JPH08176961A - Antimicrobial complex nonwoven fabric sheet - Google Patents
Antimicrobial complex nonwoven fabric sheetInfo
- Publication number
- JPH08176961A JPH08176961A JP6322731A JP32273194A JPH08176961A JP H08176961 A JPH08176961 A JP H08176961A JP 6322731 A JP6322731 A JP 6322731A JP 32273194 A JP32273194 A JP 32273194A JP H08176961 A JPH08176961 A JP H08176961A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- sheet
- paper sheet
- nonwoven fabric
- antibacterial
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は抗菌性を有する拭き布に
関するものである。更に詳しく述べるならば、本発明は
抗菌剤として銀イオンをイオン交換により置換したカル
ボキシメチルセルロース銀塩を含有するセルロース原料
からなる紙シートと疎水性の長繊維フィラメントからな
るスパンボンド不織布とを水交絡して構成されている抗
菌剤の非溶出タイプの抗菌性複合不織布シートに関す
る。FIELD OF THE INVENTION The present invention relates to a wiping cloth having antibacterial properties. More specifically, in the present invention, a paper sheet made of a cellulose raw material containing a carboxymethylcellulose silver salt in which silver ions are replaced by ion exchange as an antibacterial agent and a spunbonded nonwoven fabric made of hydrophobic long fiber filaments are water-entangled. The present invention relates to a non-elution type antibacterial composite non-woven sheet of an antibacterial agent.
【０００２】[0002]
【従来の技術】従来より住居回りを清掃したり、身体を
きれいに拭いたりするための使い捨て拭き布として、不
織布やパルプ繊維を嵩高に集積してなる乾式パルプシー
トに水や清浄剤、殺菌剤の薬剤等をしみこませたもの
（特開昭６２ー１９４８２４号公報、特開昭６２ー２３
６５１６号公報、特開昭６３ー６３４１９号公報、特開
昭６３ー２７５３１１号公報、特開平１ー２５８２１号
公報、特開平３ー１６５４２号公報、特開平３ー３７０
１７号公報、特開平３ー１６８１１８号公報等）が広く
利用されている。しかしながら、単に含浸のような処理
で抗菌性をシートに付与した場合、抗菌剤を繊維内部に
含有させたわけではないのでその抗菌効果と持続性に問
題があり、かつ加工や使用する際に薬剤が容易に脱落
し、安全面での不安があるという欠点があった。2. Description of the Related Art Conventionally, as a disposable wiping cloth for cleaning the surroundings of a house or wiping the body cleanly, a dry pulp sheet made of a large amount of non-woven fabric or pulp fibers is filled with water, a detergent or a bactericide. Those impregnated with a drug or the like (JP-A-62-194824, JP-A-62-23)
6516, JP-A-63-63419, JP-A-63-275311, JP-A-1-25821, JP-A-3-16542, and JP-A-3-370.
No. 17, Japanese Patent Laid-Open No. 3-168118, etc.) are widely used. However, when imparting antibacterial properties to the sheet simply by a treatment such as impregnation, the antibacterial agent is not contained inside the fiber, so there is a problem in its antibacterial effect and persistence, and the drug is not suitable for processing and use. It had the drawback that it could easily fall off and there was a concern about safety.
【０００３】疎水性の連続長繊維フィラメントを集積し
て、その後加熱エンボスロールで処理して融着点を設け
た連続長繊維不織布はスパンボンド不織布として知られ
ており、このスパンボンド不織布と木材パルプのような
セルロースからなる紙シートを水流交絡させて複合不織
布シートを製造する技術は、Research disclosure,1706
0,June 1978に開示されている。A continuous long-fiber non-woven fabric in which hydrophobic continuous long-fiber filaments are accumulated and then treated with a heat embossing roll to provide a fusion point is known as a spun-bonded non-woven fabric. A technique for producing a composite non-woven sheet by hydroentangling a paper sheet made of cellulose such as that described in Research disclosure, 1706
0, June 1978.
【０００４】一方、スパンボンド不織布と紙シートを積
層し、紙表面側から不織布を貫通するように高圧水ジェ
ット流を施し、不織布を構成する長繊維と紙シートを構
成するパルプ繊維を水流交絡させると共に、適度の穴を
設け、柔軟性、強度、吸水性、拭き取り性を備えた複合
不織布シートからなる拭き布の製造技術は、特開平５ー
２５３１６０号公報、特開平５ー２１４６５４号公報、
特開平５ー２７７０５３号公報、特開平５ー２８５０８
３号公報、特開平５ー２８６１００号公報、特開平６ー
１７３６５号公報等に開示されている。On the other hand, a spunbonded non-woven fabric and a paper sheet are laminated, and a high-pressure water jet stream is applied from the paper surface side so as to penetrate the non-woven fabric to hydroentangle the long fibers constituting the non-woven fabric and the pulp fibers constituting the paper sheet. At the same time, a technique for manufacturing a wiping cloth formed of a composite non-woven sheet having appropriate holes, flexibility, strength, water absorption, and wiping property is disclosed in JP-A-5-253160 and JP-A-5-214654.
JP-A-5-277053 and JP-A-5-28508
No. 3, JP-A-5-286100, JP-A-6-17365, and the like.
【０００５】さらに、カナダ特許明細書第８４１、３９
８号には、紙シートに高圧ジェット水流を施し、未処理
の紙シートと比較してより大きな耐破損性、柔軟性、伸
縮性、耐摩耗性および吸水性を付与する方法が開示され
ている。Further, Canadian Patent Specification Nos. 841, 39
No. 8 discloses a method in which a paper sheet is subjected to a high-pressure jet water stream to impart greater damage resistance, flexibility, stretchability, abrasion resistance and water absorption compared to an untreated paper sheet. .
【０００６】一方、カルボキシメチルセルロース（以下
ＣＭＣという）は、セルロースを主原料としたアニオン
性高分子である。その基本的な製造方法は、セルロース
パルプに苛性ソーダを作用させてアルカリセルロースと
し、これとモノクロル酢酸とをエーテル反応させて得ら
れるものである。一般に広く利用されているＣＭＣは、
エーテル化度が０．５〜１．５の範囲のナトリウム塩で
水溶性であるが、特殊なものとしてはカルボキシメチル
基そのものを導入した水不溶性の酸型ＣＭＣ（ＣＭＣ酸
ともいう）も知られている。On the other hand, carboxymethyl cellulose (hereinafter referred to as CMC) is an anionic polymer mainly composed of cellulose. The basic production method is obtained by reacting cellulose pulp with caustic soda to give alkali cellulose, and subjecting this to an ether reaction with monochloroacetic acid. CMC, which is widely used in general,
A sodium salt having an etherification degree in the range of 0.5 to 1.5, which is water-soluble, but as a special one, a water-insoluble acid type CMC (also called CMC acid) into which a carboxymethyl group itself is introduced is also known. ing.
【０００７】ＣＭＣは、粘着性、接着性、保水性、保護
コロイド性、膨潤性等の特性を有しており、これらの特
性を利用して医薬、化粧品、繊維、製紙等の多方面にお
いて使用されている。紙への応用としては紙力増強剤、
表面サイジング剤、接着剤等として或いは水溶解性シー
ト、吸水性シート等が挙げられる。また、ＣＭＣは、高
分子電解質物質であるため、その水溶液は塩類の影響を
受け易い。このイオン交換能を利用して、或る種の金属
を回収除去する目的でフィルターに使用することもでき
る。このような特性からＣＭＣのナトリウム塩を他の陽
イオンで置換してＣＭＣの種々の塩を作ることができ
る。CMC has properties such as tackiness, adhesiveness, water retention, protective colloid property, and swelling property, and it is used in various fields such as medicines, cosmetics, fibers and papermaking by utilizing these properties. Has been done. For paper application, paper strength enhancer,
Examples of the surface sizing agent, the adhesive or the like include a water-soluble sheet and a water absorbent sheet. Further, since CMC is a polymer electrolyte substance, its aqueous solution is easily affected by salts. By utilizing this ion exchange ability, it can also be used in a filter for the purpose of recovering and removing a certain kind of metal. Due to such characteristics, various salts of CMC can be prepared by substituting the sodium salt of CMC with other cations.
【０００８】水不溶性のＣＭＣ、すなわちゲルを生成す
る金属塩としてはカリミョウバン、硫酸アルミニウム、
酢酸アルミニウム、水酸化カルシウム、硫酸第一鉄、塩
化第二鉄、硫酸亜鉛、塩化バリウム、硝酸クロム、硝酸
銀、塩化スズ、塩化第二銅、酢酸鉛等を挙げることがで
きる。Water-insoluble CMC, that is, a metal salt forming a gel is potassium alum, aluminum sulfate,
Examples thereof include aluminum acetate, calcium hydroxide, ferrous sulfate, ferric chloride, zinc sulfate, barium chloride, chromium nitrate, silver nitrate, tin chloride, cupric chloride and lead acetate.
【０００９】銀は他の抗菌剤に比べて抗菌スペルトルの
広い金属として知られており、その抗菌作用は微量に生
成されるイオンによるものと考えられている。銀の場
合、比較的安定な金属のためカップ、皿、スプーン、フ
ォーク等の食器類、義歯等のように直接口に入れるもの
に多く使用されていることからも明らかなように、安全
性が高く、しかも菌に対しても薬剤耐性が出難いことが
知られている。しかしながら、安全性についてはアルギ
リア症（銀症）を考慮したアメリカにおける水質基準
は、５０ｐｐｂと低いが、それでも直接肌に触れるよう
な可能性の多い不織布に使用する場合、より確実に銀を
固定した上で使用する必要があった。Silver is known as a metal having a wider antibacterial spectrum than other antibacterial agents, and its antibacterial action is considered to be due to ions produced in a trace amount. Since silver is a relatively stable metal, it is often used for tableware such as cups, plates, spoons and forks, and things that can be put directly into the mouth such as dentures. It is known that it is high and that drug resistance is difficult to develop against bacteria. However, in terms of safety, the water quality standard in the United States that takes into account argiliosis (silver disease) is as low as 50 ppb, but it still fixes silver more reliably when used for non-woven fabrics that are likely to come into direct contact with the skin. Had to use above.
【００１０】本発明者等は、抗菌性を有する拭き布の安
全性、抗菌性、使い易さについて鋭意研究した結果、疎
水性の連続長繊維フィラメントからなるスパンボンド不
織布と、セルロースパルプからなる紙シートとを積層し
て、高圧ジェット水流を紙シートの表面から不織布を貫
通するように施して一体化して得られる複合不織布シー
トからなる不織布が柔軟性、強度、拭き取り性等におい
て布タオルに近いことに着眼し、紙シートを製造する際
に、ＣＭＣ銀塩を混合して抄造し、銀含有紙シートを
得、この紙シートと前記スパンボンド不織布とを積層し
て、高圧ジェット水流で水交絡させて一体化して得られ
る複合不織布シートにおいて、特定の銀含有率のものが
きわめて優れた抗菌性と、抗菌性の持続性を有すること
を見出し、本発明を完成するに至った。本発明の目的
は、疎水性の連続長繊維からなるスパンボンド不織布と
ＣＭＣ銀塩を含有し、特定の銀含有率の紙シートを高圧
ジェット水流で交絡して一体化された複合不織布シート
であって、優れた抗菌性と、抗菌性の持続性を有する抗
菌性複合不織布シートを提供することを目的とする。As a result of earnest studies on the safety, antibacterial property, and ease of use of a wiping cloth having antibacterial properties, the present inventors have found that a spunbonded non-woven fabric composed of hydrophobic continuous long fiber filaments and a paper composed of cellulose pulp. A non-woven fabric composed of a composite non-woven sheet obtained by laminating a sheet with a sheet and applying a high-pressure jet water stream from the surface of the paper sheet so as to penetrate the non-woven sheet is similar to a cloth towel in terms of flexibility, strength, wipeability, etc. When manufacturing a paper sheet, a CMC silver salt is mixed to produce a paper, and a silver-containing paper sheet is obtained. The paper sheet and the spunbonded nonwoven fabric are laminated and hydroentangled with a high-pressure jet water stream. In the composite non-woven sheet obtained by integrating the above, it was found that one having a specific silver content has extremely excellent antibacterial properties and antibacterial durability, and the present invention This has led to the formation. An object of the present invention is a composite non-woven fabric sheet containing a spunbonded non-woven fabric composed of hydrophobic continuous filaments and a CMC silver salt, and a paper sheet having a specific silver content is entangled with a high-pressure jet water stream to be integrated. And to provide an antibacterial composite non-woven sheet having excellent antibacterial properties and antibacterial durability.
【００１１】[0011]
【課題を解決するための手段】本発明の第一は、疎水性
の連続長繊維からなるスパンボンド不織布と、セルロー
スパルプ繊維からなる紙シートとを高圧水柱流で一体化
された複合不織布シートにおいて、該紙シートがカルボ
キシメチルセルロースにイオン交換により銀を固定して
生成されるカルボキシメチルセルロース銀塩を含有する
ことを特徴とする抗菌性複合不織布シートである。本発
明の第二は、前記紙シートの銀含有率が絶乾紙シート重
量当り銀として０．０１〜０．１５重量％であることを
特徴とする本発明第一に記載の抗菌性複合不織布シート
である。The first aspect of the present invention is to provide a composite non-woven fabric sheet in which a spunbonded non-woven fabric composed of hydrophobic continuous filaments and a paper sheet composed of cellulose pulp fibers are integrated by a high pressure columnar flow. An antibacterial composite non-woven sheet characterized in that the paper sheet contains a carboxymethyl cellulose silver salt produced by fixing silver to carboxymethyl cellulose by ion exchange. A second aspect of the present invention is characterized in that the silver content of the paper sheet is 0.01 to 0.15% by weight in terms of silver based on the weight of the absolutely dried paper sheet, and the antibacterial composite non-woven fabric according to the first aspect of the present invention. It is a sheet.
【００１２】本発明は、まずＣＭＣのイオン交換能を利
用して銀を吸着させ、このＣＭＣ銀塩をセルロースパル
プに混合して公知の抄紙機において抄造し、紙シートを
準備する。この際に、本発明のために使用できるＣＭＣ
は、水不溶性でなければならず、置換度が０．１〜１．
５、好ましくは０．２〜０．６の範囲の酸型ＣＭＣであ
る。ＣＭＣの酸型は、水に不溶性を示すので本発明に好
適であるが、置換度が０．１未満では銀化合物との反応
性が劣り、ＣＭＣ銀塩として用いるには銀含有量が少な
すぎて適さない。置換度が１．５を越えるＣＭＣは、置
換度を高めるのに限度があり、特殊な架橋剤を使用して
架橋構造としなければ得られなくなるので適さない。In the present invention, first, silver is adsorbed by utilizing the ion exchange capacity of CMC, and the CMC silver salt is mixed with cellulose pulp and paper-making is carried out by a known paper-making machine to prepare a paper sheet. At this time, CMC that can be used for the present invention
Must be water-insoluble and have a degree of substitution of 0.1-1.
Acid type CMC in the range of 5, preferably 0.2 to 0.6. The acid form of CMC is suitable for the present invention because it shows insolubility in water, but if the degree of substitution is less than 0.1, the reactivity with silver compounds is poor, and the silver content is too low for use as a CMC silver salt. Not suitable. CMC having a degree of substitution of more than 1.5 is not suitable because there is a limit to increase the degree of substitution and it cannot be obtained unless a cross-linking structure is formed by using a special cross-linking agent.
【００１３】ＣＭＣ銀塩を製造する方法は、酸型ＣＭＣ
を硝酸銀で中和すればよく、ＣＭＣのカルボキシメチル
基を直接硝酸銀で中和する方法、カルボキシメチル基を
ナトリウムやカルシウムのような塩に中和後、更に硝酸
銀の銀で再置換する方法等が適用できる。酸型ＣＭＣ
は、フロックを生成し易いので、撹拌を行いながら１〜
４％の固形分濃度で分散させ、これに１〜１０％固形分
濃度の硝酸銀水溶液を添加し、温度は１５〜３０℃の常
温で反応を行わせる。用いるＣＭＣ酸の置換度によって
前記の条件は変更されるが、中和反応で消費されなかっ
た硝酸銀は循環再使用される。このようにして得られた
ＣＭＣ銀塩は、絶乾ＣＭＣ銀塩重量当り銀含有率が０．
１〜４．５重量％である。銀含有率が０．１重量％未満
では、大量のＣＭＣ銀塩を使用しなければならず、４．
５重量％を越える銀含有量は、用いるＣＭＣ酸の置換度
から銀イオンの交換において限界があり、その上このよ
うな高い銀含有率のＣＭＣ銀塩を低い配合率で抄紙機に
おいて他のパルプ繊維と一緒に抄紙すると、分散性に問
題が生じるので適さない。このようにして得られたＣＭ
Ｃ銀塩は、セルロースパルプと混合されて公知の湿式抄
紙機において抄造され、抗菌性を有する紙シートとされ
る。セルロースパルプとしては、広葉樹および針葉樹材
からの化学パルプ、とりわけ針葉樹晒クラフトパルプが
好適に用いられる。A method for producing a CMC silver salt is a method for producing an acid type CMC.
May be neutralized with silver nitrate, such as a method of directly neutralizing the carboxymethyl group of CMC with silver nitrate, a method of neutralizing the carboxymethyl group with a salt such as sodium or calcium, and then resubstitution with silver of silver nitrate. Applicable. Acid type CMC
Easily generate flocs, so
It is dispersed at a solid content concentration of 4%, an aqueous silver nitrate solution having a solid content concentration of 1 to 10% is added thereto, and the reaction is carried out at room temperature of 15 to 30 ° C. The above conditions are changed depending on the substitution degree of the CMC acid used, but the silver nitrate not consumed in the neutralization reaction is recycled and reused. The CMC silver salt thus obtained has a silver content of 0.
It is 1 to 4.5% by weight. If the silver content is less than 0.1% by weight, a large amount of CMC silver salt must be used.
A silver content of more than 5% by weight has a limit in the exchange of silver ions due to the degree of substitution of the CMC acid used, and moreover, a CMC silver salt having such a high silver content at a low compounding ratio cannot be used in other pulps in a paper machine. Paper making with fibers is not suitable because it causes problems in dispersibility. CM obtained in this way
The C silver salt is mixed with cellulose pulp and made into a paper sheet by a known wet paper machine to obtain a paper sheet having antibacterial properties. As cellulose pulp, chemical pulp from hardwood and softwood, particularly bleached softwood kraft pulp is preferably used.
【００１４】ＣＭＣ銀塩とパルプ繊維は、紙シートにす
る際に、紙シートが絶乾紙シート重量当り０．０１〜
０．１５重量％の銀含有量となるように調整される。紙
シート中の銀含有率が０．０１重量％未満では抗菌性が
発現せず、０．１５重量％を越えると効果は頭打ちとな
り、コストが増加するので適さない。続いてこのように
して得られた抗菌性の紙シートは、疎水性の連続長繊維
フィラメントからなるスパンボンド不織布と積層され、
高圧ジェット水流が紙シート側から不織布を貫通するよ
うに施され、長繊維とパルプ繊維との水流交絡を行い一
体化して複合不織布シートとされるが、この水流交絡の
方法は公知の方法をそのまま応用することができる。紙
シートの米坪量は、水流交絡を行わせ、複合不織布シー
トを拭き布として使用する関係上、１０〜１５０ｇ／ｍ
2で用いられる。坪量が１０ｇ／ｍ2未満では、拭き布と
した時、十分な吸水性や保水性が得られず、坪量が１０
０ｇ／ｍ2を越えると、高圧ジェット水流を施す時にパ
ルプ繊維に十分な運動量を与えることができないので適
さない。When the CMC silver salt and pulp fiber are made into a paper sheet, the weight of the paper sheet is 0.01 to 0.01 per weight of the absolutely dry paper sheet.
It is adjusted to have a silver content of 0.15% by weight. If the silver content in the paper sheet is less than 0.01% by weight, no antibacterial property will be exhibited, and if it exceeds 0.15% by weight, the effect will reach the ceiling and the cost will increase, which is not suitable. Subsequently, the antibacterial paper sheet thus obtained is laminated with a spunbond nonwoven fabric composed of hydrophobic continuous filament filaments,
A high-pressure jet water stream is applied from the paper sheet side so as to penetrate the non-woven fabric, and hydroentanglement of long fibers and pulp fibers is carried out to be integrated into a composite non-woven fabric sheet. It can be applied. The rice basis weight of the paper sheet is 10 to 150 g / m in terms of hydroentangling and using the composite non-woven sheet as a wiping cloth.
Used in 2 . If the basis weight is less than 10 g / m 2 , sufficient water absorption and water retention cannot be obtained when using a wiping cloth, and the basis weight is 10
When it exceeds 0 g / m 2 , it is not suitable because sufficient momentum cannot be given to the pulp fibers when the high-pressure jet water stream is applied.
【００１５】本発明で使用するスパンボンド不織布は、
ナイロンのようなポリアミド系樹脂、ポリアクリル酸エ
ステル系樹脂、ポリエチレン、ポリプロピレン等のポリ
オレフィン系樹脂、ポリエチレンテレフタレートのよう
なポリエステル系樹脂を公知の加熱押出機で紡糸し、開
繊した後、ウェブを形成し、加熱エンボスを施したもの
である長繊維の繊度は、１〜４、好ましくは１．５〜３
デニールの範囲である。繊度が４デニールを越えると、
長繊維の曲げ剛度が高くなりすぎて、しなやかさが失わ
れるので適さない。繊度が１デニール未満では長繊維を
製造する条件が厳しくなって、高速度で製造できなくな
るので適さない。The spunbond nonwoven fabric used in the present invention is
A polyamide-based resin such as nylon, a polyacrylic acid ester-based resin, a polyolefin-based resin such as polyethylene and polypropylene, and a polyester-based resin such as polyethylene terephthalate are spun by a known heating extruder and opened to form a web. However, the fineness of the long fibers which have been subjected to heat embossing is 1 to 4, preferably 1.5 to 3
Range of denier. When the fineness exceeds 4 denier,
It is not suitable because the bending rigidity of long fibers becomes too high and the flexibility is lost. If the fineness is less than 1 denier, the conditions for producing long fibers become strict, and high-speed production becomes impossible, which is not suitable.
【００１６】スパンボンド不織布の坪量は、５〜３０ｇ
／ｍ2である。坪量が３０ｇ／ｍ2を越えると、前記紙シ
ートと不織布を積層して、この積層体の紙シート側から
不織布側へ向けて高圧水柱流を貫通するように施す際
に、パルプ繊維が不織布側へ移動し難くなり、複合不織
布シートの片面のみにパルプ繊維が遍在した状態となっ
て、不織布面の吸水性が低下するので適さない。一方、
不織布の坪量が５ｇ／ｍ 2未満では不織布の形態安定性
が低下し、得られる不織布の湿潤強度が低下するので適
さない。また、この場合不織布の長繊維相互間の間隔が
大きくなって、高圧水柱流を施したときに、その間隙か
らパルプ繊維が流出する恐れがある。本発明のために用
いられるスパンボンド不織布には、前記したように、加
熱エンボスによって長繊維相互間が自己融着による点融
着区域が間隔を置いて多数配置されていると共に、個々
の点融着区域の面積は、０．０１〜４ｍｍ2、その点融
着区域の総面積は、不織布の表面積に対して２〜２０面
積％であるような接着形態を有し、形態安定性に優れる
と共に、柔軟性に富んでいて、パルプ繊維と長繊維同士
が水交絡し易いものである。The basis weight of the spunbond nonwoven fabric is 5 to 30 g.
/ M2Is. Basis weight is 30g / m2If it exceeds,
Sheet and non-woven fabric are laminated, and from the paper sheet side of this laminate
When applying so as to penetrate the high pressure water column flow toward the non-woven fabric side
In addition, it becomes difficult for the pulp fibers to move to the non-woven fabric side, and the composite non-woven
The pulp fibers are ubiquitous on only one side of the cloth sheet.
In addition, the water absorbency of the non-woven fabric surface decreases, which is not suitable. on the other hand,
Nonwoven fabric basis weight is 5g / m 2Non-woven fabric morphological stability below
Is reduced, and the wet strength of the resulting nonwoven fabric is reduced.
Not. Also, in this case, the distance between the long fibers of the non-woven fabric
When it becomes large and a high pressure water column flow is applied, the gap
There is a risk that pulp fibers will flow out. For the present invention
As mentioned above, the spunbond nonwoven fabric that is used is
Point fusion due to self-fusion between long fibers due to heat embossing
A large number of wearing areas are arranged at intervals and
The area of the point fusion area is 0.01 to 4 mm2, That point fusion
The total area of the landing area is 2 to 20 with respect to the surface area of the nonwoven fabric.
It has an adhesive morphology that is product% and has excellent morphological stability.
Together with the flexibility, pulp fibers and long fibers
Is easily entangled in water.
【００１７】スパンボンド不織布と抗菌性の紙シート
は、重量比で不織布：紙シートが１：１〜１９の割合で
積層させる。この不織布：紙シートが１：１において、
紙シートの割合が１未満では長繊維に対してパルプ繊維
の量が相対的に低くなり、抗菌性複合不織布シートの吸
水性や保水性が低下するので適さない。逆に、不織布：
紙シートが１：１９において、紙シートの割合が１９を
越えて多くなると、パルプ繊維全てが長繊維と絡合し難
くなるので、抗菌性複合不織布シートを湿潤させて拭き
布として使用する際に、パルプ繊維が脱落するので適さ
ない。The spunbonded nonwoven fabric and the antibacterial paper sheet are laminated at a weight ratio of nonwoven fabric: paper sheet of 1: 1 to 19. This non-woven: paper sheet is 1: 1
If the ratio of the paper sheet is less than 1, the amount of pulp fiber is relatively low with respect to the long fiber, and the water absorption and water retention of the antibacterial composite nonwoven fabric sheet are reduced, which is not suitable. On the contrary, non-woven fabric:
When the paper sheet ratio is 1:19 and the paper sheet ratio exceeds 19 and increases, it becomes difficult for all the pulp fibers to be entangled with the long fibers. Therefore, when the antibacterial composite non-woven fabric sheet is wetted and used as a wipe, , Pulp fiber will fall off, so it is not suitable.
【００１８】前記不織布と紙シートを積層して紙シート
の表面から不織布側に向かって高圧水柱流を施すが、そ
のような高圧水柱流は、微細な直径のノズル孔を通し
て、高圧で水を噴出させて得られるものである。例え
ば、ノズル孔は、０．０１〜０．３ｍｍで、ノズルピッ
チが５〜２０個／ｃｍ、水圧が１０〜１５０ｋｇ／ｃｍ
2のような条件で得られる公知の高圧水柱流発生装置が
適用できる。以上説明したような水交絡されて得られる
抗菌性の複合不織布シートは、紙シートの高圧水柱流と
接触した部分のパルプ繊維が単離し、曲げやねじれのよ
うな変形が付与されており、長繊維とパルプ繊維の繊維
同士が絡合し、ボリューム感があって布製タオルに似た
外観と柔軟性をもっている。The non-woven fabric and the paper sheet are laminated, and a high-pressure water column flow is applied from the surface of the paper sheet toward the non-woven fabric side. Such a high-pressure water column flow ejects water at high pressure through a nozzle hole having a fine diameter. It is obtained by doing. For example, the nozzle holes are 0.01 to 0.3 mm, the nozzle pitch is 5 to 20 pieces / cm, and the water pressure is 10 to 150 kg / cm.
A known high-pressure water column flow generator that can be obtained under conditions such as 2 can be applied. The antibacterial composite non-woven sheet obtained by being water-entangled as described above, the pulp fibers of the part in contact with the high pressure water column flow of the paper sheet are isolated, and the deformation such as bending and twisting is imparted, The fibers and pulp fibers are entangled with each other, giving it a voluminous feel and the appearance and flexibility similar to cloth towels.
【００１９】[0019]
【実施例】以下に実施例を挙げて本発明をより具体的に
説明するが、もちろん本発明はこれらによって限定され
るものではない。なお、実施例および比較例中の％は、
特に断わらない限り重量％を示す。The present invention will be described in more detail with reference to the following examples, but of course the present invention is not limited thereto. Incidentally,% in Examples and Comparative Examples is
Unless otherwise specified,% by weight is shown.
【００２０】実施例１ 置換度が０．４２の酸型ＣＭＣ（ＣＭＣ酸、キッコレー
トＨＣ、ニチリン化学工業社製）に、固形分濃度２％の
硝酸銀水溶液を添加して２．５％のスラリー濃度とし
て、十分撹拌して温度２５℃に置いて６０分間静置し
た。その後、内容物を脱液して水洗を十分に行い、遠心
脱水機で３０％のパルプ濃度まで脱水し、固形分濃度３
０％のＣＭＣ銀塩を得た。このＣＭＣ銀塩中の絶乾全重
量当りの銀含有率は、１．８４％であった。このＣＭＣ
銀塩を家庭用ミキサーで１分間撹拌して開繊した後、未
叩解の針葉樹晒クラフトパルプに混合し、絶乾全重量当
りＣＭＣ銀塩の含有量が０．５４％となるように混合パ
ルプを準備し、実験室手すきマシーンで坪量が９５ｇ／
ｍ2の紙シートを作製した。得られた紙シート中の銀含
有量は、絶乾全重量当り０．０１％であった。Example 1 An acid type CMC having a degree of substitution of 0.42 (CMC acid, Kikkolate HC, manufactured by Nichirin Chemical Co., Ltd.) was added with an aqueous silver nitrate solution having a solid concentration of 2% to obtain a slurry concentration of 2.5%. As a result, the mixture was sufficiently stirred, placed at a temperature of 25 ° C., and left standing for 60 minutes. After that, the contents were deliquored, washed thoroughly with water, and dehydrated to a pulp concentration of 30% with a centrifugal dehydrator to obtain a solid concentration of 3
0% CMC silver salt was obtained. The silver content based on the total dry weight of the CMC silver salt was 1.84%. This CMC
After stirring the silver salt with a household mixer for 1 minute to open it, it is mixed with unbeaten bleached softwood kraft pulp and mixed pulp so that the content of CMC silver salt is 0.54% based on the total dry weight. Is prepared and the basis weight is 95 g /
An m 2 paper sheet was prepared. The silver content in the obtained paper sheet was 0.01% based on the total dry weight.
【００２１】次に、繊度が２．５デニール、坪量が２０
ｇ／ｍ2のポリプロピレン樹脂からなるスパンボンド不
織布を用意した。不織布には面積が０．３ｍｍ2、総面
積で７面積％の点融着区域が設けられていた。手すき紙
シートを巻取りから連続的に引き出されている不織布の
上に積層し、この積層体を回転式のエンドレス金網（３
０メッシュステンレスワイヤ）に載置し、次いで孔径が
０．１５ｍｍのノズル孔が１ｍｍ間隔で並んで設けてあ
る高圧水柱流装置の下を１０ｍ／分の速度で移動させ、
水圧９０ｋｇ／ｍ2で水柱流を噴出させ、水交絡を行わ
せ、抗菌性複合不織布シートを得た。Next, the fineness is 2.5 denier and the basis weight is 20.
A spunbonded nonwoven fabric made of polypropylene resin of g / m 2 was prepared. The non-woven fabric had an area of 0.3 mm 2 and a total area of 7 area% of spot fusion bonded areas. A sheet of handmade paper is laminated on a non-woven fabric which is continuously drawn from the winding, and this laminated body is combined with a rotary endless wire mesh (3
0 mesh stainless wire), and then moved at a speed of 10 m / min under a high pressure water column flow device in which nozzle holes having a hole diameter of 0.15 mm are arranged side by side at 1 mm intervals,
A water column flow was jetted at a water pressure of 90 kg / m 2 to cause water entanglement to obtain an antibacterial composite non-woven sheet.
【００２２】実施例２ 混合パルプ中のＣＭＣ銀塩の含有量が絶乾全重量当り
１．１０％とし、紙シート中の銀含有量を絶乾全重量当
り０．０２％としたこと以外は、実施例１と同様にして
抗菌性複合不織布シートを作製した。Example 2 Except that the content of CMC silver salt in the mixed pulp was 1.10% based on the total dry weight, and the content of silver in the paper sheet was 0.02% based on the total dry weight. An antibacterial composite non-woven sheet was prepared in the same manner as in Example 1.
【００２３】実施例３ 混合パルプ中のＣＭＣ銀塩の含有量が絶乾全重量当り
８．２０％とし、紙シート中の銀含有量を絶乾全重量当
り０．１５％としたこと以外は、実施例１と同様にして
抗菌性複合不織布シートを作製した。Example 3 Except that the content of CMC silver salt in the mixed pulp was 8.20% based on the total dry weight, and the silver content in the paper sheet was 0.15% based on the total dry weight. An antibacterial composite non-woven sheet was prepared in the same manner as in Example 1.
【００２４】比較例１ 針葉樹晒クラフトパルプからなり、銀塩を含有しない紙
シートを用いた以外は、実施例１と同様にして複合不織
布シートを作製した。Comparative Example 1 A composite non-woven sheet was prepared in the same manner as in Example 1 except that a paper sheet made of bleached softwood kraft pulp and containing no silver salt was used.
【００２５】比較例２ 混合パルプ中のＣＭＣ銀塩の含有量が絶乾全重量当り
０．２７％とし、紙シート中の銀含有量を絶乾全重量当
り０．００５％としたこと以外は、実施例１と同様にし
て抗菌性複合不織布シートを作製した。Comparative Example 2 Except that the content of CMC silver salt in the mixed pulp was 0.27% based on the total dry weight, and the silver content in the paper sheet was 0.005% based on the total dry weight. An antibacterial composite non-woven sheet was prepared in the same manner as in Example 1.
【００２６】実施例１〜３および比較例１〜２で得られ
た複合不織布シートの抗菌性の試験を次の方法で行っ
た。抗菌性の試験方法 被検菌株は、繊維製品の試験によく用いられる菌種であ
ることおよび一般的な環境下で存在するもので、グラム
陰性菌のうち代表的な肺炎桿菌（Ｋｌｅｂｓｉｅｌｌａ
ｐｎｅｕｍｏｎｉａｅ ＩＦ０１２７３２）トグラム
陽性菌のうち代表的な黄色ブドウ状球菌（Ｓｔａｐｈｙ
ｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ＩＦＯ１２７３２）
の２種類を用いた。培地は、前培養には普通ブイヨン培
地を、本培養には普通寒天培地を用いた。それぞれの培
地の組成は下記に示すとおりである。 普通ブイヨン培地 普通寒天培地 肉エキス ５ｇ 肉エキス ５ｇ ペプトン １０ｇ ペプトン １０ｇ 塩化ナトリウム ５ｇ 塩化ナトリウム ５ｇ 蒸留水 １０００ｍｌ 寒天 １５ｇ ｐＨ ７．０ 蒸留水 １０００ｍｌ ｐＨ ７．０The antibacterial properties of the composite nonwoven fabric sheets obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were tested by the following method. Test method for antibacterial activity The test strain is one that is often used for testing textile products and exists under general environment. Among the Gram-negative bacteria, Klebsiella
pneumoniae IF012732) A typical Staphylococcus aureus among Staphylococcus aureus (Staphy)
lococcus aureus IFO12732)
2 types were used. As a medium, a normal broth medium was used for the pre-culture, and a normal agar medium was used for the main culture. The composition of each medium is as shown below. Normal broth medium Normal agar medium Meat extract 5g Meat extract 5g Peptone 10g Peptone 10g Sodium chloride 5g Sodium chloride 5g Distilled water 1000ml Agar 15g pH 7.0 Distilled water 1000ml pH 7.0
【００２７】試験の手順としては、まず供試菌株を普通
ブイヨン培地において３７℃で２４時間培養し、その培
養液を高圧蒸気で殺菌済みのリン酸緩衝液で菌濃度が１
０4個／ｍｌに希釈した試験菌液を調製した。この液の
７５ｍｌを三角フラスコに入れ、次いで１６０℃、２時
間で乾熱滅菌した絶乾重量で０．７５ｇの複合不織布シ
ート（試験片）を入れた。その後、この三角フラスコを
振とう器にかけ、３４０ｒ．ｐ．ｍ．、２８℃、６０分
の条件で振とうして菌液中の菌と試験片を十分に接触さ
せた。次に、菌液の１０倍から１００、０００倍までの
１０倍希釈系列を作り、それぞれの濃度の菌液１ｍｌと
普通寒天培地１５ｍｌを用いて混釈法でプレートを作っ
た。その後３７℃の培養器で４８時間培養した後、コロ
ニー数を数え、接触前の菌数に対する減菌率を計算で求
め、抗菌性を評価した。減菌率の高いものほど抗菌性が
強いといえるが、減菌率が６５％以上あれば抗菌性があ
るといえる。The test procedure is as follows. First, the strain to be tested is cultivated in ordinary broth medium at 37 ° C. for 24 hours, and the culture solution is sterilized with high-pressure steam to give a bacterial concentration of 1
A test bacterial solution diluted to 04 cells / ml was prepared. 75 ml of this solution was placed in an Erlenmeyer flask, and then 0.75 g of composite non-woven fabric sheet (test piece) by dry heat sterilization at 160 ° C. for 2 hours was placed. Then, this Erlenmeyer flask was placed on a shaker to obtain 340 r.p.m. p. m. The test pieces were sufficiently contacted with the bacteria in the bacterial solution by shaking at 28 ° C for 60 minutes. Next, a 10-fold dilution series from 10 times to 100,000 times the bacterial solution was prepared, and a plate was prepared by the pour method using 1 ml of the bacterial solution of each concentration and 15 ml of normal agar medium. Then, after culturing for 48 hours in a 37 ° C. incubator, the number of colonies was counted, and the sterilization rate relative to the number of bacteria before contact was calculated to evaluate the antibacterial property. It can be said that the higher the sterilization rate is, the stronger the antibacterial property is, and the sterilization rate is 65% or more, the more antibacterial property is.
【００２８】実施例４ 紙シートを作製するための混合パルプ中のＣＭＣ銀塩の
含有量が絶乾全重量当り５．４３％とし、紙シート中の
銀含有量を絶乾全重量当り０．１０％とした以外は、実
施例１と同様にして抗菌性複合不織布シートを作製し
た。得られたシートの１０ｃｍ角の大きさを試験片とし
て用い、蒸留水に浸漬した後、取り出して乾いたろ紙に
挟み軽くプレスして脱水した。浸漬と脱水の操作をそれ
ぞれ０（未処理）、１、３、５、１０回繰り返した後の
それぞれの試験片を実施例１と同様にして被検菌を黄色
ブドウ球菌として抗菌性の試験を行った。Example 4 The content of CMC silver salt in the mixed pulp for producing a paper sheet was 5.43% based on the total dry weight, and the silver content in the paper sheet was 0. An antibacterial composite non-woven fabric sheet was produced in the same manner as in Example 1 except that the content was 10%. A 10 cm square piece of the obtained sheet was used as a test piece, immersed in distilled water, taken out, sandwiched between dry filter papers, and lightly pressed to dehydrate. The operation of dipping and dehydration was repeated 0 (untreated), 1, 3, 5, and 10 times, and each test piece was subjected to the same antibacterial test using Staphylococcus aureus as the test bacteria. went.
【００２９】比較例３ 比較例１で得られた複合不織布シートを硝酸銀水溶液に
含浸後、乾燥し、紙シート中の銀含有量が０．１％とな
るように調整した。得られたシートを実施例４と同様に
して蒸留水への浸漬と脱水の操作を繰り返し、それぞれ
の試験片を実施例１と同様にして抗菌性の試験を行っ
た。Comparative Example 3 The composite non-woven fabric sheet obtained in Comparative Example 1 was impregnated with an aqueous solution of silver nitrate and dried to adjust the silver content in the paper sheet to 0.1%. The obtained sheet was repeatedly immersed in distilled water and dehydrated in the same manner as in Example 4, and each test piece was subjected to the antibacterial test in the same manner as in Example 1.
【００３０】実施例１〜３および比較例１〜２で得られ
た抗菌性の試験結果を表１に、実施例４および比較例３
で得られた抗菌性の試験結果を表２に示した。The antibacterial test results obtained in Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1, and Example 4 and Comparative Example 3 are shown.
Table 2 shows the results of the antibacterial test obtained in Step 1.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】表１および表２から分かるように、本発明
の抗菌性複合不織布シートは、きわめて少ない銀含有率
でも抗菌性に優れており、また繰り返し水に浸漬して脱
水を繰り返しても抗菌剤が溶出せず、安全性があり、抗
菌性に持続性がある（実施例１〜３）。しかしながら、
銀を含有しない場合（比較例１）および銀を含有しても
含有率が低い場合（比較例２）、減菌率が低く、抗菌性
がないか或いは低いので抗菌性複合不織布シートとして
は適さない。従って、本発明の抗菌性複合不織布シート
は、不織布と紙シートを積層して、水交絡により一体化
されているので強度が強く、柔軟性があって吸水性が優
れており、拭き布として繰り返し使用できる。As can be seen from Tables 1 and 2, the antibacterial composite non-woven fabric sheet of the present invention has excellent antibacterial properties even with an extremely low silver content, and the antibacterial agent can be repeatedly immersed in water for repeated dehydration. Does not elute, is safe, and has persistent antibacterial properties (Examples 1 to 3). However,
When it does not contain silver (Comparative Example 1) and when it contains silver but has a low content rate (Comparative Example 2), it has a low sterilization rate and has no or low antibacterial properties, and is therefore suitable as an antibacterial composite nonwoven sheet. Absent. Therefore, the antibacterial composite non-woven fabric sheet of the present invention is laminated with a non-woven fabric and a paper sheet and integrated by water entanglement so that it has high strength, is flexible and has excellent water absorption, and is repeatedly used as a wiping cloth. Can be used.
【００３４】[0034]
【発明の効果】本発明は、抗菌剤が非溶出タイプで安全
性が高く、抗菌性に持続性があり、拭き布として好適に
使用し得る抗菌性複合不織布シートを提供するという効
果を奏する。INDUSTRIAL APPLICABILITY The present invention has the effect of providing an antibacterial composite non-woven sheet which is a non-eluting type antibacterial agent, has a high level of safety, has a long-lasting antibacterial property, and can be suitably used as a wiping cloth.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｄ０４Ｈ 5/02 Ｚ // Ｄ２１Ｈ 27/30 Ｄ０６Ｍ 101:06 Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location D04H 5/02 Z // D21H 27/30 D06M 101: 06
Claims (2)
ド不織布と、セルロースパルプ繊維からなる紙シートと
を高圧水柱流で一体化された複合不織布シートにおい
て、該紙シートがカルボキシメチルセルロースにイオン
交換により銀を固定して生成されるカルボキシメチルセ
ルロース銀塩を含有することを特徴とする抗菌性複合不
織布シート。1. A composite nonwoven fabric sheet in which a spunbonded nonwoven fabric composed of hydrophobic continuous filaments and a paper sheet composed of cellulose pulp fibers are integrated by a high pressure water column flow, wherein the paper sheet is ion-exchanged with carboxymethyl cellulose. An antibacterial composite non-woven sheet comprising a carboxymethyl cellulose silver salt produced by fixing silver.
重量当り銀として０．０１〜０．１５重量％であること
を特徴とする請求項１記載の抗菌性複合不織布シート。2. The antibacterial composite non-woven sheet according to claim 1, wherein the silver content of the paper sheet is 0.01 to 0.15 wt% as silver based on the weight of the absolutely dried paper sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6322731A JPH08176961A (en) | 1994-12-26 | 1994-12-26 | Antimicrobial complex nonwoven fabric sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6322731A JPH08176961A (en) | 1994-12-26 | 1994-12-26 | Antimicrobial complex nonwoven fabric sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08176961A true JPH08176961A (en) | 1996-07-09 |
Family
ID=18146999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6322731A Pending JPH08176961A (en) | 1994-12-26 | 1994-12-26 | Antimicrobial complex nonwoven fabric sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08176961A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888526A (en) * | 1996-04-05 | 1999-03-30 | Mitsubishi Paper Mills Limited | Antibacterial antifungal agent and fibrous material containing the same |
| JP2005501982A (en) * | 2001-09-12 | 2005-01-20 | アコーディス スペシャリティー ファイバーズ リミティド | Antibacterial wound dressing |
| KR100693293B1 (en) * | 2005-02-15 | 2007-03-12 | 한국타미나 주식회사 | The water tissue and manufacture method of water tissue use of metallic Nano particles that have anti-fungi and smell exclusion function |
| CN105030123A (en) * | 2015-08-31 | 2015-11-11 | 陈剑 | Manufacturing technology for antibiosis bamboo fiber towel |
| CN105147167A (en) * | 2015-08-31 | 2015-12-16 | 陈剑 | Process for manufacturing cotton pulp fiber towel |
| CN105167691A (en) * | 2015-08-31 | 2015-12-23 | 陈剑 | Preparation process of modal fiber towel |
| CN105231935A (en) * | 2015-08-31 | 2016-01-13 | 陈剑 | Production process of antibacterial Modal fiber towels |
| CN105231933A (en) * | 2015-08-31 | 2016-01-13 | 陈剑 | Production process of antibacterial blended fiber towels |
| CN105231934A (en) * | 2015-08-31 | 2016-01-13 | 陈剑 | Production process of antibacterial cotton pulp fiber towels |
| CN105249871A (en) * | 2015-08-31 | 2016-01-20 | 陈剑 | Process for producing dacron composite fiber towels |
| CN105249872A (en) * | 2015-08-31 | 2016-01-20 | 陈剑 | Process for producing Richcel fiber towels |
| CN105249874A (en) * | 2015-08-31 | 2016-01-20 | 陈剑 | Process for producing antibacterial chitosan fiber towels |
| CN105249873A (en) * | 2015-08-31 | 2016-01-20 | 陈剑 | Process for producing chitosan fiber towels |
| JP2017113428A (en) * | 2015-12-25 | 2017-06-29 | 日本製紙クレシア株式会社 | Laminated wet sheet |
| JP2020051010A (en) * | 2018-09-28 | 2020-04-02 | 日本製紙クレシア株式会社 | Complex nonwoven fabric wiper and manufacturing method thereof |
| CN114790612A (en) * | 2022-05-30 | 2022-07-26 | 上海哈克过滤科技股份有限公司 | Non-woven mop base cloth with antibacterial function and preparation method thereof |
-
1994
- 1994-12-26 JP JP6322731A patent/JPH08176961A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888526A (en) * | 1996-04-05 | 1999-03-30 | Mitsubishi Paper Mills Limited | Antibacterial antifungal agent and fibrous material containing the same |
| JP2005501982A (en) * | 2001-09-12 | 2005-01-20 | アコーディス スペシャリティー ファイバーズ リミティド | Antibacterial wound dressing |
| JP4800573B2 (en) * | 2001-09-12 | 2011-10-26 | コンバテック リミティド | Antibacterial wound dressing |
| KR100693293B1 (en) * | 2005-02-15 | 2007-03-12 | 한국타미나 주식회사 | The water tissue and manufacture method of water tissue use of metallic Nano particles that have anti-fungi and smell exclusion function |
| CN105231933A (en) * | 2015-08-31 | 2016-01-13 | 陈剑 | Production process of antibacterial blended fiber towels |
| CN105147167A (en) * | 2015-08-31 | 2015-12-16 | 陈剑 | Process for manufacturing cotton pulp fiber towel |
| CN105167691A (en) * | 2015-08-31 | 2015-12-23 | 陈剑 | Preparation process of modal fiber towel |
| CN105231935A (en) * | 2015-08-31 | 2016-01-13 | 陈剑 | Production process of antibacterial Modal fiber towels |
| CN105030123A (en) * | 2015-08-31 | 2015-11-11 | 陈剑 | Manufacturing technology for antibiosis bamboo fiber towel |
| CN105231934A (en) * | 2015-08-31 | 2016-01-13 | 陈剑 | Production process of antibacterial cotton pulp fiber towels |
| CN105249871A (en) * | 2015-08-31 | 2016-01-20 | 陈剑 | Process for producing dacron composite fiber towels |
| CN105249872A (en) * | 2015-08-31 | 2016-01-20 | 陈剑 | Process for producing Richcel fiber towels |
| CN105249874A (en) * | 2015-08-31 | 2016-01-20 | 陈剑 | Process for producing antibacterial chitosan fiber towels |
| CN105249873A (en) * | 2015-08-31 | 2016-01-20 | 陈剑 | Process for producing chitosan fiber towels |
| JP2017113428A (en) * | 2015-12-25 | 2017-06-29 | 日本製紙クレシア株式会社 | Laminated wet sheet |
| JP2020051010A (en) * | 2018-09-28 | 2020-04-02 | 日本製紙クレシア株式会社 | Complex nonwoven fabric wiper and manufacturing method thereof |
| CN114790612A (en) * | 2022-05-30 | 2022-07-26 | 上海哈克过滤科技股份有限公司 | Non-woven mop base cloth with antibacterial function and preparation method thereof |
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