変形が発生し作業性が低下する。また、例えば繊維と化粧料を含む流動性組成物とを一体とすることからなる含液シート（後述）として使用した場合では装着性が劣る。それに対して、本発明の抗菌性不織布シートはウェット条件下でも強力低下がほとんど発生しないため、形態変化が発生せず装着性に優れるため非常に好ましい。   As a preferable example of the solvent-spun cellulose-based fiber used in the present invention, it is manufactured by a method of further stretching the fiber obtained by dry-wet spinning a stock solution of cellulose dissolved in amine oxide in water to precipitate cellulose. A cellulose fiber is mentioned. A typical example of such a fiber is Lyocell, which is sold under the trade name "Tensel" (registered trademark) by Lenzing, Austria. Such a fiber is very preferable because it has a round or elliptical cross-sectional shape, unlike the regenerated cellulose-based fiber that is generally used, and it has a low risk of damaging the skin when it is used by another person. Furthermore, since the viscose rayon fiber has a decrease in fiber strength under wet conditions, the sheet obtained by mixing the fibers is deformed in a wet state impregnated with a fluid composition containing a drug solution etc. Sex is reduced. Moreover, for example, when it is used as a liquid-containing sheet (described later) formed by integrating a fiber and a flowable composition containing a cosmetic, the wearing property is inferior. On the other hand, the antibacterial non-woven sheet of the present invention is very preferable because it hardly causes a decrease in strength even under wet conditions, and therefore, the form change does not occur and the wearability is excellent.

通常、該溶剤紡糸セルロース系繊維は、ビーター、リファイナー、高速離解機などにより叩解して繊維をフィブリル化させるケースが多いが、本発明においては、繊維のフィブリル化により、細かい繊維が顔面に付着することを防ぐために実質的にフィブリル化していない溶剤紡糸セルロース系繊維を用いることが望ましい。   Usually, the solvent-spun cellulose-based fiber is often beaten by a beater, refiner, high-speed disintegrator or the like to fibrillate the fiber, but in the present invention, fine fiber adheres to the face by fibrillation of the fiber. It is desirable to use substantially non-fibrillated solvent-spun cellulosic fibers to prevent this.

該溶剤紡糸セルロース系繊維の単繊維繊度は、特に限定するものではないが、特に皮膚へ接触したときの風合は柔らかい方が好まれることが多いため、１〜３ｄｔｅｘであることが好ましく、より好ましくは１〜２ｄｔｅｘ、さらに好ましくは１．３〜１．７ｄｔｅｘである。単繊維繊度が３ｄｔｅｘを超えると、皮膚への肌触りが悪くなったり、化粧料を含む流動性組成物の吸液性さらには保液性などが劣ったりする場合がある。一方で、１ｄｔｅｘ未満になると不織布密度が高くなり繊維間空隙が減少するため、流動性組成物の含浸量が低下するため好ましくない。   The single fiber fineness of the solvent-spun cellulose-based fiber is not particularly limited, but in particular, when it comes in contact with the skin, the softness is often preferred, so 1 to 3 dtex is preferable. Preferably it is 1 to 2 dtex, more preferably 1.3 to 1.7 dtex. When the single fiber fineness exceeds 3 dtex, the touch on the skin may be deteriorated, or the liquid absorption and further liquid retention of the flowable composition containing the cosmetic may be deteriorated. On the other hand, if it is less than 1 dtex, the density of the non-woven fabric is increased and the inter-fiber voids are reduced, which is not preferable because the amount of impregnation of the flowable composition is reduced.

さらに、抗菌性ＥＶＯＨ含有繊維と溶剤紡糸セルロース系繊維の混合比や、抗菌性エチレン−ビニルアルコール系共重合体の樹脂極性によって、抗菌性不織布シート全体の極性を調整することができ、流動性組成物の含浸量と肌触りを決定できるが、それぞれの繊維の太さを調節することで、流動性組成物の含浸量に影響を与えることなく、肌触りの調節が可能となる。すなわち溶剤紡糸セルロース系繊維を太くすると、同一目付では、該セルロース系繊維本数が少なくなると共に、表面積も少なくなり、できた抗菌性不織布シートの親水性が低下する。逆に該セルロース系繊維を細くすると該抗菌性不織布シートの親水性が増加する。また、肌触りについては、同じく該セルロース系繊維を太くすることにより粗くなる。   Furthermore, the polarity of the entire antibacterial non-woven sheet can be adjusted by the mixing ratio of the antibacterial EVOH-containing fiber and the solvent-spun cellulose-based fiber, and the resin polarity of the antibacterial ethylene-vinyl alcohol copolymer, and the flowable composition Although it is possible to determine the amount of impregnation of the material and the touch, by adjusting the thickness of each fiber, it is possible to adjust the touch without affecting the amount of impregnation of the flowable composition. That is, when the solvent-spun cellulose-based fiber is thickened, the number of the cellulose-based fiber decreases and the surface area decreases with the same fabric weight, and the hydrophilicity of the resulting antibacterial non-woven sheet decreases. Conversely, when the cellulose-based fibers are thinned, the hydrophilicity of the antibacterial non-woven sheet is increased. In addition, with regard to the touch, it is also roughened by thickening the cellulose fiber.

例えば、抗菌性ＥＶＯＨ含有繊維と溶剤紡糸セルロース系繊維の混合比が６０：４０で、抗菌性エチレン−ビニルアルコール系共重合体のエチレン成分が５０モル％、ケン化度９８％であるとき、顔などを被覆して用いる抗菌性不織布シートと化粧料を含む流動性組成物とを一体化させた含液シート（特に、フェイスマスク）（後述）の用途では溶剤紡糸セルロース系繊維に対する抗菌性ＥＶＯＨ含有繊維の太さの比は０．３〜３．０の範囲であることが好ましく、０．３〜２．０の範囲であることがより好ましい。   For example, when the mixing ratio of the antibacterial EVOH-containing fiber to the solvent-spun cellulose-based fiber is 60:40, and the ethylene component of the antibacterial ethylene-vinyl alcohol copolymer is 50 mol%, and the saponification degree is 98% In a liquid-containing sheet (in particular, a face mask) (described later) in which an antibacterial non-woven sheet and a flowable composition containing a cosmetic material are integrated to coat and use an antibacterial EVOH containing solvent-spun cellulose fiber The fiber thickness ratio is preferably in the range of 0.3 to 3.0, and more preferably in the range of 0.3 to 2.0.

抗菌性ＥＶＯＨ含有繊維と溶剤紡糸セルロース系繊維の繊維長については、５〜６０ｍｍの範囲が好適である。抗菌性ＥＶＯＨ含有繊維および溶剤紡糸セルロース系繊維の繊維長が長すぎると、繊維同士の均一な交絡が困難となり、特に両繊維の交絡が不充分であると抗菌性不織布シートの均一性が不充分となって、肌触りが悪化するだけでなく、流動性組成物の吸液と放出の効率が低下するといった問題が生じるので好ましくない。また、抗菌性ＥＶＯＨ含有繊維および溶剤紡糸セルロース系繊維の繊維長が短すぎると抗菌性不織布シートからの繊維の抜けが発生しやすくなるだけでなく、柔軟性、伸縮性が低下するので好ましくない。このような観点から本発明に用いる抗菌性ＥＶＯＨ含有繊維および溶剤紡糸セルロース系繊維の繊維長は、好ましくは５〜６０ｍｍであり、さらに好ましくは１０〜５０ｍｍである。また、溶剤紡糸セルロース系繊維と抗菌性ＥＶＯＨ含有繊維の繊維長の比は０．５〜２が好ましく、０．８〜１．５であればなお良い。   The fiber length of the antimicrobial EVOH-containing fiber and the solvent-spun cellulose fiber is preferably in the range of 5 to 60 mm. When the fiber length of the antibacterial EVOH-containing fiber and the solvent-spun cellulose fiber is too long, it is difficult to uniformly intermingle the fibers, and when the entanglement of both the fibers is insufficient, the uniformity of the antibacterial non-woven sheet is insufficient. As a result, not only the feel of the skin is deteriorated but also the efficiency of absorption and release of the fluid composition is lowered, which is not preferable. In addition, if the fiber length of the antibacterial EVOH-containing fiber and the solvent-spun cellulose-based fiber is too short, not only the release of the fiber from the antibacterial non-woven sheet is likely to occur, but the flexibility and the stretchability are reduced. From such viewpoints, the fiber length of the antimicrobial EVOH-containing fiber and the solvent-spun cellulose-based fiber used in the present invention is preferably 5 to 60 mm, more preferably 10 to 50 mm. In addition, the ratio of the fiber length of the solvent-spun cellulose-based fiber to the antibacterial EVOH-containing fiber is preferably 0.5 to 2, and more preferably 0.8 to 1.5.

本発明において、抗菌性ＥＶＯＨ含有繊維と、溶剤紡糸セルロース系繊維を均一に混綿した後にウェブ化し、水流絡合により交絡させて目的の抗菌性不織布シートとすることができるが、ウェブ形成に関しては、スパンボンド法あるいはメルトブロー法のような直接法、ステープル繊維を用いてカード法、エアレイド法などの乾式法、あるいは湿式法を用いて形成することが可能である。このうち、本発明の抗菌性不織布シートの製造方法としては、繊維の混合、及び流動性組成物を含浸する空間を確保することがより容易に行える点から、乾式法が最適である。この場合のステープル繊維ウェブとしては、ランダムウェブ、セミランダムウェブ、パラレルウェブ、クロスラップウェブなどが好ましく用いられる。該ウェブを形成するに当たり、前記した混率で抗菌性ＥＶＯＨ含有繊維と溶剤紡糸セルロース系繊維とが混綿されることが好ましい。   In the present invention, the antibacterial EVOH-containing fiber and the solvent-spun cellulose-based fiber can be uniformly blended and then formed into a web, and can be entangled by hydroentanglement to form an objective antibacterial non-woven sheet, but regarding web formation It is possible to form using a direct method such as a spun bond method or a melt blow method, a dry method such as a card method using staple fibers, an air laid method, or a wet method. Among them, the dry method is most preferable as the method for producing the antibacterial non-woven sheet of the present invention, from the viewpoint that mixing of fibers and a space for impregnating the flowable composition can be more easily performed. As the staple fiber web in this case, a random web, a semi-random web, a parallel web, a cross lap web, etc. are preferably used. In forming the web, it is preferable that the antibacterial EVOH-containing fiber and the solvent-spun cellulose-based fiber are mixed at the above-mentioned mixing ratio.

本発明の抗菌性不織布シートにおいて、表面が凹凸を有することが好ましく、上記のように、得られたウェブに対し水流絡合処理を施すことで構成繊維同士を交絡させると共に、表面に凹凸を形成させることができる。この凹凸は水流絡合時に所定の条件下において製造を実施することにより、抗菌性不織布シートの表面に形成されるものである。これにより不織布内の空隙だけでなく、この抗菌性不織布シートの表面の凹部に流動性組成物を保持することが可能になるため、必ずしも抗菌性不織布シートを厚くすることなく表面にも多くの化粧料を保持することが可能になる。さらにこの時、水流から繊維全体が吸水すると共に、水流の力により動きやすい溶剤紡糸セルロース系繊維の一部が水流方向、すなわち凸部高さ方向に延びる構造とすると同時に、親水性と共に親油性を示す抗菌性ＥＶＯＨ含有繊維は、特に疎水性樹脂との鞘芯型複合繊維とした場合、その芯部の疎水性、及び剛性のため、凸部高さ方向へは動き難いため、ほとんどの繊維が不織布面方向に延びる形になる。これら繊維は基本的には互いに混合した状態にあるため、本発明の抗菌性不織布シートは親水性と親油性を両立することとなり、この凹凸形状内に親水性、及び親油性流動性組成物のどちらもが保持できるのである。また、ここに保持される流動性組成物は不織布の組織内に入り込んでおらず、このため本発明の抗菌性不織布シートと化粧料を含む流動性組成物とが一体となった含液シートは、抗菌性不織布シートの表面に化粧料が存在することで非常に肌に移行しやすく、極めて良好な肌への移行性を発現するのである。また、化粧料が抗菌性不織布シートの表面の凹凸にある場合でも、繊維自体が親水性と親油性の両方の性質を有しているため、化粧料が流れ落ちる現象は発生しない。   In the antibacterial nonwoven fabric sheet of the present invention, the surface preferably has irregularities, and as described above, the obtained web is subjected to a hydroentanglement treatment to entangle constituent fibers with each other and to form irregularities on the surface. It can be done. The unevenness is formed on the surface of the antibacterial non-woven sheet by carrying out production under predetermined conditions at the time of hydroentanglement. This makes it possible to retain the flowable composition not only in the voids in the non-woven fabric but also in the recesses on the surface of the non-woven antimicrobial sheet. It will be possible to hold the fee. Further, at this time, the entire fiber absorbs water from the water flow, and a part of the solvent-spun cellulosic fiber which is easily moved by the force of the water flow extends in the water flow direction, that is, in the height direction of the convex portion. Particularly, when the antibacterial EVOH-containing fiber is a sheath-core type composite fiber with a hydrophobic resin, most fibers hardly move in the height direction of the convex portion because of the hydrophobicity and rigidity of the core portion. It becomes a form extending in the nonwoven fabric surface direction. Since these fibers are basically in the state of being mixed with each other, the antibacterial nonwoven sheet of the present invention is compatible with hydrophilicity and lipophilicity, and the hydrophilic and oleophilic flowable composition in the uneven shape is obtained. Both can hold. Moreover, the fluid composition held here does not penetrate into the structure of the non-woven fabric, and hence the liquid-containing sheet in which the antimicrobial non-woven sheet of the present invention and the fluid composition containing the cosmetic are integrated The presence of the cosmetic on the surface of the antibacterial non-woven sheet makes it very easy to move to the skin, and exhibits extremely good transferability to the skin. In addition, even when the cosmetic is on the unevenness of the surface of the antibacterial non-woven sheet, since the fiber itself has both hydrophilic and lipophilic properties, the phenomenon of the cosmetic does not run off does not occur.

上述した凹凸とは、凹部と凸部の高低差が０．１〜０．４ｍｍの範囲にあると共に０．０４〜０．５ｍｍのピッチで、一定方向に連続していることが好ましい。この高低差が０．１ｍｍ未満である場合は不織布表面が平滑になりすぎ、表面凹凸を利用して流動性組成物を保持することが出来なくなるため、含浸性が低下し好ましくない。さらに、面全体で肌と接触してしまうため、着用時にムレ感やベタツキ感が生じ好ましくない。また高低差が０．４ｍｍを超える場合は、流動性組成物を保持する部分が大きくなるため、保液量が向上するものの、凸部先端付近に溶剤紡糸セルロース系繊維の比率が高くなりやすく、この部分での吸液挙動が溶剤紡糸セルロース系繊維の性質に依存することとなるため、保液量が向上する一方で放液性が低下する可能性が高くなる。さらに表面の滑らかさが阻害され肌触りが低下し、着用感が低下するため好ましくない。また、ピッチが０．０４ｍｍ未満になると凹部が狭くなりすぎて化粧料を含む流動性組成物が入り込めず表面凹凸を有効に利用して流動性組成物を保持することが難しくなり好ましくない。さらにピッチが０．５ｍｍを超えると凸部を構成する部分の繊維間距離が広がりすぎて凹部に入り込んだ流動性組成物を保持することが難しくなり好ましくない。   The unevenness mentioned above is preferably continuous in a fixed direction with a pitch difference of 0.04 to 0.5 mm while the height difference between the concave and the convex portion is in the range of 0.1 to 0.4 mm. If the height difference is less than 0.1 mm, the surface of the non-woven fabric becomes too smooth and the flowable composition can not be held utilizing the surface irregularities, which is not preferable because the impregnation property is lowered. Furthermore, since the entire surface comes into contact with the skin, a sense of stuffiness and stickiness occur when wearing, which is not preferable. When the height difference exceeds 0.4 mm, the portion holding the flowable composition is large, so the liquid holding amount is improved, but the ratio of the solvent-spun cellulose fiber tends to be high near the tip of the convex portion, Since the liquid absorption behavior in this portion depends on the properties of the solvent-spun cellulose-based fiber, while the liquid retention amount is improved, the possibility that the liquid discharging property is reduced is increased. Furthermore, the smoothness of the surface is inhibited, the touch is reduced, and the wearing feeling is reduced, which is not preferable. If the pitch is less than 0.04 mm, the recesses become too narrow, and the flowable composition containing the cosmetic can not enter and it is difficult to effectively use the surface irregularities to hold the flowable composition, which is not preferable. Further, if the pitch exceeds 0.5 mm, the distance between fibers of the portion constituting the convex portion is too wide, and it is difficult to hold the flowable composition which has entered the concave portion, which is not preferable.

上述した不織布表面の凹凸は、あらかじめウェブを水流絡合により繊維同士を絡合されたシートについて処理できる。あらかじめ処理される水流絡合とは、ウェブを金属多孔板あるいは織物構造の支持体上にノズル径０．０８〜０．２ｍｍ、ピッチ０．４〜１ｍｍのノズルを１〜３列に配列したノズルプレートから、水圧１〜６ＭＰａ、より好ましくは２〜４ＭＰａの水流で、１回または複数回処理する方法が好適に挙げられる。   The irregularities on the surface of the non-woven fabric described above can be treated in advance on a sheet in which the web is intertwined with each other by hydroentanglement. The hydroentanglement to be treated in advance means a nozzle in which the nozzles are arranged in 1 to 3 rows with a nozzle diameter of 0.08 to 0.2 mm and a pitch of 0.4 to 1 mm on a porous metal plate or a support having a woven structure. Preferred is a method of treating the plate one or more times with a water flow at a water pressure of 1 to 6 MPa, more preferably 2 to 4 MPa.

上述した不織布表面の凹凸は、水流絡合処理の少なくとも最後の処理において、繊維の織り構造体上で水流処理により形成されるのが好ましい。織り構造の支持体として、経糸及び緯糸がそれぞれ線径０．０１〜１ｍｍが好ましく、より好ましくは０．０２〜０．５ｍｍのモノフィラメントから成り、織り構造体の厚みが０．１〜１ｍｍであるものを使用するのが好ましい。モノフィラメントの径が１ｍｍを超えると、経糸が緯糸の上に存在する箇所において、繊維が周囲に移動して、不織布表面に孔が開いてしまい表面の平滑性が劣るため好ましくない。さらに織り構造体上方から孔径０．０５〜０．３ｍｍ、より好ましくは０．０８〜０．２ｍｍのオリフィスが０．４〜１ｍｍの間隔で設けられたノズルから、水圧６〜１５ＭＰａ、より好ましくは８〜１０ＭＰａの柱状水流を前段階である程度絡合されたウェブに噴射するとよい。   The irregularities on the surface of the non-woven fabric described above are preferably formed by water flow treatment on the fiber woven structure in at least the final treatment of the hydroentanglement treatment. As a support of a woven structure, a warp and a weft each preferably have a wire diameter of 0.01 to 1 mm, more preferably a monofilament of 0.02 to 0.5 mm, and the thickness of the woven structure is 0.1 to 1 mm. It is preferred to use one. If the diameter of the monofilament exceeds 1 mm, the fibers move to the periphery at the location where the warp is present on the weft, and the surface of the non-woven fabric is unfavorably opened, resulting in poor surface smoothness. Furthermore, from the nozzle provided with an orifice with a hole diameter of 0.05 to 0.3 mm, more preferably 0.08 to 0.2 mm, from above the woven structure at a distance of 0.4 to 1 mm, the water pressure is 6 to 15 MPa, more preferably A columnar water stream of 8 to 10 MPa may be injected onto the partially entangled web in the previous stage.

このような水流絡合処理により、流動性組成物の保持に好適な凹凸を表面に持つ抗菌性不織布シートが得られる。   By such hydroentanglement treatment, an antibacterial non-woven sheet having on its surface irregularities suitable for holding the flowable composition can be obtained.

本発明の抗菌性不織布シートは、後述するように、水と一体化させて含水シートとしたり、化粧料を含む流動性組成物と一体化させて含液シートとしたりすることで、好適に用いることができる。本発明の抗菌性不織布シートを含液シートとして用いる場合、前記化粧料を含む流動性組成物の極性に応じて本発明に用いるエチレン−ビニルアルコール系共重合体の共重合組成を調節することで、該流動性組成物の含浸性を高めることができる。   The antimicrobial nonwoven fabric sheet of the present invention is suitably used by being integrated with water to form a water-containing sheet or integrated with a flowable composition containing a cosmetic to form a liquid-containing sheet, as described later. be able to. When the antimicrobial nonwoven fabric sheet of the present invention is used as a liquid-containing sheet, the copolymerization composition of the ethylene-vinyl alcohol copolymer used in the present invention is adjusted according to the polarity of the flowable composition containing the cosmetic. The impregnatability of the flowable composition can be enhanced.

すなわち親油性の前記流動性組成物を用いる場合は、エチレン組成の高い共重合体を用い、親水性の前記流動性組成物を用いる場合は、エチレンの組成を低い共重合体を用いることが好ましい。同様にケン化度によっても親水性は調節できる。さらに未ケン化のエステルの種類や水酸基の官能基修飾などによってケン化度だけでなく種々の流動体との親和性を調節することもできる。   That is, it is preferable to use a copolymer having a high ethylene composition when using the above-mentioned flowable composition, and to use a copolymer having a low ethylene composition when using the above-mentioned flowable composition having hydrophilicity. . Similarly, the hydrophilicity can be adjusted by the degree of saponification. Furthermore, not only the degree of saponification but also the affinity to various fluids can be adjusted by the type of unsaponified ester and the functional group modification of the hydroxyl group.

また溶剤紡糸セルロース系繊維の割合を調整することでも前記含浸性を高めることができる。すなわち親油性の流動性組成物を用いる場合は、溶剤紡糸セルロース系繊維の割合を低くすること、親水性の流動性組成物を用いる場合は、溶剤紡糸セルロース系繊維の割合を高くすることが好ましい。   The impregnation can also be enhanced by adjusting the proportion of the solvent-spun cellulose-based fiber. That is, when using a lipophilic flowable composition, it is preferable to lower the ratio of solvent-spun cellulose-based fibers, and when using a hydrophilic flowable composition, it is preferable to increase the ratio of solvent-spun cellulose-based fibers .

実際の含浸性は流動性組成物の粘度などによっても異なるが、肌触り、保液性などとのバランスも考慮して、エチレン−ビニルアルコール系共重合体の共重合組成、及び／または、溶剤紡糸セルロース系繊維の割合によって調節することができる。   The actual impregnating ability varies depending on the viscosity of the flowable composition, etc., but in consideration of the balance with the touch, the liquid retention, etc., the copolymer composition of the ethylene-vinyl alcohol copolymer, and / or the solvent spinning It can be adjusted by the proportion of cellulosic fibers.

このような性質を持つ、抗菌性ＥＶＯＨ含有繊維と溶剤紡糸セルロース系繊維を均一に混綿し、単一層とした上で、所定の繊維間空隙を有するよう、空隙率が８０〜９５％となるようにした水流絡合不織布とすることにより、軽量で、トータルとして親水性と親油性が高次元にバランスの取れた、油性成分と水性成分の両方を同程度に吸収しやすく放出しやすいウェブとすることが可能になるのである。   The antibacterial EVOH-containing fiber and the solvent-spun cellulose-based fiber having such properties are uniformly mixed and made into a single layer, and the porosity is 80 to 95% so as to have a predetermined interfiber space. By forming a hydroentangled non-woven fabric, it is possible to create a web which is lightweight, has a high degree of balance of hydrophilicity and lipophilicity as a total, and easily absorbs and releases both an oil component and an aqueous component to the same extent. Is possible.

本発明の抗菌性不織布シートはこの柔軟性、特にウェット状態における柔軟性により複雑な形状を有する表面に沿うことが可能になるのであるが、これは不織布の少なくとも一方向におけるウェット５０％伸長時の応力に相関しており、この値が５００ｇ／５０ｍｍ以下であることが好ましい。より好ましくは４００ｇ／５０ｍｍ以下であり、さらに好ましくは３００ｇ／５０ｍｍ以下である。この値が５００ｇ／５０ｍｍを超えると、顔の凹凸に基材の沿いにくくなり、顔全体への化粧料を補給し難くなり好ましくない。一方で、例えば交絡をさせない状態であったり、交絡が不十分な状態の不織布シートなどにおいて、ウェット５０％伸張時の応力が１００ｇ／５０ｍｍ未満となった場合には、不織布作製時の工程性が不良となったり、取り扱い性が悪くなるといったトラブルが発生することがあるため、本発明の抗菌性不織布シートには不適である。   The softness, in particular the softness in the wet state, of the antimicrobial nonwoven sheet of the present invention makes it possible to conform to a surface having a complicated shape, but this is at the time of the wet 50% elongation of the nonwoven in at least one direction. It correlates with stress, and it is preferable that this value is 500 g / 50 mm or less. More preferably, it is 400 g / 50 mm or less, still more preferably 300 g / 50 mm or less. If this value exceeds 500 g / 50 mm, it becomes difficult for the substrate to follow the unevenness of the face, which makes it difficult to replenish the cosmetic with the whole face, which is not preferable. On the other hand, for example, when the stress at the time of 50% wet expansion is less than 100 g / 50 mm in a non-woven sheet or the like in a state in which the entanglement is not performed or in a state in which the entanglement is insufficient, It is unsuitable for the antibacterial nonwoven fabric sheet of the present invention because problems such as defects and poor handleability may occur.

本発明の抗菌性不織布シートに適した目付は、３０〜１００ｇ／ｍ2の範囲が肌への密着性や、吸液性の点から好ましく、特に４０〜７０ｇ／ｍ2の範囲が好ましい。目付が３０ｇ／ｍ2に満たない場合は絶対繊維量が少なくなり、繊維間に吸液し保持できる流動性組成物量が極端に少なくなってしまうため好ましくない。また、１００ｇ／ｍ2を超える場合は繊維量が多くなりすぎ抗菌性不織布シートの厚みが厚くなりすぎるため、沿い性が低下し好ましくない。Basis weight suitable for the antibacterial nonwoven fabric sheet of the present invention, the range and adhesion to the skin 30 to 100 g / m 2, preferably from the viewpoint of the absorbent, in particular in the range of 40~70g / m 2 is preferred. When the weight per unit area is less than 30 g / m 2 , the absolute fiber amount is small, and the amount of the fluid composition which can be absorbed and held between the fibers is extremely small, which is not preferable. Moreover, when it exceeds 100 g / m 2 , the fiber amount is too large and the thickness of the antibacterial non-woven fabric sheet is too thick, so the running property is unfavorably reduced.

本発明の抗菌性不織布シートの見掛け密度は、特に制限されるものではないが、好ましくは０．０３〜０．２０ｇ／ｃｍ3、より好ましくは０．０５〜０．１７ｇ／ｃｍ3、さらに好ましくは０．０６〜０．１５ｇ／ｃｍ3、特に好ましくは０．０８〜０．１２ｇ／ｃｍ3である。見掛け密度が低すぎると、抗菌性不織布シートの液体保持能力が低くなり、使用時の取り扱いにおいても液だれが生じやすくなる。一方、抗菌性不織布シートの見掛け密度が高すぎると、保液量が低下する。The apparent density of the antibacterial nonwoven fabric sheet of the present invention is not particularly limited, but is preferably 0.03 to 0.20 g / cm 3 , more preferably 0.05 to 0.17 g / cm 3 , further preferably the 0.06~0.15g / cm 3, particularly preferably 0.08~0.12g / cm 3. If the apparent density is too low, the liquid-holding capacity of the non-woven antimicrobial sheet will be low and it will be prone to dripping during handling. On the other hand, when the apparent density of the antibacterial nonwoven fabric sheet is too high, the amount of liquid retention decreases.

本発明の抗菌性不織布シートの厚さは、特に制限されるものではないが、好ましくは１００〜３０００μｍ、より好ましくは２００〜２０００μｍ、さらに好ましくは３００〜１５００μｍ、さらにまた好ましくは４００〜１２００μｍ、特に好ましくは５００〜１０００μｍである。   The thickness of the antibacterial nonwoven sheet of the present invention is not particularly limited, but is preferably 100 to 3000 μm, more preferably 200 to 2000 μm, still more preferably 300 to 1500 μm, still more preferably 400 to 1200 μm, particularly Preferably it is 500-1000 micrometers.

また、本発明の抗菌性不織布シートは、目的の吸液性と共に放液性を同時に確保することが必要である。即ち本発明の抗菌性不織布シートが親水性及び親油性の両方を有する繊維を構成繊維としていることにより、両方の性質を有する液体が吸収、吸着されることで保持されるのであるが、これら液体のうち、親油性成分は主に抗菌性ＥＶＯＨ含有繊維部分が保持し、親水性成分は抗菌性ＥＶＯＨ含有繊維に一部保持されると共に大半が溶剤紡糸セルロース系繊維に保持されると考えることができる。そして、これら液体は繊維表面に保持されると共に、これ以上の量となるために繊維表面に直接保持できないものについては、同種の繊維（抗菌性ＥＶＯＨ含有繊維同士あるいは溶剤紡糸セルロース系繊維同士）に囲まれて形成された繊維空隙内に充填保持されることにより不織布構成繊維の吸着量以上の液量を確保可能になるのである。そこで、便宜上ここで述べた液体が充填保持される空隙の存在を明確にするために空隙率を用いる。本発明の抗菌性不織布シートは、空隙率が８０〜９５％であることが好ましい。さらに好ましくは８５〜９３％である。この空隙率が９５％を超える場合は、繊維間距離が広がりすぎて、流動性組成物を繊維の親水性部分により保持できなくなり好ましくない。また８０％未満の場合は繊維間距離が狭すぎて流動性組成物が不織布内に入り込めず吸液量が少なくなるため好ましくない。   Moreover, it is necessary for the antibacterial nonwoven fabric sheet of the present invention to simultaneously secure the liquid absorption property as well as the liquid discharge property. That is, when the antibacterial nonwoven fabric sheet of the present invention uses fibers having both hydrophilicity and lipophilicity as constituent fibers, liquids having both properties are held by being absorbed and adsorbed. Among them, it is considered that the lipophilic component is mainly retained by the antibacterial EVOH-containing fiber portion, and the hydrophilic component is partially retained by the antibacterial EVOH-containing fiber and the majority is retained by the solvent-spun cellulose-based fiber it can. These liquids are held on the fiber surface and can not be held directly on the fiber surface because they become more than this amount, the same kind of fibers (antibacterial EVOH-containing fibers or solvent-spun cellulose fibers) By filling and holding in the fiber void formed by being enclosed, it becomes possible to secure a liquid amount equal to or more than the adsorption amount of the nonwoven fabric constituent fiber. Therefore, for the sake of convenience, the porosity is used to clarify the existence of the void in which the liquid described herein is filled and held. The antibacterial nonwoven fabric sheet of the present invention preferably has a porosity of 80 to 95%. More preferably, it is 85 to 93%. If this porosity exceeds 95%, the distance between fibers is too large, and the flowable composition can not be held by the hydrophilic portion of the fibers, which is not preferable. On the other hand, if the amount is less than 80%, the distance between fibers is too narrow, the flowable composition can not enter into the non-woven fabric, and the amount of liquid absorption decreases, which is not preferable.

＜含液シート、フェイスマスク＞
本発明は、パラベンなどを含有しなくても優れた防腐性・抗菌性を有し、柔らかく肌触りがよく、且つ美容液などの化粧料を含む流動性組成物を含浸した状態で、指で押しても流動性組成物の戻りが速い含液シートおよびフェイスマスクについても提供する。すなわち、本発明者らは、特定の抗菌性エチレン−ビニルアルコール系共重合体を一成分とした抗菌性ＥＶＯＨ含有繊維を溶剤紡糸セルロース系繊維とともに互いに交絡させて、流動性組成物を吸収可能な抗菌性不織布シートを形成し、当該抗菌性不織布シートと流動性組成物とを一体化させた含液シートにおいて、厚み方向の圧縮に対する復位を制御することにより、美容液などの化粧料を含む流動性組成物を含浸した状態で、指で押しても、流動性組成物の戻りを早くできることをも見出した。Liquid-containing sheet, face mask
The present invention has excellent antiseptic and antibacterial properties even without containing parabens, is soft and has a good touch, and is pressed with a finger while impregnated with a fluid composition containing a cosmetic such as a cosmetic fluid. Also provided is a liquid containing sheet and face mask for quick return of the flowable composition. That is, the present inventors are capable of absorbing the flowable composition by intermingling the antibacterial EVOH-containing fiber containing the specific antibacterial ethylene-vinyl alcohol copolymer as one component together with the solvent-spun cellulose fiber. In a liquid-containing sheet in which an antibacterial nonwoven sheet is formed and the antibacterial nonwoven sheet and the flowable composition are integrated, the flow including a cosmetic such as a cosmetic liquid by controlling reversion to compression in the thickness direction. It has also been found that the flowable composition can be quickly returned even when pressed with a finger while being impregnated with the sex composition.

本発明の含液シートにおいて、流動性組成物は、水であってもよいし（この場合、「含水シート」と呼称する）、化粧料を含んでいてもよい。化粧料を含む流動性組成物を用いた場合、スキンケアシートに好適に用いることができ、特にフェイスマスクに用いることが好ましい。すなわち、本発明の抗菌性不織布シートは、流動性組成物を吸収させて使用するための用途、例えば、ナプキンやおむつなどの表面材、おむつライナー、ウェットティッシュなどの体液吸収用シート（または皮膚洗浄用シート）などにも用いることができるが、保液性と放出性とのバランスに優れ、容易に皮膚に密着できるため、美容成分や薬効成分などを含む流動性組成物を上述した本発明の抗菌性不織布シートに含浸させたシート（含液シート）を皮膚に密着させる用途、例えば、フェイスマスク、メイク除去シートまたはクレンジングシート、身体洗浄用シート（汗拭きシート、油取りシートなど）、冷却シート、薬用または治療用シート（かゆみ抑制シート、湿布など）などの各種スキンケアシートに用いるのが好ましく、指で押しても流動性組成物の戻りが速いため、フェイスマスクに用いるのが特に好ましい。   In the liquid-containing sheet of the present invention, the flowable composition may be water (in this case, referred to as "water-containing sheet") or may contain a cosmetic. When a flowable composition containing a cosmetic is used, it can be suitably used for a skin care sheet, and it is particularly preferable to use it for a face mask. That is, the antibacterial non-woven sheet of the present invention is used for absorbing and using a fluid composition, for example, a surface material such as a napkin or a diaper, a sheet for absorbing body fluid such as a diaper liner or a wet tissue (or skin washing Sheet, etc., but it is excellent in balance between liquid retention and releasability, and can be easily in close contact with the skin, so that the flowable composition of the present invention described above contains a cosmetic component, a pharmaceutically active component, etc. Applications that adhere the sheet (liquid-containing sheet) impregnated with the antibacterial non-woven sheet to the skin, for example, face mask, makeup removal sheet or cleansing sheet, body washing sheet (sweat wipe sheet, oil removal sheet, etc.), cooling sheet , It is preferable to use it for various skin care sheets such as medicated or therapeutic sheets (itch control sheets, compressibles etc) For even faster return of the flowable composition, particularly preferably used in a face mask.

本発明の含液シートは、使用時にこれらの流動性組成物を含浸させて使用するシートであってもよく、予め流動性組成物を含浸させて使用するシート（いわゆるウェットシート）であってもよい。   The liquid-containing sheet of the present invention may be a sheet impregnated with the flowable composition at the time of use, or may be a sheet previously impregnated with the flowable composition (so-called wet sheet) Good.

本発明の抗菌性不織布シートに流動性組成物を含浸させる用途においては、流動性組成物には特に制限はない。水、水溶液、水性エマルジョンなどの水性の流動性組成物、有機溶剤やこれらを媒体とする溶液、これらの混合物などが挙げられる。また良好に溶解または分散する種々の固体、液体、気体をこれらの流動性組成物に溶解、及び／または分散した流動性組成物も好適に用いられる。種々の有効成分を溶解、及び／または分散した流動性組成物によって機能性の優れた抗菌性不織布シートとすることができる。また、流動性組成物は、美容成分または薬効（効能）成分などの有効成分を含有する溶液または分散液（化粧料、乳液、美容液など）も含む。このうち、水性の流動性組成物や極性有機溶剤を含む流動性組成物などを含む親水性の流動性組成物が含浸性の観点から有利であり、人体への安全性などの点からも有利である。特に水性の流動性組成物は保液性の観点から最も有利である。極性有機溶剤とは極性官能基を有する種々の有機溶剤が挙げられ、極性官能基としては、水酸基、アルデヒド基、カルボキシル基、アルコキシカルボニル基、エーテル基、カルボニル基、アミノ基、ニトロ基、チオ水酸基、などが挙げられる。これら親水性の流動性組成物としては、例えば、水、低級脂肪族アルコール（例えば、エタノール、イソプロパノールなどのＣ1-6アルキルアルコールなど）、アルキレングリコール類（例えば、エチレングリコール、ジエチレングリコール、プロピレングリコールなど）などが挙げられる。また、不飽和高級脂肪酸類（例えば、オレイン酸、オレイルアルコールなど）、動植物系油（例えば、ホホバ油、オリーブ油、やし油、つばき油、マカデミアンナッツ油、アボカド油、トウモロコシ油、ゴマ油、小麦胚芽油、アマニ油、ひまし油、スクワランなど）、鉱物系油（例えば、流動パラフィン、ポリブテン、シリコーン油など）、合成系油（例えば、合成エステル油、合成ポリエーテル油など）なども好適に用いられる。The flowable composition is not particularly limited in the application of impregnating the antibacterial nonwoven sheet of the present invention with the flowable composition. Examples thereof include water, aqueous solutions, aqueous flowable compositions such as aqueous emulsions, organic solvents and solutions containing these as media, and mixtures thereof. In addition, flowable compositions in which various solids, liquids, and gases that dissolve or disperse well are dissolved and / or dispersed in these flowable compositions are also suitably used. The flowable composition in which various active ingredients are dissolved and / or dispersed can provide an antibacterial non-woven sheet with excellent functionality. The flowable composition also includes a solution or dispersion (cosmetics, emulsion, cosmetic solution, etc.) containing an active ingredient such as a cosmetic ingredient or a medicinal (efficacy) ingredient. Among them, a hydrophilic flowable composition including an aqueous flowable composition and a flowable composition containing a polar organic solvent is advantageous from the viewpoint of impregnation and is also advantageous from the viewpoint of safety to the human body, etc. It is. Particularly, an aqueous flowable composition is most advantageous from the viewpoint of liquid retention. The polar organic solvent includes various organic solvents having a polar functional group, and the polar functional group includes a hydroxyl group, an aldehyde group, a carboxyl group, an alkoxycarbonyl group, an ether group, a carbonyl group, an amino group, a nitro group and a thiohydroxy group , Etc. As these hydrophilic fluid compositions, for example, water, lower aliphatic alcohols (eg, C 1-6 alkyl alcohol such as ethanol, isopropanol etc.), alkylene glycols (eg ethylene glycol, diethylene glycol, propylene glycol etc.) And the like. In addition, unsaturated higher fatty acids (eg, oleic acid, oleyl alcohol etc.), animal and vegetable oils (eg, jojoba oil, olive oil, coconut oil, camellia oil, macadamian nut oil, avocado oil, corn oil, sesame oil, wheat) Germ oil, linseed oil, castor oil, squalane, etc., mineral oil (eg, liquid paraffin, polybutene, silicone oil etc.), synthetic oil (eg, synthetic ester oil, synthetic polyether oil etc.) are also suitably used. .

これらの流動性組成物は、単独でまたは二種以上組み合わせて使用できる。例えば、水やエタノールなどの親水性溶媒に対して、添加剤（油分）として液状油を組み合わせて使用してもよい。これらの流動性組成物のうち、通常、水、低級アルコールまたはこれらの混合物が使用され、好ましくは水及び／またはエタノール、より好ましくは水のみが使用される。例えば、水と低級アルコール（特にエタノール）とを組み合わせて使用する場合、両者の割合は、水／低級アルコール＝１００／０〜３０／７０、好ましくは１００／０〜５０／５０、さらに好ましくは１００／０〜７０／３０であり、特に好ましくは９９／１〜８０／２０である。   These flowable compositions can be used alone or in combination of two or more. For example, a liquid oil may be used as an additive (oil component) in combination with a hydrophilic solvent such as water or ethanol. Of these flowable compositions, generally, water, lower alcohols or mixtures thereof are used, preferably water and / or ethanol, more preferably only water. For example, when water and a lower alcohol (especially ethanol) are used in combination, the ratio of both is water / lower alcohol = 100/0 to 30/70, preferably 100/0 to 50/50, more preferably 100. / 0 to 70/30, particularly preferably 99/1 to 80/20.

流動性組成物には、慣用の添加剤、例えば、保湿剤またはエモリエント剤（例えば、ジプロピレングリコール、１，３−ブチレングリコール、ポリエチレングリコール、ポリオキシエチレン−ポリオキシプロピレンブロック共重合体、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンショ糖脂肪酸エステル、グリセリン、ヒアルロン酸ナトリウム、ポリオキシメチルグリコシド、ポリビニルアルコール、ポリビニルピロリドン、水溶性セルロースエーテル（メチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロースなど）、紫外線防止剤、界面活性剤、収斂剤、酵素類、清涼化剤、殺菌剤または抗菌剤、皮膚軟化剤（例えば、サリチル酸またはその誘導体、乳酸、尿素など）、抗酸化剤（例えば、トコフェロールまたはその誘導体、アントシアニンなどのポリフェノール類など）、美白剤（例えば、アスコルビン酸またはその誘導体、システイン、プラセンタエキス、アルブチン、コウジ酸、ルシノール、エラグ酸、カミツレ抽出物など）、制汗剤（例えば、アルミニウム化合物、亜鉛化合物、タンニンなどの収斂剤など）、肌荒れ防止剤（例えば、グリチルリチン酸塩、ビタミン類など）、抗炎症剤（例えば、アラントイン、グアイアズレン、グリチルリチン酸またはその塩、グリチルレチン酸またはその塩、ε−アミノカプロン酸、トラネキサム酸、イブプロフェン、インドメタシンなど）、血行促進剤（例えば、シャクヤク、ローズマリー、チョウジなど）、ビタミン類（例えば、ビタミンＡ、ビタミンＢ、ビタミンＣ、ビタミンＤ、ビタミンＥ、ビタミンＫなど）、アミノ酸（例えば、トリプトファン、システインなど）、細胞賦活剤（例えば、リボフラビン、ピリドキシン、ニコチン酸、パントテン酸、α−トコフェロール、またはこれらの誘導体、ユキノシタエキスなどの植物抽出物など）、香料（例えば、合成香料、精油、精油成分など）などが挙げられる。これらの添加剤は、単独でまたは二種以上組み合わせて使用できる。   For the flowable composition, conventional additives such as moisturizers or emollients (e.g., dipropylene glycol, 1,3-butylene glycol, polyethylene glycol, polyoxyethylene-polyoxypropylene block copolymer, polyoxy acid) Ethylene sorbitan fatty acid ester, polyoxyethylene sucrose fatty acid ester, glycerin, sodium hyaluronate, polyoxymethyl glycoside, polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose ether (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl (Eg methylcellulose), UV inhibitors, surfactants, astringents, enzymes, refreshing agents, disinfectants or antibacterial agents, emollients (eg For example, salicylic acid or its derivative, lactic acid, urea etc., antioxidant (eg tocopherol or its derivative, polyphenols such as anthocyanin etc.), whitening agent (eg ascorbic acid or its derivative, cysteine, placenta extract, arbutin, Kojic acid, rucinol, ellagic acid, chamomile extract etc., antiperspirant (eg aluminum compound, zinc compound, astringent agent such as tannin etc.), skin roughening agent (eg glycyrrhizinate, vitamins etc), anti Inflammatory agents (eg, allantoin, guaiazulene, glycyrrhizinic acid or salts thereof, glycyrrhetinic acid or salts thereof, ε-aminocaproic acid, tranexamic acid, ibuprofen, indomethacin etc.), circulation promoting agents (eg peony, rosemary, clove etc.) ), Vitamins (eg, vitamin A, vitamin B, vitamin C, vitamin D, vitamin E, vitamin K, etc.), amino acids (eg, tryptophan, cysteine etc.), cell activators (eg, riboflavin, pyridoxine, nicotinic acid, Pantothenic acid, α-tocopherol or derivatives thereof, plant extracts such as Yukinoshita extract, perfumes (eg, synthetic perfumes, essential oils, essential oil components, etc.), etc. These additives may be used alone or in combination. It can be used in combination with species.

これらの添加剤のうち、スキンケアシート用には、例えば、保湿剤、紫外線吸収剤、界面活性剤、清涼化剤、酵素類、収斂剤、殺菌剤または抗菌剤などが汎用される。特に、フェイスマスク（フェイスパック）では、例えば、親水性溶媒中に保湿剤やエモリエント剤などが配合されていてもよい。保湿剤及びエモリエント剤の合計割合は、例えば、溶液中０．１〜５０重量％、好ましくは１〜３０重量％、さらに好ましくは５〜２０重量％である。   Among these additives, for example, moisturizers, ultraviolet absorbers, surfactants, refreshing agents, enzymes, astringents, bactericides or antibacterial agents are widely used for skin care sheets. In particular, in the face mask (face pack), for example, a humectant, an emollient agent and the like may be blended in a hydrophilic solvent. The total proportion of the humectant and the emollient agent is, for example, 0.1 to 50% by weight, preferably 1 to 30% by weight, and more preferably 5 to 20% by weight in the solution.

これらの前記添加剤の割合は、用途に応じて適宜選択でき、例えば、水やエタノールなどの割合は、通常、添加剤を含む全流動性組成物中３０〜９９重量％、好ましくは４０〜９５重量％、さらに好ましくは５０〜９０重量％である。   The proportion of these additives can be appropriately selected according to the application, for example, the proportion of water, ethanol, etc. is usually 30 to 99% by weight, preferably 40 to 95% by weight in the total flowable composition containing the additives. % By weight, more preferably 50 to 90% by weight.

使用する流動性組成物の含浸量としては、所定の効果を得られれば特に限定はなく、使用者の目的によって適宜選択すればよいが、例えば本発明の提供する含水シートや化粧料を含む流動性組成物と抗菌性不織布シートとを一体化させた含液シートでは基材重量に対し２００〜１０００重量％がコスト、及び性能の面から好ましい。   The impregnation amount of the flowable composition to be used is not particularly limited as long as a predetermined effect can be obtained, and may be appropriately selected according to the purpose of the user, for example, the flow including the water-containing sheet and the cosmetic provided by the present invention In the liquid-containing sheet in which the property composition and the antibacterial non-woven sheet are integrated, 200 to 1000% by weight based on the weight of the base material is preferable in terms of cost and performance.

なお、抗菌性不織布シートと化粧料を含む流動性組成物とからなる本発明の含液シートにおいては、抗菌性不織布シートは充分な量の化粧料を保持可能な高い吸液性能を有していることが必要である。本発明においては、これを吸液速度と保液率を用いて表すものとする。   In the liquid-containing sheet of the present invention comprising the antibacterial non-woven sheet and the flowable composition containing the cosmetic, the antibacterial non-woven sheet has high liquid absorption performance capable of holding a sufficient amount of the cosmetic. Need to be In the present invention, this is expressed using a liquid absorption speed and a liquid retention rate.

まず、本発明の含液シートに好適な抗菌性不織布シートは優れた吸液性能を有していることが必要であり、好ましい吸液速度は、５秒以下である。より好ましくは３秒以下、さらに好ましくは２秒以下、特に好ましくは１．５秒以下である。吸液速度が５秒を超えると、化粧料を含む流動性組成物が含浸しにくく、特に各家庭で個人の化粧料を含む流動性組成物を含浸させて使用する場合では、流動性組成物が表面を流れ落ちる可能性があり、その結果、化粧料が抗菌性不織布シートに含浸されず無駄になり好ましくない。化粧料を含む流動性組成物としては、一般に油性の流動性組成物は粘性が高く、水性の流動性組成物は粘性が低い傾向にあり、粘性が低いと吸液速度は高まる傾向にあるので、前者では好ましい吸液速度は５秒以下であるが、後者では３秒以下である。   First, the antibacterial nonwoven fabric sheet suitable for the liquid-containing sheet of the present invention needs to have excellent liquid absorption performance, and a preferable liquid absorption speed is 5 seconds or less. More preferably, it is 3 seconds or less, still more preferably 2 seconds or less, and particularly preferably 1.5 seconds or less. When the liquid absorption speed exceeds 5 seconds, the flowable composition containing the cosmetic is difficult to be impregnated, particularly when the flowable composition containing the individual's cosmetic is impregnated and used in each home, the flowable composition Can flow down the surface, and as a result, the cosmetic is not impregnated into the antibacterial non-woven sheet, which is not preferable. As a flowable composition containing a cosmetic, an oil-based flowable composition generally has a high viscosity, an aqueous flowable composition tends to have a low viscosity, and a low viscosity tends to increase the liquid absorption speed. In the former, the preferable liquid absorption speed is 5 seconds or less, but in the latter 3 seconds or less.

化粧料を含む流動性組成物を用いた含液シートに好適な抗菌性不織布シートは、充分な化粧料を肌により多く供給可能であることが必要である。このため、化粧料を含む流動性組成物の抗菌性不織布シートへの保液量の指標となる不織布坪量に対する保液量の割合である保液率がより高いことが必要であり、好ましい保液率は９００％以上であり、より好ましくは１０００％以上である。保液率が低い抗菌性不織布シートでは目的量の化粧料を含む流動性組成物を含浸させるために、含浸量に応じて坪量や組成を変更した様々な抗菌性不織布シートを用意する必要が発生するが、本発明の抗菌性不織布シートでは１種類で様々な含浸量へ対応が可能である。   An antibacterial nonwoven fabric sheet suitable for a liquid-containing sheet using a flowable composition containing a cosmetic needs to be able to supply a sufficient amount of the cosmetic to the skin. For this reason, it is necessary that the liquid retention ratio, which is the ratio of the liquid retention amount to the nonwoven fabric basis weight, which is an indicator of the liquid retention amount of the flowable composition containing the cosmetic to the antibacterial non-woven sheet, be higher. The liquid rate is 900% or more, more preferably 1000% or more. In the case of an antimicrobial nonwoven sheet having a low liquid retention rate, in order to impregnate a fluid composition containing a target amount of a cosmetic, it is necessary to prepare various antimicrobial nonwoven sheets whose basis weight and composition are changed according to the amount of impregnation. Although it generate | occur | produces, in the antimicrobial nonwoven fabric sheet of this invention, it is possible to respond to various impregnation amount by one type.

また、本発明の含液シートを顔面に貼付した際に、化粧料を含む流動性組成物が不織布内で顔面に沿って流れ、ついには顎から滴下して衣料が汚れるなどのトラブルが発生しないことも重要である。本発明においては、この性能を液ダレ率であらわし、この値が３．５％以下であることが好ましい。より好ましくは、３％以下であり、さらに好ましくは２．５％以下である。   In addition, when the liquid-containing sheet of the present invention is applied to the face, the flowable composition containing the cosmetic flows along the face in the non-woven fabric, and finally drips from the jaws to prevent problems such as staining of clothes. It is also important. In the present invention, this performance is expressed by a liquid drip rate, and it is preferable that this value is 3.5% or less. More preferably, it is 3% or less, more preferably 2.5% or less.

そして、以上に述べたような方法により、抗菌性不織布シート中に多量に含浸され、滴下しないように保持された化粧料を含む流動性組成物が効率良く肌に移行することが極めて重要である。本発明においてはこれを放出率としてあらわし、この値は９５％以上が望ましい。放出率が９５％未満であると有効な化粧料が繊維内に取り込まれ肌へ有効に利用できなくなる。抗菌性不織布シートが保液し保持した化粧料を含む流動性組成物が放出される割合が９５％以上であることが好ましい。   And it is extremely important that the flowable composition containing the cosmetic which is impregnated in a large amount in the antibacterial non-woven sheet and held so as not to drip by the method as described above is efficiently transferred to the skin . In the present invention, this is expressed as a release rate, and this value is desirably 95% or more. If the release rate is less than 95%, effective cosmetics are incorporated into fibers and can not be effectively used on the skin. It is preferable that the ratio in which the flowable composition containing the cosmetic which the antibacterial nonwoven fabric sheet holds and holds is released is 95% or more.

特に本発明の含液シートは、化粧料を含む流動性組成物の含浸性、すなわち吸液速度と保液量、さらに液ダレ率、そして放出率において高い次元でバランスすることにより必ずしも高い目付を確保することなく、ウェット時のフィット性に優れ、さらに充分な化粧料を肌に供給可能な含液シートを実現できる。   In particular, the liquid-containing sheet of the present invention does not necessarily have a high basis weight by being balanced at a high level in the impregnation properties of the flowable composition containing the cosmetic, that is, the liquid absorption speed and the liquid holding amount, the liquid dripping rate and the release rate. It is possible to realize a liquid-containing sheet which is excellent in wet fit and which can supply sufficient cosmetic to the skin without securing it.

本発明の抗菌性不織布シートは、通常、流動性組成物を含浸させて使用するが、使用時にこれらの流動性組成物を含浸させて使用してもよく、また予め流動性組成物を含浸させもよい。前者の場合には、使用者が例えば化粧料を含む含液シートの用途では自分の好みの化粧料を選択して含浸させた含液シートとすることができるというメリットがある。また乾燥状態で供給できることで製品のパッケージを簡易とすることができる。   The antimicrobial non-woven sheet of the present invention is generally used by impregnating a flowable composition, but may be used by impregnating these flowable compositions at the time of use, and may be impregnated with a flowable composition in advance. It is also good. In the case of the former, there is an advantage that the user can use a liquid-containing sheet containing, for example, a cosmetic, to select and impregnate a cosmetic of his / her choice. Also, the ability to supply in a dry state can simplify the packaging of the product.

上述した含液シートに用いる場合、抗菌性不織布シートは、美容成分または薬効（効能）成分（例えば、保湿成分、クレンジング成分、制汗成分、香り成分、美白成分、血行促進成分、冷却成分、紫外線吸収成分、皮膚かゆみ抑制成分など）を含む流動性組成物を含浸するのに必要な濡れ性と保液するための空隙を有し、使用時の取り扱いにおいても液ダレすることなく、体の所定の部位（例えば顔）を覆うまで保持し、貼付または静置すると共に化粧料を少しずつ肌側に移行させる役割を有していることが好ましい。抗菌性不織布シートは、保液性に優れるとともに、適度なコシまたは弾性を有しており、流動性組成物を含浸したとき、圧縮に対する復位及び流動性組成物の戻りが速く、特に、上述したように抗菌性不織布シートを特定のヤング率を有する高弾性繊維で形成すると、流動性組成物の戻り性に優れるとともに、厚みも速やかに回復するため、圧縮していない箇所と同様の保液状態に短時間で回復できる。   When used in the liquid-containing sheet described above, the antibacterial non-woven sheet is a cosmetic or medicinal (effect) component (for example, moisturizing component, cleansing component, antiperspirant component, aroma component, whitening component, blood circulation promoting component, cooling component, UV component Have wettability required for impregnating a flowable composition containing an absorption component, a skin itching suppression component, etc. and a space for holding a liquid, and without dripping in handling at the time of use, the predetermined amount of the body Preferably, it has a role of holding until it covers the site (for example, the face), sticking or leaving it, and moving the cosmetic little by little to the skin side. The antibacterial nonwoven sheet is excellent in liquid retention and has appropriate stiffness or elasticity, and when impregnated with the flowable composition, the reversion to compression and the return of the flowable composition are fast, particularly, as described above. When the antibacterial non-woven fabric sheet is formed of high elastic fibers having a specific Young's modulus, the flowability of the composition is excellent in restitution and the thickness is also recovered rapidly, so the liquid retention state similar to the non-compressed area Can recover in a short time.

上述した圧縮に対する復位に関して、具体的には、流動性組成物を自重に対して９００重量％含浸させて２６０ｇ／ｃｍ2の荷重を１分間負荷して取り除いたとき、厚み方向の圧縮に対する復位が５分間で３５％以上（例えば、３５〜１００％）であることが好ましく、より好ましくは５０〜９９％（例えば、６０〜９５％）、さらに好ましくは６５〜９０％（特に７０〜８５％）である。復位が３５％未満であると、美容液などの流動性組成物が押圧部に充分に戻ることができない。なお、前記復位は、詳細には、後述する実施例に記載の方法で測定できる。Specifically, when the fluid composition is impregnated with 900% by weight of its own weight and removed by applying a load of 260 g / cm 2 for 1 minute, the reversion to compression in the thickness direction is It is preferable that it is 35% or more (for example, 35 to 100%) in 5 minutes, more preferably 50 to 99% (for example, 60 to 95%), still more preferably 65 to 90% (particularly 70 to 85%) It is. If the repositioning is less than 35%, a flowable composition such as a cosmetic solution can not fully return to the pressing portion. The repositioning can be measured in detail by the method described in the examples described later.

上述した流動性組成物の戻りに関して、具体的には、流動性組成物を自重に対して９００重量％含浸させて直径１．２ｃｍの円形状部分に荷重６２０ｇを１分間負荷して取り除いたとき、５分後の美容液の戻り率が４５％以上であってもよく、例えば、５０〜９９％、好ましくは６０〜９８％（例えば、６５〜９５％）、さらに好ましくは７０〜９２％（特に８０〜９０％）である。戻り率が低すぎると、押圧後における流動性組成物が不足し、フェイスマスクでは、美容液を肌に充分に浸透させることができない。なお、前記戻り率は、詳細には、後述する実施例に記載の方法で測定できる。   Specifically, with respect to the return of the flowable composition described above, when the flowable composition is impregnated with 900% by weight with respect to its own weight and a circular shape portion having a diameter of 1.2 cm is subjected to a load of 620 g for 1 minute and removed. , And 5% may be 45% or more, for example, 50 to 99%, preferably 60 to 98% (eg, 65 to 95%), more preferably 70 to 92% In particular, 80 to 90%). If the return rate is too low, the flowable composition will be insufficient after pressing, and with a face mask, the cosmetic solution can not sufficiently penetrate the skin. In addition, the said return rate can be measured by the method as described in the Example mentioned later in detail.

本発明の含液シートに用いる場合、抗菌性不織布シートは、湿潤時の柔軟性にも優れ、顔面などの皮膚に追随できるように、適度に絡合しており、ＪＩＳ Ｌ １９１３に準拠したウェット時の３０％伸長時応力（ウェット３０％伸長時応力）が、少なくとも一方向において、好ましくは０．５〜１０Ｎ／５ｃｍ、より好ましくは１〜８Ｎ／５ｃｍ、さらに好ましくは１．５〜５Ｎ／５ｃｍ、特に好ましくは２〜４Ｎ／５ｃｍである。ウェット３０％伸長時応力が小さすぎると、顔面などの皮膚に装着時に伸び過ぎて扱い難く、大きすぎると、皮膚に対する密着性が低下する。なお、前記３０％伸長時応力は、詳細には、後述の実施例に記載の方法で測定できる。   When used in the liquid-containing sheet of the present invention, the antibacterial non-woven sheet is excellent in softness in the wet state and appropriately entangled so that it can follow the skin of the face and the like, and is wet according to JIS L 1913 The stress at 30% elongation (wet stress at 30% elongation) is preferably 0.5 to 10 N / 5 cm, more preferably 1 to 8 N / 5 cm, still more preferably 1.5 to 5 N / at least in one direction. It is 5 cm, particularly preferably 2 to 4 N / 5 cm. When the wet 30% elongation stress is too small, it stretches too much when worn on the skin such as the face and is difficult to handle, and when it is too large, the adhesion to the skin is reduced. In addition, the said stress at the time of 30% elongation can be measured by the method as described in the below-mentioned Example in detail.

流動性組成物が水を含む場合、本発明の含水シートは、水の他に例えば上記の流動性組成物や有効成分の少なくとも１種類を含むことで機能を付加できる。これら流動性組成物や有効成分は水溶性である必要はないが、水との親和性の高いものは含水シートの均質性を高められるとともに、機能を付加する流動性組成物や有効成分を高い濃度で抗菌性不織布シートに含浸することが容易である。また水溶液、分散液、エマルジョンの状態で水と共に抗菌性不織布シートと一体化することが含水シートの均質性を高めるとともに生産効率的にも有利である。特に水溶液、水性分散液、水性エマルジョンは本発明の抗菌性不織布シートの溶剤紡糸セルロース系繊維との親和性が高く、抗菌性不織布シートにより高い濃度で一体化できるので高い機能を得られ、含水シートの均質性、生産効率性の上でも一層有利である。   When the flowable composition contains water, the water-containing sheet of the present invention can be added with a function by containing, for example, at least one of the above-described flowable composition and the active ingredient in addition to water. These fluid compositions and active ingredients do not need to be water-soluble, but those having high affinity with water can enhance the homogeneity of the water-containing sheet and increase the fluid compositions and active ingredients that add functions. It is easy to impregnate the antimicrobial non-woven sheet in concentration. In addition, it is advantageous from the viewpoint of production efficiency as well as the homogeneity of the water-containing sheet to be integrated with the antibacterial non-woven sheet together with water in the state of an aqueous solution, dispersion or emulsion. In particular, aqueous solutions, aqueous dispersions, and aqueous emulsions have high affinity for the solvent-spun cellulose-based fibers of the antibacterial non-woven sheet of the present invention, and can be integrated at a high concentration by the antibacterial non-woven sheet to obtain high functions. It is even more advantageous in terms of homogeneity and production efficiency.

本発明の含液シートに用いる化粧料を含む流動性組成物は、例えば溶液、分散液、エマルジョンなどの状態である。また例えば水や上記の流動性組成物の少なくとも１種類を含む。化粧料としては、化粧料自体が流動性を有する場合と、化粧料が固体などの形態で流動性が実質ないものを含む、少なくとも１種の化粧料機能を有する物質を含む。化粧料自体が流動性を有する場合は化粧料のみを流動性組成物として抗菌性不織布シートと一体化してもよいが、通常は他の液体と混合して流動性を高めることで流動性組成物を一体化する際の生産効率を高めると共に放出性も高める。化粧料と混合する液体は化粧料との親和性が高いことで抗菌性不織布シートにより高い濃度で一体化できるので高い機能を得られ、化粧料を含む流動性組成物と抗菌性不織布シートとを一体化させた含液シートの均質性、生産効率性の上でも一層有利である。用いる化粧料の機能としては特に制限はなく、通常知られている種々の機能を有する化粧料を１種または混合して用いることができる。   The flowable composition containing the cosmetic used in the liquid-containing sheet of the present invention is, for example, in the state of solution, dispersion, emulsion or the like. Also, it contains, for example, water and at least one of the above-mentioned flowable compositions. The cosmetic includes at least one substance having a cosmetic function, including the case where the cosmetic itself has fluidity, and the cosmetic which is in the form of a solid or the like but having substantially no fluidity. When the cosmetic itself has fluidity, only the cosmetic may be integrated with the antibacterial non-woven sheet as a flowable composition, but usually the flowable composition is mixed with another liquid to enhance the flowability. Enhance the production efficiency when integrating the The liquid to be mixed with the cosmetic can be integrated at a high concentration by the antibacterial non-woven sheet because the affinity with the cosmetic is high, so a high function can be obtained, and the flowable composition containing the cosmetic and the antibacterial non-woven sheet It is further advantageous in terms of the uniformity and production efficiency of the integrated liquid-containing sheet. There is no restriction | limiting in particular as a function of the cosmetics to be used, One type or mixture of cosmetics which have a various functions generally known can be used.

上述のように、本発明は、化粧料を含む流動性組成物と抗菌性不織布シートとを一体化させた含液シートを用いたフェイスマスクについても提供する。上述した特許文献１のように熱接着性成分を融着することで作製されたシートは、湿潤時の収縮は改善されるがシート全体が硬くなってしまい肌への沿い性が低下する。さらに、シート表面は親水性繊維を主体繊維としているため繊維内に含浸した薬液を取り込んでしまい、充分に拭き取り対象物に放出することができなくなったり、また、例えばフェイスマスクに代表される肌を被覆するシートなどの場合には、美容液のような有効成分が充分に放出することができなくなるといった問題が生じる。また、上述した特許文献２に開示された不織布シートは、柔軟性や保液性は優れるものの、シートのコシ（剛性）が小さく、フェイスマスクを顔に密着させるために、指で押すと、厚みの回復及び美容液（化粧料）の戻りが遅い。そのため、美容液を効率的に顔全体に行き渡らせるのが困難である。特に、フェイスマスクでは、美容液を補給したい箇所や密着が困難な箇所を指で押さえて密着させる必要があるにもかかわらず、従来のフェイスマスクでは、目的の部位において、フェイスマスクは密着するものの美容液の補給が不十分な状態となっていた。なお、フェイスマスクの肌（顔面）に対する沿い性を向上するために、肌の接触側に極細繊維で形成された層を配設したフェイスマスクや、立体的な構造を有するフェイスマスクなども開発されている。しかし、これらのフェイスマスクでも肌に対する沿い性は充分でなく、一度、貼り付けたフェイスマスクを指で押さえて接着させる行為を繰り返しているのが現状である。そのため、肌に押さえつける行為を繰り返すことにより、その都度、押さえた部分に蓄えられていた美容液が押し出されてしまい、美容液の不十分な状態が助長される結果となっている。   As described above, the present invention also provides a face mask using a liquid-containing sheet in which a flowable composition containing a cosmetic and an antibacterial non-woven sheet are integrated. The sheet produced by fusing the heat-adhesive component as described in Patent Document 1 described above improves the shrinkage when wet, but the entire sheet becomes hard and the runability to the skin decreases. Furthermore, since the sheet surface is mainly composed of hydrophilic fibers, the chemical solution impregnated in the fibers can be taken in, and it can not be sufficiently released to the object to be wiped off. In the case of the sheet | seat etc. which coat | cover, the problem that an active ingredient like a cosmetic fluid can not fully be released arises. Moreover, although the nonwoven fabric sheet disclosed by patent document 2 mentioned above is excellent in a softness | flexibility and liquid holding property, the stiffness (stiffness) of a sheet | seat is small, and in order to closely_contact a face mask with a face, thickness is pushed Recovery and cosmetic solution (cosmetics) return slowly. Therefore, it is difficult to efficiently spread the cosmetic solution over the entire face. In particular, in the face mask, although it is necessary to hold the part where it is desired to replenish the cosmetic solution or the part where adhesion is difficult to adhere with a finger, in the conventional face mask, the face mask adheres at the target part. Supply of beauty essence was insufficient. In addition, in order to improve the alignment of the face mask to the skin (face), a face mask with a layer of ultrafine fibers provided on the skin contact side, a face mask with a three-dimensional structure, etc. were also developed. ing. However, even with these face masks, the running property with respect to the skin is not sufficient, and at present, the action of pressing the face mask once attached with a finger to adhere is repeated. Therefore, by repeating the action of pressing on the skin, the cosmetic solution stored in the pressed portion is pushed out each time, which results in promoting an insufficient state of the cosmetic solution.

本発明によれば、このような従来の課題が解決されたフェイスマスクについても提供するものである。すなわち、本発明の抗菌性不織布シートは、上述のように、特定の抗菌性繊維と溶剤紡糸セルロース系繊維を用いて、流動性組成物を吸収可能な不織布を形成し、抗菌性不織布シートの厚み方向の圧縮に対する復位が制御されているため、抗菌性に優れ、且つ美容液などの液状成分を含浸した状態で指で押しても、流動性組成物の戻りが速い。また、流動性組成物を含浸した状態で指で押しても、厚みの回復も速い。そのため、例えば、フェイスマスクとして利用したとき、所望の部位に効率的に美容液を補給できる。さらに、エチレン−ビニルアルコール系共重合体で形成された鞘部を有する鞘芯型複合繊維を用いることにより、柔軟性、保液性、及び形態安定性を向上できる。   The present invention also provides a face mask in which such conventional problems are solved. That is, as described above, the antibacterial non-woven fabric sheet of the present invention forms a non-woven fabric capable of absorbing the flowable composition by using a specific antibacterial fiber and a solvent-spun cellulose-based fiber, and the thickness of the antibacterial non-woven fabric sheet Since the restitution to the compression of the direction is controlled, the antibacterial composition is excellent, and the return of the flowable composition is fast even if the finger is impregnated with a liquid component such as a cosmetic fluid. Moreover, even if it presses with a finger in the state which impregnated the fluid composition, thickness recovery is also quick. Therefore, for example, when it is used as a face mask, cosmetic solution can be efficiently supplied to a desired site. Furthermore, flexibility, liquid retention, and form stability can be improved by using a sheath-core type composite fiber having a sheath part formed of an ethylene-vinyl alcohol copolymer.

また本発明の抗菌性不織布シートは、皮膚に対して密着性に優れているため、フェイスマスクだけでなく、湿布などの皮膚に固定する含液シートとして特に適している。例えば、本発明の含液シートは、密着せずに浮いた部分を容易に矯正できるため、鼻の付け根など、微細な隙間にも密着可能であり、含液シートの有効成分を皮膚に有効に浸透できる。   Moreover, since the antibacterial nonwoven fabric sheet of the present invention is excellent in adhesion to the skin, it is particularly suitable not only for a face mask but also as a liquid-containing sheet to be fixed to the skin such as a compress. For example, since the liquid-containing sheet of the present invention can easily correct the floating portion without close contact, it can also be in close contact with fine gaps such as the base of the nose, and the active ingredient of the liquid-containing sheet is effectively applied to the skin. It can penetrate.

また、本発明の含液シートは、クレンジングシートや皮膚洗浄用シートなどにも適している。上述したように、本発明の含液シートは顔の微細な隙間にもシートを密着できるため、メイク（ファンデーション、白粉、口紅、アイメイクアップなどのメイクアップ化粧品など）を有効に除去できる。このように、本発明の含液シートは、液体含浸生体被膜シートとして利用する際、通常、流動性組成物を含液シートに含浸させて、生体の皮膚などに貼付または接触して使用されるため、抗菌性であることが重要である。なお、本発明の含液シートは、他の層と積層してもよく、例えば、有効成分の吸収を促進するために、肌と接触しない側に非多孔性のフィルムやシートを積層してもよい。   In addition, the liquid-containing sheet of the present invention is also suitable as a cleansing sheet, a sheet for skin cleansing, and the like. As described above, since the liquid-containing sheet of the present invention can closely adhere the sheet to minute gaps in the face, it is possible to effectively remove makeup (make-up cosmetics such as foundation, white powder, lipstick, eye makeup, etc.). As described above, when the liquid-containing sheet of the present invention is used as a liquid-impregnated biocoated sheet, the liquid-containing sheet is usually impregnated with the flowable composition and used by being attached to or in contact with the skin of a living body Therefore, it is important to be antimicrobial. In addition, the liquid-containing sheet of the present invention may be laminated with other layers, for example, even if a non-porous film or sheet is laminated on the side not in contact with the skin to promote absorption of the active ingredient. Good.

以下、実施例により本発明をさらに具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。なお、本実施例中における各物性値は、以下の方法により測定した。   Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples. In addition, each physical-property value in a present Example was measured by the following method.

［紡糸性」
繊維製造における紡糸工程において、紡糸した糸条を冷却固化した後、引き取りローラーを介してボビンに引き取る際、糸条が切れることなく引き取り可能な場合を「ａ：紡糸性良好」とし、糸条が切れて引き取りが不可能な場合、及び単糸レベルでの糸切れが生じて毛羽が発生する場合を「ｂ：紡糸性不良」として、紡糸性を評価した。Spinnability
In the spinning process in fiber production, when the spun yarn is cooled and solidified, it is taken to a bobbin via a take-up roller, and the case where the yarn can be taken without breakage is regarded as "a: good spinnability". The spinnability was evaluated as "b: poor spinnability" when it was broken and could not be taken up, and when yarn breakage occurred at the single yarn level and fuzz was generated.

［繊度］
ＪＩＳ Ｌ １０１５「化学繊維ステープル試験方法（８．５．１）」に準じて評価した。[Fineness]
It evaluated according to JIS L 1015 "chemical fiber staple test method (8.5.1)."

［強度］
ＪＩＳ Ｌ １０１５「化学繊維ステープル試験方法（８．７．１）」に準じて評価した。[Strength]
It evaluated according to JIS L 1015 "chemical fiber staple test method (8.7.1)."

［伸度］
ＪＩＳ Ｌ １０１５「化学繊維ステープル試験方法（８．７．１）」に準じて評価した。Elongation
It evaluated according to JIS L 1015 "chemical fiber staple test method (8.7.1)."

［ヤング率］
実施例７〜１１、比較例９〜１７について、ＪＩＳ Ｌ １０１５「化学繊維ステープル試験方法（８．１１）」に準じて評価した。[Young's modulus]
Examples 7 to 11 and Comparative Examples 9 to 17 were evaluated according to JIS L 1015 "Chemical fiber staple test method (8.11)".

［抗菌性］
実施例または比較例で得られた抗菌性不織布シート１５０ｇを、温度６０℃の水２０リットルを入れたバケツに投入して、３０分間精練処理した後、すすぎを３０分間行い、脱水後乾燥した。精練処理済の不織布シートをＪＩＳ Ｌ １９０２「繊維製品の抗菌性試験方法及び抗菌効果」に準拠して抗菌性を試験した。なお、試験菌として、黄色ブドウ球菌、及び肺炎桿菌を用い（菌液濃度１／２０ＮＢ、菌液滴下量０．２ｍｌ）、無加工検体には綿布を用い、下記式より殺菌活性値を算出した。なお、殺菌活性値が０以上の場合、制菌効果があると認められる。[Antibacterial]
150 g of the antibacterial non-woven fabric sheet obtained in the example or the comparative example was put into a bucket containing 20 liters of water at a temperature of 60 ° C., and after scouring treatment for 30 minutes, it was rinsed for 30 minutes, dried and dried. The antibacterial property of the scoured non-woven sheet was tested in accordance with JIS L 1902 "Testing method of antibacterial property and antibacterial effect of fiber products". In addition, Staphylococcus aureus and Klebsiella pneumoniae were used as test bacteria (fungus liquid concentration 1/20 NB, drop volume of bacteria drop 0.2 ml), cotton cloth was used as the unprocessed sample, and the bactericidal activity value was calculated according to the following equation. . In addition, when a bactericidal activity value is 0 or more, it is recognized that there is a bactericidal effect.

・静菌活性値：作用時間前後の生菌数の差を対数で表した値
静菌活性値＝Ｌｏｇ（Ａ／Ｂ）
Ａ＝無加工検体の接種直後に分散回収した菌数
Ｂ＝加工検体の１８時間培養後に分散回収した菌数
［厚さ］
実施例または比較例で得られた抗菌性不織布シートの厚さは、ＪＩＳ Ｌ １０９６「織物及び編物の生地試験方法（８．５）」に準じて測定した。厚み計は、Ｍｉｔｕｔｏｙｏ Ｃｏｒｐｏｒａｔｉｏｎ製デジマチックインジケーターを使用し、測定子１インチ（直径）、荷重１２ｇ／ｃｍ2で測定した。Bacteriostatic activity value: value representing the difference between the number of viable bacteria before and after the action time in logarithm
A = The number of bacteria dispersed and collected immediately after inoculation of the unprocessed sample B = The number of bacteria dispersed and collected after 18 hours of culture of the processed sample [Thickness]
The thickness of the antibacterial nonwoven fabric sheet obtained in the example or the comparative example was measured according to JIS L 1096 "Dough test method for woven and knitted fabric (8.5)". The thickness gauge was measured using a digitadic indicator manufactured by Mitutoyo Corporation with a 1-inch gauge (diameter) and a load of 12 g / cm 2 .

［目付］
実施例または比較例で得られた抗菌性不織布シートの目付は、ＪＩＳ Ｐ ８１２４「紙及び板紙 坪量測定方法」に準じて測定した。[Weight per unit]
The basis weight of the antibacterial non-woven fabric sheet obtained in Examples or Comparative Examples was measured in accordance with JIS P 8124 "Method of measuring basis weight of paper and paperboard".

［空隙率］
実施例または比較例で得られた抗菌性不織布シートの空隙率（％）は、不織布坪量（ｇ／ｍ2）、繊維比重（ｇ／ｃｍ3）、不織布厚さ（ｃｍ）から、下式で算出した。[Void ratio]
The porosity (%) of the antibacterial non-woven fabric sheet obtained in the example or the comparative example is calculated by the following formula based on the non-woven basis weight (g / m 2 ), the fiber specific gravity (g / cm 3 ) and the non-woven thickness (cm) Calculated by.

空隙率（％）＝１００−｛（不織布坪量／繊維比／不織布厚さ）／１００｝
［肌触り］
実施例または比較例で得られた抗菌性不織布シートを触った時の肌触りを、５名の被験者により、以下の基準に従って官能評価した。
＜評価基準＞
Ｘ：肌触りが良い
Ｙ：肌触りがやや良くない
Ｚ：肌触りが良くない
［吸液速度］
実施例または比較例で得られた抗菌性不織布シートの吸液速度は、ＪＩＳ Ｌ １９０７「繊維製品の吸水性試験方法（７．１．１（滴下法））」に準じて測定した。周りを把持し、中に浮いた状態の不織布の上方１ｃｍからビュレットで液体を一滴滴下し、表面の液滴の特別な光の反射をしなくなるまでの時間を測定した。滴下する液体により下記試験ＩとＩＩを実施した。Porosity (%) = 100-{(non-woven basis weight / fiber ratio / non-woven layer thickness) / 100}
[touch]
The touch when touching the antibacterial non-woven fabric sheet obtained in the example or the comparative example was organoleptically evaluated by five subjects according to the following criteria.
<Evaluation criteria>
X: Good feel Y: Not good feel Z: Not good feel [wicking speed]
The liquid absorption speed of the antibacterial nonwoven fabric sheet obtained in the example or the comparative example was measured according to JIS L 1907 "Test method of water absorption of fiber product (7.1.1 (dropping method))". Holding the periphery, 1 drop of liquid was dropped by buret from 1 cm above the non-woven fabric in a floating state, and the time until no special light reflection of the surface droplet was measured was measured. The following tests I and II were carried out according to the liquid to be dropped.

試験Ｉ：イオン交換水
試験ＩＩ：日清オイリオグループ株式会社製 食用調合油
［保液率］
実施例または比較例で得られた抗菌性不織布シートの保液率は、ＪＩＳ Ｌ １９０７「繊維製品の吸水性試験方法（７．２（吸水率法））」に準じて測定した。試験片を５ｃｍ角に切り出して重量Ｃ（ｇ）を測定する。その試験片を、化粧料を含む流動性組成物（株式会社エーサン製エーサンローラローション）の中に３０秒間浸した。その後試験片の一辺を持って液から取り出し１０秒後の重量Ｄ（ｇ）、さらに１分後の重量Ｅ（ｇ）を測定した。Test I: Ion-exchanged water Test II: Nisshin Oillio Group, Inc. prepared edible oil [Retention of liquid]
The liquid retention rate of the antibacterial nonwoven fabric sheet obtained in the example or the comparative example was measured in accordance with JIS L 1907 “Test method of water absorption of fiber product (7.2 (water absorption method))”. A test piece is cut out to 5 cm square, and the weight C (g) is measured. The test piece was immersed for 30 seconds in a flowable composition (a sun roller lotion made by Asan Co., Ltd.) containing a cosmetic. After that, one side of the test piece was held and taken out of the solution, and a weight D (g) after 10 seconds and a weight E (g) after 1 minute were measured.

保液率Ｆ（％）は下記式にて算出される。
保液率Ｆ（％）＝｛（Ｅ−Ｃ）／Ｃ｝×１００
［放出率］
実施例１〜６、比較例１〜８の抗菌性不織布シートの放出率は、以下のようにして測定した。前述の保液率を測定したサンプルを、１０ｃｍ角に切り出して約２．５ｇに裁量した濾紙（訂正濾紙Ｎｏ．２）間にはさみ、上から２ｋｇの重りを置いて１分間静置する。１分後サンプルを取り出し濾紙重量の増加重量Ｈ（ｇ）を測定する。The liquid retention rate F (%) is calculated by the following equation.
Liquid retention rate F (%) = {(EC) / C} x 100
[Emission rate]
The release rates of the antibacterial non-woven sheets of Examples 1 to 6 and Comparative Examples 1 to 8 were measured as follows. The sample for which the liquid retention rate was measured was cut into 10 cm square pieces, sandwiched between filter papers (corrected filter paper No. 2) cut to about 2.5 g, placed a 2 kg weight from the top, and allowed to stand for 1 minute. After one minute, the sample is taken out and the increase in filter paper weight H (g) is measured.

化粧料組成物を含む流動性組成物の放出率Ｇ（％）は下記式で算出した。
Ｇ（％）＝｛Ｈ／（Ｅ−Ｃ）｝×１００
［復位］
実施例７〜１１、比較例９〜１７の抗菌性不織布シートの原反復位は以下のように測定した。ＭＤ方向５ｃｍ×ＣＤ方向５ｃｍに切断したサンプルを準備し、サンプル重量に対し、９００％の美容液（カネボウ化粧品（株）製「フレッシェル エッセンスローション ＮＡ」）を含浸させ、図１に示すように、アクリル板（測定台）４の上にサンプル３を広げて静置し、レーザー変位計１で初期の厚みを測定した。次に、原反（不織布）の中心に２６０ｇ／ｃｍ2の荷重２を６０秒載置し、荷重を取り除いた直後から３００秒後までの変位を測定した。測定前の原反の厚みをＩ、荷重を取り除いた直後の厚みをＪ、荷重を取り除いて３００秒後の厚みをＫとしたとき、原反復位（％）を下記式に従って求めた。The release rate G (%) of the flowable composition containing the cosmetic composition was calculated by the following equation.
G (%) = {H / (E-C)} × 100
[Reposition]
The original repeat positions of the antibacterial nonwoven fabric sheets of Examples 7 to 11 and Comparative Examples 9 to 17 were measured as follows. Prepare a sample cut in the MD direction 5 cm × CD direction 5 cm, impregnate 900% cosmetic solution (Kanebo Cosmetics Co., Ltd. “Freschel Essence Lotion NA”) with respect to the sample weight, and as shown in FIG. The sample 3 was spread on an acrylic plate (measuring table) 4 and allowed to stand, and the initial thickness was measured by the laser displacement meter 1. Next, a load 2 of 260 g / cm 2 was placed on the center of the raw fabric (non-woven fabric) for 60 seconds, and the displacement from immediately after removing the load to 300 seconds after was measured. Assuming that the thickness of the raw fabric before measurement is I, the thickness immediately after removing the load is J, and the thickness after 300 seconds is K after removing the load, the original repetitive position (%) was determined according to the following equation.

原反復位（％）＝［（Ｉ−Ｋ）／（Ｉ−Ｊ）］×１００
［液戻り］
実施例７〜１１、比較例９〜１７の抗菌性不織布シートの原反への液戻りは以下のように測定した。ＭＤ方向５ｃｍ×ＣＤ方向５ｃｍに切断したサンプルを準備し、サンプル重量に対し、９００％の美容液（カネボウ化粧品（株）製「フレッシェル エッセンスローション ＮＡ」）を含浸させ、図２に示すように、アクリル板（測定台）１４の上にサンプル３を広げて静置し、直径１．２ｃｍの円形状の中央部に６２０ｇの荷重１２を６０秒載置し、荷重を取り除いた直後の美容液がない部分の幅を測定した。さらに、荷重を取り除いて３００秒後の美容液のない部分の幅を測定した。荷重を取り除いた直後の美容液のない部分の幅をＬ、荷重を取り除いて３００秒後の美容液のない部分の幅をＭとしたとき、原反への液戻り（％）を下記式に従って求めた。Original repeat position (%) = [(I−K) / (I−J)] × 100
[Liquid return]
The liquid return to the raw fabric of the antibacterial nonwoven fabric sheet of Examples 7-11 and Comparative Examples 9-17 was measured as follows. Prepare a sample cut in the MD direction 5 cm × CD direction 5 cm, impregnate 900% beauty fluid (Kanebo Cosmetics Co., Ltd. “Freschel Essence Lotion NA”) with respect to the sample weight, and as shown in FIG. , Spread sample 3 on acrylic plate (measuring table) 14 and let stand, place 620 g of load 12 for 60 seconds in the central part of circular shape with a diameter of 1.2 cm and immediately remove the load The width of the part without was measured. Furthermore, after removing the load, the width of the portion without cosmetic solution after 300 seconds was measured. Assuming that the width of the portion without cosmetic fluid immediately after removing the load is L, and the width of the portion without cosmetic fluid after 300 seconds after removing the load is M, the liquid return (%) to the original fabric according to the following formula I asked.

原反への液戻り（％）＝［（Ｌ−Ｍ）／Ｌ］×１００
［凹凸高低差］
実施例または比較例で得られた抗菌性不織布シートの表面における凹部と凸部の高低差は、キーエンス社製マイクロスコープＶＨ−６３００を使用して不織布断面を観察しとなりあう凹部と凸部の高低差を３箇所計測し平均することで算出した。Liquid return to raw fabric (%) = [(L-M) / L] × 100
[Revenness difference]
The height difference between the concave and the convex on the surface of the antibacterial non-woven fabric sheet obtained in the example or the comparative example corresponds to the height difference between the concave and the convex when the cross section of the non-woven fabric is observed using a microscope VH-6300 manufactured by Keyence Corporation. The difference was calculated by measuring and averaging three points.

［ウェット５０％伸長時応力］
実施例１〜６、比較例１〜８の抗菌性不織布シートのウェット５０％伸長時の応力は、島津製作所製オートグラフＡＧＳ−５０Ｄを使用し、試料巾５０ｍｍ、測定長１００ｍｍ、測定スピード２００ｍｍ／ｍｉｎで引張試験を行った時、伸度が５０％に到達した時点の強力値で示される。[Wet stress at 50% elongation]
The stress at 50% wet elongation of the antibacterial non-woven sheets of Examples 1 to 6 and Comparative Examples 1 to 8 is obtained by using Shimadzu autograph AGS-50D, sample width 50 mm, measurement length 100 mm, measurement speed 200 mm / When a tensile test is performed at min, it is indicated by the strength value when the elongation reaches 50%.

［ウェット３０％伸長時応力］
実施例７〜１１、比較例９〜１７の抗菌性不織布シートのウェット３０％伸長時応力は、ＪＩＳ Ｌ １９１３「一般不織布試験方法（６．３．２（湿潤時の引張強さ及び伸び率試験））」に記載の方法に準拠して測定した。具体的には、サンプルを２０℃±２℃の水中に自重で沈降するまで置くか、または１時間以上水中に沈めておいた後、浸漬液から取り出して速やかに３０％伸長時応力を測定した。[Wet stress at 30% elongation]
The wet 30% elongation stress of each of the antibacterial non-woven sheets of Examples 7 to 11 and Comparative Examples 9 to 17 is measured according to JIS L 1913 “General non-woven fabric test method (6.3.2 (Tensile strength at wet and elongation percentage test) It measured based on the method as described in ").". Specifically, the sample was placed in water at 20 ° C. ± 2 ° C. until it settled by its own weight, or after it was submerged in water for 1 hour or more, it was removed from the immersion liquid and the stress at 30% elongation was measured immediately. .

（参考例１：単独繊維）
（１）エチレン含有量４４モル％のエチレン−ビニルアルコール系共重合体９９重量部に、無機イオン交換体に銀イオンを担持させた銀系無機系抗菌微粒子（シナネンゼオミック社製「ＡＶ１０Ｄ」、平均粒径２．５μｍ、略立方体形）１重量部を配合して溶融押出機にて、紡糸温度２４０℃で紡出した。紡出した糸条を冷却固化した後、引き取りローラーを介してボビンに引き取った。(Reference example 1: single fiber)
(1) Silver-based inorganic antimicrobial particles ("AV10D" manufactured by Sinanen Zeomic Co., Ltd.), in which silver ions are supported on an inorganic ion exchanger in 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% One part by weight of a particle diameter of 2.5 μm and a substantially cubic shape was compounded and spun at a spinning temperature of 240 ° C. in a melt extruder. After the spun yarn was cooled and solidified, it was taken up on a bobbin via a take-up roller.

（２）次いで、この捲取糸を延伸温度８０℃にて、延伸倍率２倍で熱延伸し、油剤浴にて油剤を付与後、スタッファ型捲縮付与装置などの捲縮付与装置を用いて捲縮処理を行なった。捲縮付与処理に引き続き、繊維を１００℃の熱風で乾燥した後、５１ｍｍにカットすることで抗菌性ＥＶＯＨ含有繊維を得た（１．７ｄｔｅｘ、５１ｍｍ長、円形断面）。紡糸性、延伸性ともに良好であり、強度は２．４ｃＮ／ｄｔｅｘ、伸度は３３％であった。評価した結果を表１に示す。   (2) Next, this twill yarn is thermally drawn at a drawing temperature of 80 ° C. at a draw ratio of 2 times, and after an oil agent is applied in an oil agent bath, a crimper such as a stuffer-type crimp applicator is used I performed a crimp process. Subsequently to the crimp application treatment, the fiber was dried with hot air at 100 ° C., and cut to 51 mm to obtain an antimicrobial EVOH-containing fiber (1.7 dtex, 51 mm length, circular cross section). Both spinnability and stretchability were good, strength was 2.4 cN / dtex and elongation was 33%. The evaluated results are shown in Table 1.

（参考例２：複合繊維）
（１）エチレン含有量４４モル％のエチレン−ビニルアルコール系共重合体９９重量部に、無機イオン交換体に銀イオンを担持させた銀系無機系抗菌微粒子（シナネンゼオミック社製「ＡＶ１０Ｄ」、平均粒径２．５μｍ、略立方体形）１重量部を配合させた共重合体を鞘部とし、ポリエチレンテレフタレートから成る熱可塑性重合体を芯部として、溶融押出機から成る複合紡糸装置を用いて、丸断面口金にて、紡糸温度２８０℃、鞘芯重量比率５０：５０で鞘芯型に接合して紡出した。紡出した糸条を冷却固化した後、引き取りローラーを介してボビンに捲き取った。(Reference example 2: Composite fiber)
(1) Silver-based inorganic antimicrobial particles ("AV10D" manufactured by Sinanen Zeomic Co., Ltd.), in which silver ions are supported on an inorganic ion exchanger in 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% Using a composite spinning apparatus comprising, as a sheath, a copolymer compounded with 1 part by weight of a particle diameter of 2.5 μm and a substantially cubic shape) and a thermoplastic polymer consisting of polyethylene terephthalate as a core, a melt extruder In a round cross-section die, it was bonded to a sheath-core type at a spinning temperature of 280 ° C. and a sheath-core weight ratio of 50:50 and spun. After cooling and solidifying the spun yarn, it was wound onto a bobbin via a take-up roller.

（２）次いで、この捲取糸を延伸温度８０℃にて、延伸倍率２倍で熱延伸し、油剤浴にて油剤を付与後、スタッファ型捲縮付与装置などの捲縮付与装置を用いて捲縮処理を行なった。捲縮付与処理に引き続き、繊維を１００℃の熱風で乾燥した後、５１ｍｍにカットすることで抗菌性ＥＶＯＨ含有繊維を得た（３．４ｄｔｅｘ、５１ｍｍ長、鞘芯重量比率５０：５０、円形断面、芯部の径１２．５μｍ）。紡糸性、延伸性ともに良好であり、強度は２．９ｃＮ／ｄｔｅｘ、伸度は２７％であった。   (2) Next, this twill yarn is thermally drawn at a drawing temperature of 80 ° C. at a draw ratio of 2 times, and after an oil agent is applied in an oil agent bath, a crimper such as a stuffer-type crimp applicator is used I performed a crimp process. Subsequently to the crimp application treatment, the fiber was dried with hot air at 100 ° C. and cut to 51 mm to obtain an antimicrobial EVOH-containing fiber (3.4 dtex, 51 mm length, sheath core weight ratio 50: 50, circular cross section , Core diameter 12.5 μm). Both spinnability and stretchability were good, strength was 2.9 cN / dtex, and elongation was 27%.

（参考例３：複合繊維）
（１）参考例２の捲取糸を延伸温度８０℃にて、延伸倍率２倍で熱延伸し、油剤浴にて油剤を付与後、１０ｍｍにカットすることで下記、表１に示す抗菌性ＥＶＯＨ含有繊維を得た（３．４ｄｔｅｘ、１０ｍｍ長、鞘芯重量比率５０：５０、円形断面、芯部の径１２．５μｍ）。紡糸性、延伸性ともに良好であり、強度は２．９ｃＮ／ｄｔｅｘ、伸度は２７％であった。(Reference example 3: composite fiber)
(1) The twill yarn of Reference Example 2 is thermally drawn at a drawing temperature of 80 ° C. at a draw ratio of 2 times, applied with an oil agent in an oil agent bath, and cut into 10 mm to have the antibacterial properties shown in Table 1 below. An EVOH-containing fiber was obtained (3.4 dtex, 10 mm length, sheath-core weight ratio 50: 50, circular cross section, core diameter 12.5 μm). Both spinnability and stretchability were good, strength was 2.9 cN / dtex, and elongation was 27%.

（参考例４：単独繊維）
エチレン含有量８５モル％のエチレン−ビニルアルコール系共重合体９９重量部に、無機イオン交換体に銀イオンを担持させた銀系無機系抗菌微粒子（シナネンゼオミック社製「ＡＶ１０Ｄ」、平均粒径２．５μｍ、略立方体形）１重量部を配合して、参考例１と同様に製糸し、抗菌性ＥＶＯＨ含有繊維を得た（１．７ｄｔｅｘ、５１ｍｍ長、円形断面）。紡糸性、延伸性ともに良好であり、強度は３．１ｃＮ／ｄｔｅｘ、伸度は３８％であった。(Reference example 4: single fiber)
Silver-based inorganic antibacterial particles ("AV10D" manufactured by Sinanen Zeomic, average particle diameter 2) in which silver ions are supported on an inorganic ion exchanger in 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 85 mol%. 1 part by weight of approximately 5 μm, substantially cube shape was blended, and spun as in Reference Example 1 to obtain an antimicrobial EVOH-containing fiber (1.7 dtex, 51 mm in length, circular cross section). Both the spinnability and the stretchability were good, the strength was 3.1 cN / dtex and the elongation was 38%.

（参考例５：複合繊維）
繊度が５．５ｄｔｅｘとなるように樹脂の吐出量、引き取り速度、延伸倍率を調整した以外は、参考例２と同様に製糸し、抗菌性ＥＶＯＨ含有繊維を得た（３．４ｄｔｅｘ、５１ｍｍ長、鞘芯重量比率５０：５０、円形断面、芯部の径１６．０μｍ）。紡糸性、延伸性ともに良好であり、強度は２．９ｃＮ／ｄｔｅｘ、伸度は３６％であった。(Reference Example 5: Composite Fiber)
An antibacterial EVOH-containing fiber was obtained in the same manner as in Reference Example 2 except that the discharge amount of the resin, the take-up speed, and the draw ratio were adjusted so that the fineness was 5.5 dtex. Sheath core weight ratio 50: 50, circular cross section, core diameter 16.0 μm). Both spinnability and stretchability were good, strength was 2.9 cN / dtex, and elongation was 36%.

（参考例６：複合繊維）
（１）エチレン含有量４４モル％のエチレン−ビニルアルコール系共重合体を鞘部とし、ポリエチレンテレフタレートから成る熱可塑性重合体を芯部として、溶融押出機から成る複合紡糸装置を用いて、丸断面口金にて、紡糸温度２８０℃、鞘芯重量比率５０：５０で鞘芯型に接合して紡出した。紡出した糸条を冷却固化した後、引き取りローラーを介してボビンに捲き取った。(Reference Example 6: Composite Fiber)
(1) A round cross section using a composite spinning apparatus comprising a melt extruder and a thermoplastic polymer consisting of polyethylene terephthalate as a core, with an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% as a sheath At a spinneret, a sheath-core type was bonded and spun at a spinning temperature of 280 ° C. and a sheath-core weight ratio of 50:50. After cooling and solidifying the spun yarn, it was wound onto a bobbin via a take-up roller.

（２）次いで、この捲取糸を延伸温度８０℃にて、延伸倍率２倍で熱延伸し、油剤浴にて油剤を付与後、スタッファ型捲縮付与装置などの捲縮付与装置を用いて捲縮処理を行なった。捲縮付与処理に引き続き、繊維を１００℃の熱風で乾燥した後、５１ｍｍにカットすることでＥＶＯＨ含有繊維を得た（３．４ｄｔｅｘ、５１ｍｍ長、鞘芯重量比率５０：５０、円形断面、芯部の径１２．５μｍ）。紡糸性、延伸性ともに良好であり、強度は３．６ｃＮ／ｄｔｅｘ、伸度は３８％であった。   (2) Next, this twill yarn is thermally drawn at a drawing temperature of 80 ° C. at a draw ratio of 2 times, and after an oil agent is applied in an oil agent bath, a crimper such as a stuffer-type crimp applicator is used I performed a crimp process. Subsequently to the crimp application treatment, the fiber was dried with hot air at 100 ° C. and cut to 51 mm to obtain an EVOH-containing fiber (3.4 dtex, 51 mm length, sheath core weight ratio 50: 50, circular cross section, core Part diameter 12.5 μm). Both spinnability and stretchability were good, strength was 3.6 cN / dtex, and elongation was 38%.

［実施例１］
参考例１の抗菌性ＥＶＯＨ含有繊維を７０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、３８ｍｍ長）を３０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。Example 1
A card web of about 60 g / m 2 in basis weight was prepared by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 1 and 30% by weight of solvent-spun cellulose-based fiber (Lyocell manufactured by Lenzing Co., 1.7 dtex, 38 mm length) .

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９２％であった。各評価の結果を表１に示す。Then, a water stream was jetted to the card web and subjected to entanglement to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 92%. The results of each evaluation are shown in Table 1.

このシートは充分な保液性、放出性を有すると共に良好な肌触りを有していた。
［実施例２］
参考例２の抗菌性ＥＶＯＨ含有繊維を７０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、３８ｍｍ長）を３０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。This sheet had sufficient liquid retention and release and had a good touch.
Example 2
A card web of about 60 g / m 2 in basis weight was prepared by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 2 and 30% by weight of solvent-spun cellulose-based fiber (Lyocell, 1.7 dtex, 38 mm length) .

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９５％であった。各評価の結果を表１に示す。このシートは充分な保液性、放出性を有すると共に良好な肌触りを有していた。Then, a water stream was jetted to the card web and subjected to entanglement to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 95%. The results of each evaluation are shown in Table 1. This sheet had sufficient liquid retention and release and had a good touch.

［実施例３］
参考例３の抗菌性ＥＶＯＨ含有繊維を７０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、１２ｍｍ長）を３０重量％とし、水中に分散させ、湿式法にて目付約６０ｇ／ｍ2の湿式不織布を作製した。[Example 3]
70% by weight of the antibacterial EVOH-containing fiber of Reference Example 3 and 30% by weight of solvent-spun cellulose-based fiber (Lyocell, 1.7 dtex, 12 mm length) manufactured by Lenting Co., dispersed in water, and wetted to about 60 g A wet nonwoven fabric of 1 / m 2 was produced.

次いで、この湿式不織布に水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９０％であった。各評価の結果を表１に示す。このシートは充分な保液性、放出性を有すると共に良好な肌触りを有していた。Subsequently, a water stream was jetted to the wet nonwoven fabric and subjected to entanglement treatment to obtain a hydroentangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 90%. The results of each evaluation are shown in Table 1. This sheet had sufficient liquid retention and release and had a good touch.

［実施例４］
参考例５の抗菌性ＥＶＯＨ含有繊維を７０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、３８ｍｍ長）を３０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。Example 4
A card web having a basis weight of about 60 g / m 2 was prepared by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 5 and 30% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm length) .

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９７％であった。各評価の結果を表１に示す。このシートは充分な保液性、放出性を有すると共に良好な肌触りを有していた。Then, a water stream was jetted to the card web and subjected to entanglement to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 97%. The results of each evaluation are shown in Table 1. This sheet had sufficient liquid retention and release and had a good touch.

［実施例５］
実施例２で得たカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１５ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧８ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９９％であった。各評価の結果を表１に示す。このシートは充分な保液性、放出性を有する一方で肌触りはやや劣る結果となった。[Example 5]
The card web obtained in Example 2 was sprayed with a water stream and subjected to entanglement to obtain a water-entangled non-woven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.15 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 8 MPa was injected on two sides of each side to cause entanglement. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 99%. The results of each evaluation are shown in Table 1. While this sheet had sufficient liquid retention and release properties, the touch was slightly inferior.

［実施例６］
参考例２で得た抗菌性ＥＶＯＨ含有繊維を１０重量％、溶剤紡糸セルロース系繊維を９０重量％混綿し、目付６０ｇ／ｍ2のカードウェブを作製したこと以外は、実施例１と同様にして抗菌性不織布シートを得た。また得られた抗菌性不織布シートの空隙率は８８％であった。各評価の結果を表１に示す。このシートは保液性、放出性にやや劣るものの良好な肌触りを有していた。[Example 6]
Same as Example 1 except that 10% by weight of the antibacterial EVOH-containing fiber obtained in Reference Example 2 and 90% by weight of solvent-spun cellulose-based fiber were mixed and a card web with a basis weight of 60 g / m 2 was prepared. An antimicrobial non-woven sheet was obtained. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 88%. The results of each evaluation are shown in Table 1. This sheet had a good touch, although it was slightly inferior in liquid retention and release properties.

［比較例１］
無機イオン交換体に銀イオンを担持させた銀系無機系抗菌微粒子（シナネンゼオミック社製、平均粒径０．００８μｍ、略立方体形）を配合させた以外は、参考例２と同様に製糸しようとしたが、紡糸性不良により安定に製糸することが出来なかった。Comparative Example 1
An attempt was made to make a yarn in the same manner as in Example 2 except that a silver based inorganic antibacterial fine particle (Sinanen Zeomic Co., Ltd., average particle diameter 0.008 μm, substantially cubic shape) having silver ions supported on an inorganic ion exchanger was blended. However, stable spinning could not be performed due to poor spinnability.

［比較例２］
無機イオン交換体に銀イオンを担持させた銀系無機系抗菌微粒子（シナネンゼオミック社製、平均粒径２５μｍ、略立方体形）を配合させた以外は、参考例２と同様に製糸しようとしたが、紡糸性不良により安定に製糸することが出来なかった。Comparative Example 2
A yarn was tried to be produced in the same manner as in Reference Example 2 except that a silver based inorganic type antimicrobial fine particle (Sinanen Zeomic Co., Ltd., average particle diameter 25 μm, substantially cubic shape) having silver ion supported on an inorganic ion exchanger was blended. The yarn could not be stably produced due to poor spinnability.

［比較例３］
エチレン含有量８モル％のエチレン−ビニルアルコール系共重合体９９重量部に、無機イオン交換体に銀イオンを担持させた銀系無機系抗菌微粒子（シナネンゼオミック社製「ＡＶ１０Ｄ」、平均粒径２．５μｍ、略立方体形）１重量部を配合して、参考例１と同様に製糸しようとしたが、紡糸性不良により安定に製糸することが出来なかった。Comparative Example 3
Silver-based inorganic antibacterial particles (“AV10D” manufactured by Sinanen Zeomic, average particle diameter 2) in which silver ions are supported on an inorganic ion exchanger in 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 8 mol%. Although 1 part by weight of .5 .mu.m (approximately cubic shape) was blended and it was tried to make a yarn in the same manner as in Reference Example 1, stable spinning could not be performed due to poor spinnability.

［比較例４］
参考例４の抗菌性ＥＶＯＨ含有繊維を７０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、３８ｍｍ長）を３０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。Comparative Example 4
A card web of about 60 g / m 2 in basis weight was prepared by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 4 and 30% by weight of solvent-spun cellulose fiber (Lyocell manufactured by Lenzing Co., 1.7 dtex, 38 mm length) .

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９３％であった。各評価の結果を表２に示す。このシートは、良好な肌触りを有していたものの、保液性、放出性に劣り、吸水速度が遅いため使用しにくいものであった。Then, a water stream was jetted to the card web and subjected to entanglement treatment to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 93%. The results of each evaluation are shown in Table 2. Although this sheet had a good touch, it had poor liquid retention and release properties, and was difficult to use due to its slow water absorption rate.

［比較例５］
参考例２で得た抗菌性ＥＶＯＨ含有繊維を１００重量％用いて目付６０ｇ／ｍ2のカードウェブを作製したこと意外は、実施例１と同様にして抗菌性不織布シートを得た。また得られた抗菌性不織布シートの空隙率は９６％であった。各評価の結果を表２に示す。このシートは、優れた保液性、放出性を有していたが、吸水速度が遅いため使用しづらく、肌触りもやや劣るものであった。Comparative Example 5
An antibacterial nonwoven fabric sheet was obtained in the same manner as in Example 1 except that a card web having a basis weight of 60 g / m 2 was produced using 100% by weight of the antibacterial EVOH-containing fiber obtained in Reference Example 2. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 96%. The results of each evaluation are shown in Table 2. Although this sheet had excellent liquid retention and release properties, it was difficult to use due to its slow water absorption speed, and the touch was also somewhat inferior.

［比較例６］
参考例２の抗菌性ＥＶＯＨ含有繊維を７０重量％、丸三株式会社製コットン繊維を３０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。Comparative Example 6
A card web having a basis weight of about 60 g / m 2 was prepared by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 2 and 30% by weight of cotton fiber manufactured by Marusan Co., Ltd.

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９４％であった。各評価の結果を表２に示す。このシートは、保液性、放出性、柔軟性、及び肌へのフィット性の点で満足されるものではなかった。Then, a water stream was jetted to the card web and subjected to entanglement treatment to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 94%. The results of each evaluation are shown in Table 2. This sheet was not satisfactory in terms of liquid retention, release, flexibility, and fit to the skin.

［比較例７］
実施例３で得られた湿式不織布を、水流絡合処理なしのまま抗菌性不織布シートとした。各評価の結果を表２に示す。この不織布シートの空隙率は７８％であり、まずまず良好な肌触りを有していたものの、保液性、放出性に劣り、取り扱い性においても満足されるものではなかった。Comparative Example 7
The wet non-woven fabric obtained in Example 3 was used as an antibacterial non-woven fabric sheet without hydroentanglement treatment. The results of each evaluation are shown in Table 2. The void ratio of this non-woven fabric sheet was 78%, and although it first had a good touch, it had inferior liquid retention and release properties, and was not satisfactory in handleability.

［比較例８］
参考例６のＥＶＯＨ含有繊維を５０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、３８ｍｍ長）を５０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。Comparative Example 8
A card web having a basis weight of about 60 g / m 2 was prepared by blending 50% by weight of the EVOH-containing fiber of Reference Example 6 and 50% by weight of a solvent-spun cellulosic fiber (Lyocell manufactured by Lenzing Co., 1.7 dtex, 38 mm length).

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた不織布シートの空隙率は９５％であった。各評価の結果を表２に示す。このシートは充分な保液性、放出性を有すると共に良好な肌触りを有していたが、抗菌性の点で著しく劣るものであった。Next, a water stream was jetted to the card web and subjected to entanglement treatment to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain a non-woven sheet. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained nonwoven fabric sheet was 95%. The results of each evaluation are shown in Table 2. This sheet had sufficient liquid retention and release properties, as well as good touch, but was significantly inferior in terms of antibacterial properties.

Figure 0006480335
Figure 0006480335

Figure 0006480335
Figure 0006480335

（参考例７：単独繊維）
（１）エチレン含有量４４モル％のエチレン−ビニルアルコール系共重合体９９重量部に、無機イオン交換体に銀イオンを担持させた銀系抗菌微粒子（シナネンゼオミック社製「ＡＶ１０Ｄ」、平均粒径２．５μｍ、略立方体形）１重量部を配合して溶融押出機にて、紡糸温度２４０℃で紡出した。紡出した糸条を冷却固化した後、引き取りローラーを介してボビンに引き取った。(Reference example 7: single fiber)
(1) Silver-based antibacterial fine particles ("Sanen Zeomic Co., Ltd." AV10D "), in which silver ions are supported on an inorganic ion exchanger in 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% 1 part by weight of 2.5 μm, substantially cube-shaped) was blended and spun at a spinning temperature of 240 ° C. in a melt extruder. After the spun yarn was cooled and solidified, it was taken up on a bobbin via a take-up roller.

（２）次いで、この捲取糸を延伸温度８０℃にて、延伸倍率２．４倍で熱延伸し、油剤浴にて油剤を付与後、スタッファ型捲縮付与装置などの捲縮付与装置を用いて捲縮処理を行なった。捲縮付与処理に引き続き、繊維を１００℃の熱風で乾燥した後、任意のカット長にカットすることで抗菌性ＥＶＯＨ含有繊維を得た（１．４ｄｔｅｘ、円形断面）。紡糸性、延伸性ともに良好であり、強度は３．１ｃＮ／ｄｔｅｘ、伸度は２６％、ヤング率は３０．８ｃＮ／ｄｔｅｘであった。   (2) Next, this twill yarn is thermally drawn at a drawing temperature of 80 ° C. at a draw ratio of 2.4 times, and after applying an oil agent in an oil agent bath, a crimper such as a stuffer-type crimper The crimp process was performed using Subsequently to the crimp application treatment, the fiber was dried with hot air at 100 ° C., and cut to an arbitrary cut length to obtain an antimicrobial EVOH-containing fiber (1.4 dtex, circular cross section). Both the spinnability and the stretchability were good, the strength was 3.1 cN / dtex, the elongation was 26%, and the Young's modulus was 30.8 cN / dtex.

（参考例８：複合繊維）
（１）エチレン含有量４４モル％のエチレン−ビニルアルコール系共重合体９９重量部に、無機イオン交換体に銀イオンを担持させた銀系抗菌微粒子（シナネンゼオミック社製「ＡＶ１０Ｄ」、平均粒径２．５μｍ、略立方体形）１重量部を配合させた共重合体を鞘部とし、ポリエチレンテレフタレートから成る熱可塑性重合体を芯部として、溶融押出機から成る複合紡糸装置を用いて、丸断面口金にて、紡糸温度２８０℃、鞘芯重量比率５０：５０で鞘芯型に接合して紡出した。紡出した糸条を冷却固化した後、引き取りローラーを介してボビンに捲き取った。(Reference Example 8: Composite Fiber)
(1) Silver-based antibacterial fine particles ("Sanen Zeomic Co., Ltd." AV10D "), in which silver ions are supported on an inorganic ion exchanger in 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% Round cross section using a composite spinning apparatus comprising a melt extruder and a copolymer comprising 1 part by weight of 2.5 μm (approximately cubic) as a sheath and a thermoplastic polymer of polyethylene terephthalate as a core At a spinneret, a sheath-core type was bonded and spun at a spinning temperature of 280 ° C. and a sheath-core weight ratio of 50:50. After cooling and solidifying the spun yarn, it was wound onto a bobbin via a take-up roller.

（２）次いで、この捲取糸を延伸温度８０℃にて、延伸倍率２．６倍で熱延伸し、油剤浴にて油剤を付与後、スタッファ型捲縮付与装置などの捲縮付与装置を用いて捲縮処理を行なった。捲縮付与処理に引き続き、繊維を１００℃の熱風で乾燥した後、任意のカット長にカットすることで下記、表３に示す抗菌性ＥＶＯＨ含有繊維を得た（１．７ｄｔｅｘ、鞘芯重量比率５０：５０、円形断面、芯部の径８．９μｍ）。紡糸性、延伸性ともに良好であり、強度は３．６ｃＮ／ｄｔｅｘ、伸度は３１％、ヤング率は３３．９ｃＮ／ｄｔｅｘであった。   (2) Next, this twill yarn is thermally drawn at a drawing temperature of 80 ° C. at a draw ratio of 2.6 times, and after applying an oil agent in an oil agent bath, a crimper such as a stuffer-type crimper The crimp process was performed using Subsequently to the crimp application treatment, the fiber was dried with hot air at 100 ° C., and cut to an arbitrary cut length to obtain an antimicrobial EVOH-containing fiber shown in Table 3 below (1.7 dtex, sheath-core weight ratio 50: 50, circular cross section, core diameter 8.9 μm). Both spinnability and stretchability were good, strength was 3.6 cN / dtex, elongation was 31%, and Young's modulus was 33.9 cN / dtex.

（参考例９：複合繊維）
（１）参考例８の捲取糸を延伸温度８０℃にて、延伸倍率２倍で熱延伸し、油剤浴にて油剤を付与後、１０ｍｍにカットすることで下記、表３に示す抗菌性ＥＶＯＨ含有繊維を得た（１．７ｄｔｅｘ、１０ｍｍ長、鞘芯重量比率５０：５０、円形断面、芯部の径８．９μｍ）。紡糸性、延伸性ともに良好であり、強度は３．６ｃＮ／ｄｔｅｘ、伸度は３１％、ヤング率は３３．９ｃＮ／ｄｔｅｘであった。(Reference Example 9: Composite Fiber)
(1) The twill yarn of Reference Example 8 is thermally drawn at a drawing temperature of 80 ° C. at a draw ratio of 2 times, applied with an oil agent in an oil agent bath, and cut into 10 mm to have the antibacterial properties shown in Table 3 below. An EVOH-containing fiber was obtained (1.7 dtex, 10 mm length, sheath-core weight ratio 50: 50, circular cross section, diameter 8.9 μm of core portion). Both spinnability and stretchability were good, strength was 3.6 cN / dtex, elongation was 31%, and Young's modulus was 33.9 cN / dtex.

（参考例１０：単独繊維）
エチレン含有量８５モル％のエチレン−ビニルアルコール系共重合体９９重量部に、無機イオン交換体に銀イオンを担持させた銀系無機系抗菌微粒子（シナネンゼオミック社製「ＡＶ１０Ｄ」、平均粒径２．５μｍ、略立方体形）１重量部を配合して、参考例７と同様に製糸し、抗菌性ＥＶＯＨ含有繊維を得た（１．４ｄｔｅｘ、５１ｍｍ長、円形断面）。紡糸性、延伸性ともに良好であり、強度は３．７ｃＮ／ｄｔｅｘ、伸度は２４％、ヤング率は３５．１ｃＮ／ｄｔｅｘであった。(Reference Example 10: Single fiber)
Silver-based inorganic antibacterial particles ("AV10D" manufactured by Sinanen Zeomic, average particle diameter 2) in which silver ions are supported on an inorganic ion exchanger in 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 85 mol%. 1 part by weight of 5 .mu.m, substantially cubic shape was blended, and spun as in Reference Example 7 to obtain an antimicrobial EVOH-containing fiber (1.4 dtex, 51 mm in length, circular cross section). Both spinnability and stretchability were good, strength was 3.7 cN / dtex, elongation was 24%, Young's modulus was 35.1 cN / dtex.

（参考例１１：複合繊維）
繊度が５．５ｄｔｅｘとなるように樹脂の吐出量、引き取り速度、延伸倍率を調整した以外は、参考例８と同様に製糸し、抗菌性ＥＶＯＨ含有繊維を得た（５．５ｄｔｅｘ、５１ｍｍ長、鞘芯重量比率５０：５０、円形断面、芯部の径１６．０μｍ）。紡糸性、延伸性ともに良好であり、強度は２．７ｃＮ／ｄｔｅｘ、伸度は３６％、ヤング率は２８．７ｃＮ／ｄｔｅｘであった。(Reference Example 11: Composite Fiber)
An antibacterial EVOH-containing fiber was obtained in the same manner as in Reference Example 8 except that the discharge amount of the resin, take-up speed, and draw ratio were adjusted so that the fineness was 5.5 dtex (5.5 dtex, 51 mm length, Sheath core weight ratio 50: 50, circular cross section, core diameter 16.0 μm). Both spinnability and stretchability were good, strength was 2.7 cN / dtex, elongation was 36%, and Young's modulus was 28.7 cN / dtex.

（参考例１２：複合繊維）
（１）エチレン含有量４４モル％のエチレン−ビニルアルコール系共重合体を鞘部とし、ポリエチレンテレフタレートから成る熱可塑性重合体を芯部として、溶融押出機から成る複合紡糸装置を用いて、丸断面口金にて、紡糸温度２８０℃、鞘芯重量比率５０：５０で鞘芯型に接合して紡出した。紡出した糸条を冷却固化した後、引き取りローラーを介してボビンに捲き取った。(Reference Example 12: Composite Fiber)
(1) A round cross section using a composite spinning apparatus comprising a melt extruder and a thermoplastic polymer consisting of polyethylene terephthalate as a core, with an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% as a sheath At a spinneret, a sheath-core type was bonded and spun at a spinning temperature of 280 ° C. and a sheath-core weight ratio of 50:50. After cooling and solidifying the spun yarn, it was wound onto a bobbin via a take-up roller.

（２）次いで、この捲取糸を延伸温度８０℃にて、延伸倍率２倍で熱延伸し、油剤浴にて油剤を付与後、スタッファ型捲縮付与装置などの捲縮付与装置を用いて捲縮処理を行なった。捲縮付与処理に引き続き、繊維を１００℃の熱風で乾燥した後、５１ｍｍにカットすることでＥＶＯＨ含有繊維を得た（３．４ｄｔｅｘ、５１ｍｍ長、鞘芯重量比率５０：５０、円形断面、芯部の径１２．５μｍ）。紡糸性、延伸性ともに良好であり、強度は３．６ｃＮ／ｄｔｅｘ、伸度は３８％、ヤング率は３８．５ｃＮ／ｄｔｅｘであった。   (2) Next, this twill yarn is thermally drawn at a drawing temperature of 80 ° C. at a draw ratio of 2 times, and after an oil agent is applied in an oil agent bath, a crimper such as a stuffer-type crimp applicator is used I performed a crimp process. Subsequently to the crimp application treatment, the fiber was dried with hot air at 100 ° C. and cut to 51 mm to obtain an EVOH-containing fiber (3.4 dtex, 51 mm length, sheath core weight ratio 50: 50, circular cross section, core Part diameter 12.5 μm). Both spinnability and stretchability were good, strength was 3.6 cN / dtex, elongation was 38%, Young's modulus was 38.5 cN / dtex.

［実施例７］
参考例７の抗菌性ＥＶＯＨ含有繊維を５０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、３８ｍｍ長）を５０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。[Example 7]
A card web of about 60 g / m 2 in basis weight was prepared by blending 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 7 and 50% by weight of solvent-spun cellulose-based fiber (Lyocell manufactured by Lenzing Co., 1.7 dtex, 38 mm length) .

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９０％であった。各評価の結果を表３に示す。このシートは充分な保液性、原反への液戻りをすると共に良好な肌触りを有していた。Then, a water stream was jetted to the card web and subjected to entanglement to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 90%. The results of each evaluation are shown in Table 3. This sheet had sufficient liquid retention, liquid return to the raw fabric and had a good touch.

［実施例８］
参考例８の抗菌性ＥＶＯＨ含有繊維を５０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、３８ｍｍ長）を５０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。[Example 8]
A card web of about 60 g / m 2 in basis weight was prepared by blending 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 8 and 50% by weight of solvent-spun cellulose-based fiber (Lyocell manufactured by Lenzing Co., 1.7 dtex, 38 mm length) .

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９２％であった。各評価の結果を表３に示す。このシートは充分な保液性、原反への液戻りを有すると共に良好な肌触りを有していた。Then, a water stream was jetted to the card web and subjected to entanglement to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 92%. The results of each evaluation are shown in Table 3. This sheet had sufficient liquid retention, liquid return to the raw fabric and had a good touch.

［実施例９］
参考例９の抗菌性ＥＶＯＨ含有繊維を５０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、１２ｍｍ長）を５０重量％とし、水中に分散させ、湿式法にて目付約６０ｇ／ｍ2の湿式不織布を作製した。[Example 9]
50 weight% of the antibacterial EVOH-containing fiber of Reference Example 9 and 50 weight% of solvent-spun cellulose-based fiber (Lyothel, 1.7 dtex, 12 mm length) manufactured by Lenting Co., dispersed in water, wet weight method to about 60 g A wet nonwoven fabric of 1 / m 2 was produced.

次いで、この湿式不織布に水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は８６％であった。各評価の結果を表３に示す。このシートは充分な保液性、原反への液戻りを有すると共に良好な肌触りを有していた。Subsequently, a water stream was jetted to the wet nonwoven fabric and subjected to entanglement treatment to obtain a hydroentangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 86%. The results of each evaluation are shown in Table 3. This sheet had sufficient liquid retention, liquid return to the raw fabric and had a good touch.

［実施例１０］
参考例１１の抗菌性ＥＶＯＨ含有繊維を５０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、３８ｍｍ長）を５０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。[Example 10]
A card web of about 60 g / m 2 in basis weight was prepared by blending 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 11 and 50% by weight of solvent-spun cellulosic fiber (Lynodel, 1.7 dtex, 38 mm long) manufactured by Lenzing Co. .

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９４％であった。各評価の結果を表３に示す。このシートは充分な保液性、原反への液戻りを有すると共に良好な肌触りを有していた。Then, a water stream was jetted to the card web and subjected to entanglement to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 94%. The results of each evaluation are shown in Table 3. This sheet had sufficient liquid retention, liquid return to the raw fabric and had a good touch.

［実施例１１］
実施例８で得たカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１５ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧８ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９８％であった。各評価の結果を表３に示す。このシートは充分な保液性、原反への液戻りを有する一方で肌触りはやや劣る結果となった。[Example 11]
The card web obtained in Example 8 was sprayed with a water stream and subjected to entanglement to obtain a water-entangled non-woven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven fabric sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.15 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 8 MPa was injected on two sides of each side to cause entanglement. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 98%. The results of each evaluation are shown in Table 3. While this sheet had sufficient liquid retention and liquid return to the raw fabric, the touch was slightly inferior.

［比較例９］
無機イオン交換体に銀イオンを担持させた銀系無機系抗菌微粒子（シナネンゼオミック社製、平均粒径０．００８μｍ、略立方体形）を配合させた以外は、参考例８と同様に製糸しようとしたが、紡糸性不良により安定に製糸することが出来なかった。Comparative Example 9
An attempt was made to produce a yarn in the same manner as in Reference Example 8, except that a silver based inorganic antibacterial particle (in a product made by Sinanen Zeomic, average particle diameter 0.008 μm, substantially cubic shape) having silver ions supported on an inorganic ion exchanger was blended. However, stable spinning could not be performed due to poor spinnability.

［比較例１０］
無機イオン交換体に銀イオンを担持させた銀系無機系抗菌微粒子（シナネンゼオミック社製、平均粒径２５μｍ、略立方体形）を配合させた以外は、参考例８と同様に製糸しようとしたが、紡糸性不良により安定に製糸することが出来なかった。Comparative Example 10
A yarn was tried to be produced in the same manner as in Reference Example 8 except that a silver based inorganic type antibacterial fine particle (Sinanen Zeomic Co., Ltd., average particle diameter 25 μm, substantially cubic shape) having silver ions supported on an inorganic ion exchanger was blended. The yarn could not be stably produced due to poor spinnability.

［比較例１１］
エチレン含有量８モル％のエチレン−ビニルアルコール系共重合体９９重量部に、無機イオン交換体に銀イオンを担持させた銀系無機系抗菌微粒子（シナネンゼオミック社製「ＡＶ１０Ｄ」、平均粒径２．５μｍ、略立方体形）１重量部を配合して、参考例７と同様に製糸しようとしたが、紡糸性不良により安定に製糸することが出来なかった。Comparative Example 11
Silver-based inorganic antibacterial particles (“AV10D” manufactured by Sinanen Zeomic, average particle diameter 2) in which silver ions are supported on an inorganic ion exchanger in 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 8 mol%. .5 μm, approximately cube shape) 1 part by weight was blended, and it was tried to make a yarn in the same manner as in Reference Example 7. However, stable spinning could not be performed due to poor spinnability.

［比較例１２］
参考例１０の抗菌性ＥＶＯＨ含有繊維を５０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、３８ｍｍ長）を５０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。Comparative Example 12
A card web of about 60 g / m 2 in basis weight was prepared by blending 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 10 and 50% by weight of solvent-spun cellulose fiber (Lyothel, 1.7 dtex, 38 mm length) .

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付約６０ｇ／ｍ2の水流絡合不織布とし、抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた保液シートの空隙率は９１％であった。各評価の結果を表４に示す。Then, a water stream was jetted to the card web and subjected to entanglement to obtain a water entangled nonwoven fabric having a basis weight of about 60 g / m 2 , to obtain an antibacterial non-woven sheet. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained liquid holding sheet was 91%. The results of each evaluation are shown in Table 4.

このシートは、良好な肌触りを有していたものの、保液性や原反への液戻りが十分ではなかった。   Although this sheet had a good touch, it did not have sufficient liquid retention and liquid return to the original fabric.

［比較例１３］
参考例８で得た抗菌性ＥＶＯＨ含有繊維を１００重量％目付６０ｇ／ｍ2のカードウェブを作製したこと意外は、実施例７と同様にして抗菌性不織布シートを得た。また得られた抗菌性不織布シートの空隙率は９６％であった。各評価の結果を表４に示す。Comparative Example 13
An antibacterial nonwoven fabric sheet was obtained in the same manner as in Example 7, except that the antibacterial EVOH-containing fiber obtained in Reference Example 8 was used to prepare a card web with a basis weight of 60 g / m 2 . Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 96%. The results of each evaluation are shown in Table 4.

このシートは、原反への液戻りが満足されるものではなく、さらには吸水速度が遅いため使用しづらく、肌触りも劣るものであった。   This sheet was not satisfactory for the liquid return to the raw fabric, and furthermore, it was difficult to use because the water absorption speed was slow, and the touch was inferior.

［比較例１４］
参考例８の抗菌性ＥＶＯＨ含有繊維を３５重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセ”、１．７ｄｔｅｘ、３８ｍｍ長）を６５重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。Comparative Example 14
A card web of about 60 g / m 2 in weight is prepared by blending 35% by weight of the antibacterial EVOH-containing fiber of Reference Example 8 and 65% by weight of a solvent-spun cellulose fiber (Lyingse manufactured by Liyose, 1.7 dtex, 38 mm length) did.

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９５％であった。各評価の結果を表４に示す。Then, a water stream was jetted to the card web and subjected to entanglement treatment to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 95%. The results of each evaluation are shown in Table 4.

このシートは保液性、吸液速度、原反への液戻りの点で十分満足できるものではなかった。   This sheet was not sufficiently satisfactory in terms of liquid retention, liquid absorption speed, and liquid return to the raw fabric.

［比較例１５］
参考例８の抗菌性ＥＶＯＨ含有繊維を７０重量％、丸三株式会社製コットン繊維を３０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。Comparative Example 15
A card web having a basis weight of about 60 g / m 2 was prepared by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 8 and 30% by weight of cotton fiber manufactured by Marusan Co., Ltd.

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、本発明の抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９３％であった。各評価の結果を表４に示す。Then, a water stream was jetted to the card web and subjected to entanglement to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet of the present invention. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 93%. The results of each evaluation are shown in Table 4.

このシートは、保液性、柔軟性、及び肌へのフィット性の点で満足されるものではなかった。   This sheet was not satisfactory in terms of liquid retention, flexibility, and skin fit.

［比較例１６］
実施例９で得られた湿式不織布を、水流絡合処理なしのまま抗菌性不織布シートとした。この抗菌性不織布シートの空隙率は７４％であり、まずまず良好な肌触りを有していたものの、ウェット時の３０％伸張時応力に劣り、取り扱い性において満足されるものではなかった。Comparative Example 16
The wet non-woven fabric obtained in Example 9 was used as an antibacterial non-woven fabric sheet without hydroentanglement treatment. The porosity of this antibacterial non-woven fabric sheet was 74%, and although it had a good touch first, it was inferior to the stress at the time of 30% elongation when wet, and was not satisfactory in handleability.

［比較例１７］
参考例１２のＥＶＯＨ含有繊維を５０重量％、溶剤紡糸セルロース系繊維（レンチング社製リヨセル、１．７ｄｔｅｘ、３８ｍｍ長）を５０重量％混綿した目付約６０ｇ／ｍ2のカードウェブを作製した。Comparative Example 17
A card web having a basis weight of about 60 g / m 2 was prepared by blending 50% by weight of the EVOH-containing fiber of Reference Example 12 and 50% by weight of a solvent-spun cellulosic fiber (Lyocell manufactured by Lenzing Co., 1.7 dtex, 38 mm length).

次いで、このカードウェブに水流を噴射し、絡合処理を施して目付６０ｇ／ｍ2の水流絡合不織布とし、抗菌性不織布シートを得た。なお、水流絡合処理は、直径０．１ｍｍのオリフィスがウェブの幅方向に間隔０．６ｍｍ毎に設けられたノズルを用い、水圧６ＭＰａを表裏２段ずつで噴射し交絡させた。また得られた抗菌性不織布シートの空隙率は９５％であった。各評価の結果を表４に示す。Then, a water stream was jetted to the card web and subjected to entanglement treatment to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m 2 to obtain an antibacterial non-woven sheet. In the hydroentanglement process, nozzles having a diameter of 0.1 mm were provided at intervals of 0.6 mm in the width direction of the web, and water pressure of 6 MPa was jetted on two sides of each side to entangle. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 95%. The results of each evaluation are shown in Table 4.

このシートは充分な保液性、放出性を有すると共に良好な肌触りを有していたが、抗菌性の点で著しく劣るものであった。   This sheet had sufficient liquid retention and release properties, as well as good touch, but was significantly inferior in terms of antibacterial properties.

Figure 0006480335
Figure 0006480335

Figure 0006480335
Figure 0006480335

本発明の抗菌性不織布シートは、液状成分を吸収し、皮膚に接触させる用途、例えば、体液吸収用シート（例えば、ナプキンやおむつなどの表面材、おむつライナー、ウェットティッシュなど）、スキンケアシート（例えば、フェイスマスク、メイク除去シート、クレンジングシートまたは身体洗浄用シート（汗拭きシート、油取りシート、冷却シートなど）、薬用シート（痒み抑制シート、湿布など）などに利用できる。特に、本発明の抗菌性不織布シートは、美容液（化粧料）などの液状成分を含浸した状態で、指で押しても、液状成分の戻りが速いため、顔全体、鼻、目元、口元、首などの保湿、美白などの効能成分を含浸し、抗菌性を兼備したフェイスマスクに有用である。   The antibacterial non-woven sheet of the present invention is used for absorbing liquid components and contacting the skin, for example, sheets for absorbing body fluid (for example, surface materials such as napkins and diapers, diaper liners, wet tissues, etc.), skin care sheets (for example, , Face mask, make-up removal sheet, cleansing sheet or body washing sheet (sweat wipe sheet, oil removal sheet, cooling sheet etc.), medical use sheet (anti-stain sheet, wet cloth etc.) etc. Especially, the antibacterial of the present invention Non-woven fabric sheet in which liquid components such as cosmetic fluid (cosmetics) are impregnated, the quick return of the liquid component is possible even when pressed with a finger, so moisturizing the whole face, nose, eyes, mouth, neck, etc., whitening etc. It is useful for the face mask which is impregnated with the effect ingredient of the above and is also equipped with the antibacterial property.

１ レーザー変位計、２，５…荷重、３，６…サンプル、４，７…測定台。   1 Laser displacement meter, 2, 5 load, 3, 6 sample, 4, 7 measurement stand.

Claims (8)

無機系抗菌微粒子を内部に分散した状態で含有する抗菌性エチレン−ビニルアルコール系共重合体が繊維表面の少なくとも一部に存在し、該無機系抗菌微粒子の平均粒径が０．０１〜２０μｍであって、且つ該抗菌性エチレン−ビニルアルコール系共重合体のエチレン含有率が１０〜７０モル％である抗菌性繊維と、溶剤紡糸セルロース系繊維とが、互いに交絡してなり、抗菌性繊維径に対する無機系抗菌微粒子の径の比が０．８以下である抗菌性不織布シートと、流動性組成物とが一体となった含液シートを用いたフェイスマスクであって、
前記流動性組成物を自重に対して９００重量％含浸させて、２６０ｇ／ｃｍ 2 の荷重を１分間負荷して取り除いたとき、厚み方向の圧縮に対する復位が５分間で３５％以上であることを特徴とする、フェイスマスク。 An antibacterial ethylene-vinyl alcohol copolymer containing inorganic antibacterial particles dispersed therein is present in at least a part of the fiber surface, and the average particle diameter of the inorganic antibacterial particles is 0.01 to 20 μm. And the antibacterial fiber having an ethylene content of 10 to 70 mol% of the antibacterial ethylene-vinyl alcohol copolymer and the solvent-spun cellulose-based fiber are mutually entangled, and the antibacterial fiber diameter and an inorganic antibacterial particle diameter antibacterial nonwoven fabric sheet ratio Ru der 0.8 of the flowable composition is a facemask using the liquid content sheets together against,
When the flowable composition is impregnated at 900% by weight with respect to its own weight and removed by applying a load of 260 g / cm 2 for 1 minute, reciprocation with respect to compression in the thickness direction is 35% or more in 5 minutes Feature, face mask . 前記抗菌性繊維、及び溶剤紡糸セルロース系繊維の繊維長が５〜６０ｍｍであり、これらが互いに交絡してなることを特徴とする、請求項１に記載のフェイスマスク。 2. The face mask according to claim 1, wherein the fiber length of the antibacterial fiber and the solvent-spun cellulose-based fiber is 5 to 60 mm, and they are entangled with each other. 前記抗菌性繊維が鞘芯型複合繊維であって、該鞘部が、平均粒径が０．０１〜２０μｍの無機系抗菌微粒子を内部に分散した状態で含有する抗菌性エチレン−ビニルアルコール系共重合体であるとともに、該芯部が疎水性樹脂からなりその径が５〜１５μｍであることを特徴とする、請求項１または２に記載のフェイスマスク。 The antibacterial ethylene-vinyl alcohol copolymer fiber wherein the antibacterial fiber is a sheath-core type composite fiber, and the sheath part contains inorganic antibacterial fine particles having an average particle diameter of 0.01 to 20 μm dispersed therein. The face mask according to claim 1 or 2, wherein the core portion is made of a hydrophobic resin and has a diameter of 5 to 15 μm while being a polymer. 前記抗菌性不織布シートの表面が凹凸を有することを特徴とする、請求項１〜３のいずれか１項に記載のフェイスマスク。 The surface of the said antibacterial nonwoven fabric sheet has an unevenness | corrugation, The face mask of any one of Claims 1-3 characterized by the above-mentioned. 前記抗菌性繊維を３０〜９０重量％含むことを特徴とする、請求項１〜４のいずれか１項に記載のフェイスマスク。 The face mask according to any one of claims 1 to 4, wherein the antibacterial fiber is contained in an amount of 30 to 90% by weight. 前記抗菌性繊維を４０〜９０重量％含み、前記抗菌性繊維のヤング率が２５ｃＮ／ｄｔｅｘ以上であることを特徴とする、請求項５に記載のフェイスマスク。 The face mask according to claim 5, comprising 40 to 90% by weight of the antibacterial fiber, and a Young's modulus of the antibacterial fiber is 25 cN / dtex or more. 前記流動性組成物が水を含む、請求項１に記載のフェイスマスク。 The face mask according to claim 1 , wherein the flowable composition comprises water. 前記流動性組成物が、化粧料を含む、請求項１に記載のフェイスマスク。 The face mask according to claim 1 , wherein the flowable composition comprises a cosmetic.
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