JP2571738B2 - Non-woven - Google Patents
Non-wovenInfo
- Publication number
- JP2571738B2 JP2571738B2 JP4023146A JP2314692A JP2571738B2 JP 2571738 B2 JP2571738 B2 JP 2571738B2 JP 4023146 A JP4023146 A JP 4023146A JP 2314692 A JP2314692 A JP 2314692A JP 2571738 B2 JP2571738 B2 JP 2571738B2
- Authority
- JP
- Japan
- Prior art keywords
- regenerated
- performance
- weight
- chitosan
- fiber
- 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.)
- Expired - Fee Related
Links
Landscapes
- Biological Depolymerization Polymers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、衣料分野、衛生材料分
野、医療分野、土木建築分野、更には農業分野等で使用
される不織布に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nonwoven fabric used in the fields of clothing, sanitary materials, medical care, civil engineering, and agriculture.
【０００２】[0002]
【従来の技術】従来より不織布は、オムツや洗浄および
払拭布，衛生ナプキンカバー，病院用ガウン，シーツ，
土木建築材，包材，芯地，育苗ポット，育苗マット等に
幅広く利用されている。これらのうち近年では、オムツ
や洗浄および払拭布，衛生ナプキンカバーのような、人
間の皮膚と接触する状態で使用される例が急増している
為、これらの用途に使われる不織布には、サニタリー性
の面からバクテリアやカビの生育を抑制するものと、こ
れらにより発生する悪臭を消すものが好ましく、抗菌性
能や抗カビ性能，脱臭性能を付与した不織布がいくつか
提案されている。2. Description of the Related Art Conventionally, non-woven fabrics include diapers, cleaning and wiping cloths, sanitary napkin covers, hospital gowns, sheets,
It is widely used for civil engineering building materials, packaging materials, interlining, nursery pots, nursery mats, etc. In recent years, the use of diapers, cleaning and wiping cloths, and sanitary napkin covers in contact with human skin has been increasing rapidly. From the viewpoint of properties, those which suppress the growth of bacteria and mold and those which eliminate the bad odor generated by them are preferable, and some nonwoven fabrics provided with antibacterial performance, antifungal performance and deodorizing performance have been proposed.
【０００３】ここで、従来より用いられていた抗菌性能
や抗カビ性能を与える物質としては、例えば銅や銀，亜
鉛等の金属イオンを有するものや、塩化ベンザルコニウ
ム，有機シリコン系第 4級アンモニウム塩，ヘキサメチ
レンビグアミド塩酸塩等があり、一方、脱臭性能を与え
る物質としては例えば活性炭やシリカゲル，金属フタロ
シアニン誘導体等がある。そして、これらを不織布もし
くは不織布を構成する繊維の表面にある官能基に化学結
合で固定させたり、不織布を構成する繊維の製造段階に
おいて、反応性樹脂を用いて加熱硬化させ、或いは樹脂
中や紡糸原液中に添加させるといった方法により、抗菌
性能や抗カビ性能，脱臭性能を付与した不織布を得てい
る。しかし、これらの用途分野の多くは使い捨て商品で
あるにもかかわらず、使用される抗菌性能や抗カビ性
能，脱臭性能を与える物質は、土壌中で非分解性又は難
分解性の為、環境破壊の原因物質として社会問題となっ
ている。また育苗ポット，育苗マット，土木建築材の分
野においても、使用期間中は抗菌性能や抗カビ性能を保
持し、使用後土壌中にて分解もしくは崩壊するものが望
まれているが、これらについても未だ充分なものは開発
されていない。[0003] Here, as substances conventionally used to provide antibacterial and antifungal properties, for example, substances having metal ions such as copper, silver and zinc, benzalkonium chloride, and organic silicon-based quaternary substances There are ammonium salt, hexamethylene bigamide hydrochloride and the like, while on the other hand, substances giving deodorizing performance include activated carbon, silica gel, metal phthalocyanine derivative and the like. Then, these are fixed to the functional group on the surface of the nonwoven fabric or the fibers constituting the nonwoven fabric by chemical bonding, or in the production stage of the fibers constituting the nonwoven fabric, heat-cured using a reactive resin, A nonwoven fabric having antibacterial, antifungal, and deodorizing properties has been obtained by adding it to a stock solution. However, despite the fact that many of these application fields are disposable products, the substances used to provide antibacterial, antifungal and deodorizing properties are non-degradable or hardly decomposable in soil, so they are environmentally destructive. Has become a social problem as a causative substance. In the fields of seedling pots, seedling mats, and civil engineering and construction materials, it is desirable that the potatoes retain antibacterial and antifungal properties during use and decompose or disintegrate in the soil after use. Not enough has yet been developed.
【０００４】一方、蟹や海老，昆虫類の外骨格に存在す
るキチンの脱アセチル化物であるキトサンに、抗菌性能
や抗カビ性能，脱臭性能と、土壌中での分解性能のある
ことが確認されるようになり、キトサンを用いること
で、上記の問題点を解決しようとする試みが、特開平 3
− 27165号に開示されている。しかし本発明のような、
微小粒状再生キトサンを含有させたセルロース再生繊維
を用いた不織布は知られていない。On the other hand, it has been confirmed that chitosan, which is a deacetylated product of chitin present in the exoskeleton of crabs, shrimps, and insects, has antibacterial performance, antifungal performance, deodorizing performance, and decomposition performance in soil. Thus, an attempt to solve the above-mentioned problems by using chitosan is disclosed in
-Disclosed in 27165. However, as in the present invention,
A nonwoven fabric using regenerated cellulose fibers containing regenerated fine chitosan has not been known.
【０００５】[0005]
【発明が解決しようとする課題】特開平 3− 27165号に
記載の発明は、セルロース系の天然繊維及び半合成繊維
からなる繊維ウェブに、繊維間結合剤としてキトサンを
用いているもので、土壌中での分解性能に極めて優れた
ものとなっている。しかし不織布として人間の皮膚と接
触する状態で使用するには、キトサンが表面に露出して
いる為、脱落しやすい上に風合いが悪く、湿強度が低い
為、実用に耐えられるものではないという欠点があっ
た。そこで本発明は、抗菌性能や抗カビ性能，脱臭性能
を具備した風合いや湿強度に優れた不織布であって、使
用後土壌中に廃棄した際、土壌中の微生物によって、抗
菌性能や抗カビ性能，脱臭性能を持つ物質が完全に分解
される不織布を提供することを目的とする。The invention described in Japanese Patent Application Laid-Open No. 3-27165 discloses a method in which chitosan is used as a fiber-to-fiber binder in a fibrous web composed of cellulosic natural fibers and semi-synthetic fibers. It has extremely excellent decomposition performance in the inside. However, when used as a non-woven fabric in contact with human skin, chitosan is exposed on the surface, so it is easy to fall off, has poor texture, and has low moisture strength, so it is not practically usable. was there. Accordingly, the present invention is directed to a nonwoven fabric having excellent antibacterial performance, antifungal performance, and deodorizing performance and excellent in texture and wet strength. When disposed in soil after use, the antibacterial performance and antifungal performance are caused by microorganisms in the soil. It is an object of the present invention to provide a nonwoven fabric in which a substance having a deodorizing performance is completely decomposed.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、微小粒状
化した再生キトサンが抗菌性能や抗カビ性能，脱臭性能
と、土壌中の微生物による分解性能に優れている点に着
目し、鋭意研究の結果、本発明に到達した。即ち本発明
は、粒子径10μｍ以下の微小粒状再生キトサンを 0.4〜
2.7重量％含有するセルロース再生繊維を構成要素とす
る不織布であって、該セルロース再生繊維の構成比率が
不織布を構成する繊維全体の20重量％であることを特徴
とする不織布に関するものである。Means for Solving the Problems The present inventors have focused on the fact that regenerated chitosan which has been made into fine particles is excellent in antibacterial performance, antifungal performance, deodorizing performance, and decomposition performance by microorganisms in soil. As a result of research, the present invention has been reached. That is, the present invention provides a fine granular regenerated chitosan having a particle diameter of 10 μm or less from 0.4 to
The present invention relates to a nonwoven fabric comprising a regenerated cellulose fiber containing 2.7% by weight as a component, wherein the composition ratio of the regenerated cellulose fiber is 20% by weight of the whole fiber constituting the nonwoven fabric.
【０００７】本発明の不織布は以下の様にして得る事が
出来る。先ず微小粒状再生キトサンを含有するセルロー
ス再生繊維を得るには、本出願人が先に出願した特願平
3−22002号に記載の方法が採用される。即ち、キトサ
ンを酸性水溶液に溶解してキトサン酸性水溶液とし、該
水溶液を塩基性溶液中に落下等の手段で加え、凝固再生
させた再生キトサンを、中性になるまで充分洗浄した
後、該再生キトサンを更に微小粒状化することによっ
て、微小粒状再生キトサンとする。The nonwoven fabric of the present invention can be obtained as follows. First, in order to obtain a regenerated cellulose fiber containing regenerated chitosan in the form of fine particles, the applicant of the present invention has filed Japanese Patent Application No.
The method described in 2-22002 is adopted. That is, chitosan is dissolved in an acidic aqueous solution to form a chitosan acidic aqueous solution, the aqueous solution is added to a basic solution by means such as dropping, and the regenerated chitosan that has been coagulated and regenerated is sufficiently washed until neutral, and then regenerated. The chitosan is further refined into fine particles to obtain regenerated fine chitosan.
【０００８】ここで実施される微小粒状化には、通常の
粉砕機や噴霧乾燥機を使用することができるが、噴霧乾
燥して微小粒状化するには、ホモジナイザー等の通常の
湿式粉砕機で、予め粉砕分散せしめて乳状の懸濁液と
し、噴霧乾燥機のノズルの周辺から吐出される加圧空気
と共に、高温雰囲気中に吐出乾燥させ、所望の微小粒状
再生キトサンを得ることができる。この時噴霧乾燥機の
高温雰囲気中の温度は、微小粒状再生キトサンが乾燥さ
れるに充分な温度であれば良く、 100〜 250℃の範囲で
自由に選択できる。[0008] The usual granulation or spray drier can be used for the fine granulation carried out here. However, for the fine granulation by spray drying, a usual wet pulverizer such as a homogenizer is used. It is preliminarily pulverized and dispersed to form a milky suspension, and is discharged and dried in a high-temperature atmosphere together with pressurized air discharged from around the nozzle of the spray dryer to obtain a desired fine granular regenerated chitosan. At this time, the temperature in the high-temperature atmosphere of the spray dryer may be any temperature that is sufficient to dry the fine granular regenerated chitosan, and can be freely selected in the range of 100 to 250 ° C.
【０００９】得られる微小粒状再生キトサンの粒子径
は、10μｍを越えると、セルロースビスコース原液中に
配合した際、これを紡糸すると、糸切れを起こす恐れが
あり好ましくない。粒子径を小さくすると、繊維強度の
低下が起きにくい上、単位重量当たりの表面積が大きく
なり、抗菌性能や抗カビ性能，脱臭性能と、土壌中での
分解性能も増加することから、微小粒状再生キトサンの
粒子径は10μｍ以下とすることが好ましい。このような
微小粒状再生キトサンを得るには、高温雰囲気中に吐出
する際の吐出量と、加えた空気圧を適宜調節する事によ
って、任意に調整を可能とするが、確実に所望の粒子径
の微小粒状再生キトサンを得る為には、更に分級操作を
加えることが好ましい。また必要に応じて微小粒状再生
キトサンを従来公知の方法により、アセチル化等の化学
処理を施しても良い。If the particle size of the obtained fine-grained regenerated chitosan exceeds 10 μm, when it is mixed with a stock solution of cellulose viscose, if it is spun, the yarn may break, which is not preferable. When the particle size is reduced, the fiber strength is hardly reduced, the surface area per unit weight is increased, and the antibacterial performance, antifungal performance, deodorizing performance, and decomposition performance in soil are also increased. It is preferable that the particle diameter of chitosan be 10 μm or less. In order to obtain such fine-grained regenerated chitosan, it is possible to arbitrarily adjust the discharge amount when discharging into a high-temperature atmosphere and by appropriately adjusting the applied air pressure. In order to obtain fine granular regenerated chitosan, it is preferable to further perform a classification operation. If necessary, the fine granular regenerated chitosan may be subjected to a chemical treatment such as acetylation by a conventionally known method.
【００１０】ここで得られた微小粒状再生キトサンをセ
ルロース再生繊維に含有させるには、そのままか又は予
め水又はアルカリ水溶液或いは添加させる適量のセルロ
ースビスコース中に分散させて添加溶液とし、紡糸直前
にセルロースビスコースと混合して紡糸すれば良い。こ
の時の紡糸条件等は、通常のセルロース再生繊維の製造
条件が適用される。又、ここでいうセルロースビスコー
スは、通常レーヨンビスコースとポリノジックビスコー
スであり、従って本発明でいうセルロース再生繊維と
は、通常レーヨンとポリノジックレーヨンであって、そ
の形状はステープル，フィラメントの何れでもよい。更
に、ダル化等の為に酸化チタン等の無機顔料を共に用い
ても良い。該微小粒状再生キトサンの該セルロース再生
繊維中への含有量は、 0.4重量％よりも少ないと、所望
の抗菌性能や抗カビ性能，脱臭効果が得られないことか
ら、 0.4重量％以上であることが好ましく、一方 3.0重
量％より多くすると、繊維強度の低下が見られ、また紡
糸上も困難となるので、最大含有量は 2.7重量％が限度
である。[0010] In order to incorporate the obtained fine-grained regenerated chitosan into the regenerated cellulose fiber, the regenerated fiber may be used as it is or may be previously dispersed in water or an aqueous alkali solution or an appropriate amount of added cellulose viscose to form an addition solution. It may be mixed with cellulose viscose and spun. As for the spinning conditions and the like at this time, ordinary production conditions for regenerated cellulose fibers are applied. The cellulose viscose referred to here is usually rayon viscose and polynosic viscose. Therefore, the regenerated cellulose fibers referred to in the present invention are usually rayon and polynosic rayon, and the shape thereof may be any of staples and filaments. Good. Further, an inorganic pigment such as titanium oxide may be used for dulling or the like. If the content of the microgranular regenerated chitosan in the regenerated cellulose fiber is less than 0.4% by weight, desired antibacterial performance, antifungal performance and deodorizing effect cannot be obtained. On the other hand, if it is more than 3.0% by weight, a decrease in fiber strength is observed and spinning becomes difficult, so the maximum content is limited to 2.7% by weight.
【００１１】次に不織布を製造するが、その方法につい
ては特別な手法を必要とせず、通常実施される製造方法
を適用することができる。更に必要に応じてエンボス加
工等の二次加工を施すこともできる。又、該セルロース
再生繊維単独以外に他の繊維、例えばナイロン，アクリ
ル，ポリビニルアルコール，ポリエステル，ポリプロピ
レン，ポリエチレン等の合成繊維や綿，レーヨン，パル
プ等の天然由来繊維、及びアセテート等の半合成繊維の
一種又は数種を混繊することもできる。これら繊維に対
する該セルロース再生繊維の配合量は、抗菌性能や抗カ
ビ性能，脱臭性能を十分に発揮させる為に、不織布を構
成する繊維全体の20重量％以上とすることが必要であ
る。更に、土壌中に廃棄することを考慮する時は、生分
解性の繊維、例えば綿やレーヨン，パルプ等の天然由来
繊維を用いることが好ましい。Next, a non-woven fabric is manufactured, and a special method is not required for the method, and a generally-used manufacturing method can be applied. Further, secondary processing such as embossing can be performed as necessary. Further, other than the regenerated cellulose fibers alone, other fibers such as synthetic fibers such as nylon, acrylic, polyvinyl alcohol, polyester, polypropylene and polyethylene, natural fibers such as cotton, rayon and pulp, and semi-synthetic fibers such as acetate. One or several kinds can be mixed. The amount of the regenerated cellulose fibers to be added to these fibers must be 20% by weight or more of the entire fibers constituting the nonwoven fabric in order to sufficiently exhibit antibacterial performance, antifungal performance and deodorizing performance. Further, when considering disposal in the soil, it is preferable to use biodegradable fibers, for example, fibers of natural origin such as cotton, rayon, and pulp.
【００１２】このようにして得られた不織布は抗菌性能
や抗カビ性能，脱臭性能を有しつつも、抗菌性能や抗カ
ビ性能，脱臭性能を与える物質、つまり微小粒状再生キ
トサンが、土壌中微生物により有害物質の生成もなく分
解され、しかも該セルロース再生繊維単独の不織布又
は、生分解性繊維と混繊した不織布は、土壌微生物によ
り完全に分解される。また抗菌性能や抗カビ性能を与え
る微小粒状再生キトサンが繊維の内部にまで存在してい
る為、キトサンが脱落せず、風合いも極めて良好な不織
布である。The nonwoven fabric thus obtained has antibacterial performance, antifungal performance and deodorizing performance, but also a substance imparting antibacterial performance, antifungal performance and deodorizing performance, that is, fine-grained regenerated chitosan is used for the microorganisms in the soil. As a result, the nonwoven fabric of the cellulose regenerated fiber alone or the nonwoven fabric mixed with the biodegradable fiber is completely decomposed by soil microorganisms. In addition, since fine-grained regenerated chitosan for imparting antibacterial performance and antifungal performance is present even inside the fiber, the chitosan does not fall off and the texture is extremely good.
【００１３】[0013]
【実施例】以下、本発明について、実施例により具体的
に説明するが、本発明はこの範囲に限定されるものでは
ない。なお、本実施例で測定している各数値は、以下の
方法に基づいて測定した。EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these ranges. In addition, each numerical value measured in this example was measured based on the following method.
【００１４】・セルロース再生繊維中の微小粒状再生キ
トサン含有量の測定方法 JIS K-0102 (1986年) 工業排水試験方法 44-1 有機体
窒素測定方法に準じて試料を前処理（ケルダール法）
し、有機物を分解後、水蒸気蒸留してインドフェノール
青吸光光度法でアンモニウムイオンを定量、これをキト
サンに換算して求めた。即ち前処理としては、試料 2.5
ｇに硫酸30ml，硫酸カリウム10ｇ及び硫酸銅 5水和物 1
ｇを加え、ケルダールフラスコ 300mlに入れ、ヒーター
上で試料が黒褐色から青褐色になるまで加熱分解後、放
冷し、蒸留フラスコに水 300mlと共に仕込み、50％（Ｗ
／Ｖ）苛性ソーダ溶液を加えてpH 8.3〜10に調整し、0.
05Ｎ硫酸50mlを加えた 200ml共栓付きメスシリンダーを
受器として、蒸留フラスコを加熱し、留出速度 5〜 7ml
／min で水蒸気蒸留を行った。ここで発生したアンモニ
ウムイオンをインドフェノール青吸光光度計で定量する
が、その方法としては、先ず前処理を行った試料液 5ml
を50mlメスフラスコに採取し、 5％（Ｗ／Ｖ）のＥＤＴ
Ａ水溶液を 1ml加え、ナトリウムフェラート溶液（フェ
ノール25ｇを 5Ｎ苛性ソーダ溶液55mlに溶解し、冷却後
アセトン 6mlを加え、 200mlとしたもの）を10ml，有効
塩素 1％（Ｗ／Ｖ）の次亜塩素酸ナトリウム溶液 5mlを
加え、水で標線を合わせ30分間放置後吸光度（波長 630
nm）を測定した。定量は 1容量％アンモニウム標準液を
0〜10mlに段階的採取したもので検量線を作成し、定量
されたアンモニウムイオンをキトサンの分子量に換算し
て求めた。Method for measuring the content of fine and granular regenerated chitosan in regenerated cellulose fiber JIS K-0102 (1986) Industrial wastewater test method 44-1 Pretreatment of sample according to organic nitrogen measurement method (Kjeldahl method)
After decomposing the organic matter, steam distillation was performed, and ammonium ion was quantified by indophenol blue absorptiometry, which was converted to chitosan. That is, as pretreatment, sample 2.5
30 g of sulfuric acid, 10 g of potassium sulfate and copper sulfate pentahydrate in 1 g
g into a Kjeldahl flask, heat-decompose the sample on a heater until the sample turns from black-brown to blue-brown, then stood to cool, charged in a distillation flask with 300 ml of water, and added 50% (W
/ V) Adjust the pH to 8.3-10 by adding caustic soda solution,
The distillation flask was heated using a 200 ml graduated cylinder fitted with a stopper to which 50 ml of 05N sulfuric acid was added, and the distillation rate was 5 to 7 ml.
/ Min steam distillation. The ammonium ions generated here are quantified using an indophenol blue absorption spectrophotometer.
Was collected in a 50 ml volumetric flask, and 5% (W / V) EDT
A solution (1 ml), sodium ferrate solution (25 g of phenol dissolved in 55 ml of 5N caustic soda solution, cooled and added with 6 ml of acetone to make 200 ml), 10 ml of available chlorine 1% (W / V) hypochlorous acid Add 5 ml of sodium acid solution, adjust the marked line with water and leave for 30 minutes.
nm). For quantification, use 1 volume% ammonium standard solution
A calibration curve was prepared from those sampled stepwise from 0 to 10 ml, and the quantified ammonium ion was converted to the molecular weight of chitosan and determined.
【００１５】・不織布の目付，厚み，破断時強度の測定
方法 目付は、試料の重量を測定し、平方メートル当たりに換
算した。厚みは試料の100ｇ／ 5cm2 荷重下における 9
点の測定値の平均値とした。強度は 5cm×15cmの試料を
2点作成して縦，横方向に測定し、夫々の平均値とし
た。Method for measuring the basis weight, thickness, and strength at break of nonwoven fabric The basis weight was obtained by measuring the weight of a sample and converting the weight per square meter. The thickness of the sample under a load of 100 g / 5 cm 2
The average value of the measured values at the points was used. The strength is 5cm x 15cm.
Two points were created, measured in the vertical and horizontal directions, and averaged for each.
【００１６】・抗菌性能測定試験（菌数測定法） 繊維製品衛生加工協議会の、抗菌防臭加工製品の加工効
果評価試験マニュアルの、菌数測定法を採用した。即ち
黄色ブドウ状球菌ＩＦＯ 12732を試験菌体とし、これを
予め普通ブイヨン培地で 5〜30×105 個／mlとなるよう
に培養調整し、試験菌懸濁液とする。該懸濁液 0.2mlを
滅菌処理したネジ付きバイアル瓶中の試料 0.2ｇに均一
に接種し、35〜37℃，18時間静置培養後、容器内に滅菌
緩衝生理食塩液を20ml加え、手で振幅幅30cmで25〜30回
強く振盪して試験中の生菌を液中に分散させた後、滅菌
緩衝生理食塩液で適当な希釈系列を作り、各段階の希釈
液1mlを夫々滅菌シャーレに入れ標準寒天培地の約15ml
混釈平板を同一希釈液に付き各 2枚づつ作成した。これ
を35〜37℃で24〜48時間培養した後、生育コロニー数を
計測し、その希釈倍率を乗じて試料中の生菌数を算出し
た。そして効果の判定は、微小粒状再生キトサンの無添
加試料検体と各混合試料検体の平均菌数を基に次式で増
減値差を求め、 1.6以上を抗菌効果有りとした。 増減値差＝ｌｏｇ（Ｂ／Ａ）−ｌｏｇ（Ｃ／Ａ） Ａ：無添加試料に試験菌を接種直後、分散回収した平均
菌数 Ｂ：無添加試料に試験菌を接種後、18時間培養し分散回
収した平均菌数 Ｃ：添加試料に試験菌を接種後、18時間培養し分散回収
した平均菌数Antimicrobial performance measurement test (microbial count measurement method) The microbial count measurement method of the processing effect evaluation test manual for antibacterial and deodorized processed products of the Textile Sanitation Processing Council was adopted. That is, Staphylococcus aureus IFO 12732 is used as a test cell, which is previously cultured in a normal broth medium so as to have a concentration of 5 to 30 × 10 5 cells / ml to prepare a test cell suspension. 0.2 ml of the suspension was uniformly inoculated to 0.2 g of a sample in a sterilized screw vial, incubated at 35 to 37 ° C. for 18 hours, and 20 ml of sterile buffered saline was added to the container. After vigorously shaking 25-30 times with an amplitude width of 30 cm to disperse the viable bacteria under test in the solution, make an appropriate dilution series with sterile buffered saline, and add 1 ml of the diluted solution in each step to a sterile petri dish. About 15ml of standard agar medium
Two pour plates were prepared for each dilution. After this was cultured at 35 to 37 ° C. for 24 to 48 hours, the number of growing colonies was counted, and the number of viable bacteria in the sample was calculated by multiplying by the dilution factor. The effect was determined based on the average cell count of the sample containing no microparticle regenerated chitosan and the average number of bacteria of each mixed sample according to the following formula. Difference in increase / decrease value = log (B / A) -log (C / A) A: Average number of cells dispersed and recovered immediately after inoculation of the test bacterium into the non-added sample B: Incubation for 18 hours after inoculation of the test bacterium into the non-added sample Average number of cells collected and dispersed C: Average number of cells collected and dispersed for 18 hours after inoculating the test sample with the added sample
【００１７】・抗カビ性能測定試験 ＪＩＳ Ｚ−2911（1960年）カビ抵抗性試験方法 6−2
繊維製品の試験方法（乾式法）を採用した。但しカビは
アスペルギルス・ニゲル（Aspergillus niger）ＡＴＣ
Ｃ 9642を用いた。-Antifungal performance measurement test JIS Z-2911 (1960) Mold resistance test method 6-2
A textile product test method (dry method) was employed. However, mold is Aspergillus niger ATC
C9642 was used.
【００１８】・脱臭性能測定法 試料を70℃， 1時間予備乾燥した後に標準状態の雰囲気
下にさらし、試料10ｇを 3Ｌのテドラーバック内夫々ト
リメチルアミン 100ppm ，硫化水素 100ppm ，アンモニ
ア 100ppm の濃度を封入した雰囲気下で 1時間処理し、
処理後のガス濃度の変化を測定し次式で求めた。 脱臭率（％）＝［（初期ガス濃度−残留ガス濃度）／
（初期ガス濃度）］×100Deodorizing performance measurement method A sample was pre-dried at 70 ° C. for 1 hour, and then exposed to a standard atmosphere. 10 g of the sample was placed in a 3 L Tedlar bag in an atmosphere containing 100 ppm of trimethylamine, 100 ppm of hydrogen sulfide, and 100 ppm of ammonia. Process for 1 hour below,
The change in gas concentration after the treatment was measured and determined by the following equation. Deodorization rate (%) = [(initial gas concentration-residual gas concentration) /
(Initial gas concentration)] x 100
【００１９】・分解性能測定法 試料を地面より 8cm土壌内に埋設し、 4ケ月後の状況を
肉眼判定した。Decomposition performance measurement method The sample was buried in the soil 8 cm from the ground, and the condition 4 months later was visually judged.
【００２０】実施例１ 脱アセチル化度82％，平均分子量45,000のキトサン9.75
kgを、酢酸 4.875kgを含む水140.25kgに加えて溶解し、
キトサン酢酸水溶液を得た。この溶液の20℃に於ける粘
度は、回転粘度計で測定したところ、 3,600 cpsであっ
た。このキトサン酸性水溶液を、 5％苛性ソーダ水溶液
中に落下させて、粒状に凝固再生させた。この凝固物を
中性になるまで十分水で洗浄した後、予め最終固形分濃
度が 3.0〜 3.5％になるよう水を加えて分散液とし、粉
砕分散機（商品名：キャビトロン、日鉄鉱業（株）製）
により10,000 rpmの回転数で 800ｌ／ｈの流量で供給
し、これを 7回繰り返して粉砕分散させ乳状の懸濁液と
した。これを攪拌機で攪拌しながら、ろ液を 5.0kg／cm
2 の加圧空気と共に毎時20ｌの流量で、 230〜 250℃の
高温雰囲気中に吐出して乾燥し、乾燥物をサイクロンコ
レクターに捕集した。該乾燥物を風力分級機（商品名：
スペディック 250、（株）セイシン企業製）を用いて、
分級して粒子径10μｍ以下の微小粒状再生キトサン5.85
kgを得た。Example 1 9.75 chitosan having a degree of deacetylation of 82% and an average molecular weight of 45,000
kg, dissolved in 140.25 kg of water containing 4.875 kg of acetic acid,
An aqueous solution of chitosan acetic acid was obtained. The viscosity of this solution at 20 ° C. was 3,600 cps as measured by a rotational viscometer. The chitosan acidic aqueous solution was dropped into a 5% aqueous solution of caustic soda, and solidified and regenerated in granular form. After sufficiently washing the coagulated product with water until it becomes neutral, water is added in advance to a final solid concentration of 3.0 to 3.5% to form a dispersion, and a pulverizer / disperser (trade name: Cavitron, Nippon Mining ( Co., Ltd.)
At a rotational speed of 10,000 rpm at a flow rate of 800 l / h, and this was repeated seven times to pulverize and disperse to obtain a milky suspension. While stirring this with a stirrer, the filtrate was removed at 5.0 kg / cm.
The mixture was discharged into a high-temperature atmosphere at 230 to 250 ° C. at a flow rate of 20 l / h together with the pressurized air of 2 , dried and collected in a cyclone collector. The dried product is subjected to an air classifier (trade name:
Spedick 250, manufactured by Seishin Enterprise Co., Ltd.)
Classified fine regenerated chitosan 5.85 with a particle size of 10 μm or less 5.85
kg gained.
【００２１】この微小粒状再生キトサンを、従来法によ
って得られたレーヨンビスコース（セルロース 9.0重量
％，全アルカリ 6.0重量％，全硫黄 2.5重量％）に、セ
ルロースに対し、 0.3重量％， 0.5重量％及び 2.0重量
％の混合量になるように予め水に分散させておいた微小
粒状再生キトサン分散液を夫々添加し、均一にレーヨン
ビスコースに混合し、脱泡後、直ちに0.09mm× 100Ｈの
ノズルを使用し、紡糸速度55ｍ／分で、硫酸 110ｇ／
ｌ，硫酸ナトリウム 300ｇ／ｌ，硫酸亜鉛15ｇ／ｌ，温
度50℃の紡糸浴中に紡糸し、通常の二浴緊張紡糸法によ
り延伸し、51mmに切断後、通常の精練乾燥処理をして、
2デニールのセルロース再生繊維夫々30kgを製造した。
これらのセルロース再生繊維中の微小粒状再生キトサン
の含有量を測定したところ、夫々0.26重量％（繊維
１），0.42重量％（繊維２），1.73重量％（繊維３）で
あった。The fine particulate regenerated chitosan is added to rayon viscose (9.0% by weight of cellulose, 6.0% by weight of total alkali, 2.5% by weight of total sulfur) obtained by a conventional method in 0.3% by weight and 0.5% by weight based on cellulose. And 2.0% by weight of a fine-grained regenerated chitosan dispersion previously dispersed in water were added, and the mixture was uniformly mixed with rayon viscose. Immediately after defoaming, a 0.09 mm × 100H nozzle was used. At a spinning speed of 55 m / min and sulfuric acid of 110 g /
1, 300 g / l of sodium sulfate, 15 g / l of zinc sulfate, and spinning in a spinning bath at a temperature of 50 ° C., stretching by a usual two-bath tension spinning method, cutting to 51 mm, and performing a usual scouring and drying treatment.
30 kg each of 2 denier cellulose regenerated fiber was produced.
The content of the fine granular regenerated chitosan in these regenerated cellulose fibers was measured to be 0.26% by weight (fiber 1), 0.42% by weight (fiber 2), and 1.73% by weight (fiber 3).
【００２２】得られた繊維１を20重量％と、ポリプロピ
レン繊維 3Ｄ×64mmを80重量％混繊し、カード及びクロ
スラッパのウェブ成形機でウェブとし、加熱圧着と95Ｐ
／cm2 のニードリングを施して不織布（試料１）を得
た。別に繊維２のみを用いて、試料１と同様の操作でウ
ェブとし、水流絡合させ不織布（試料２）を得た。別に
繊維３を75重量％と、ポリプロピレン繊維 3Ｄ×64mmを
25重量％混繊し、試料１と同様な操作を施して不織布
（試料３）を得た。別に繊維３を50重量％と、普通ビス
コースレーヨン 2Ｄ×51mmを50重量％混繊し、試料２と
同様にウェブを得、95Ｐ／cm2 のニードリングを施して
不織布（試料４）を得た。20% by weight of the obtained fiber 1 and 80% by weight of 3D × 64 mm polypropylene fiber were mixed to form a web with a card and cross-wrapper web forming machine, and then heat-pressed and pressed to 95P.
A nonwoven fabric (Sample 1) was obtained by needling at / cm 2 . Separately, a web was formed using only the fiber 2 by the same operation as in the sample 1, and the web was hydroentangled to obtain a nonwoven fabric (sample 2). Separately, 75% by weight of fiber 3 and polypropylene fiber 3D x 64mm
The mixture was subjected to the same operation as in Sample 1 to obtain a nonwoven fabric (Sample 3). Separately, 50% by weight of fiber 3 and 50% by weight of ordinary viscose rayon 2D × 51 mm were mixed to obtain a web in the same manner as in Sample 2, and subjected to needling of 95 P / cm 2 to obtain a nonwoven fabric (Sample 4). Was.
【００２３】得られた試料１〜４の不織布について、目
付，厚み，破断時強度，抗菌性能，抗カビ性能，脱臭性
能及び分解性能を測定したところ、表１の通りであっ
た。The basis weight, thickness, strength at break, antibacterial performance, antifungal performance, deodorizing performance, and decomposition performance of the obtained nonwoven fabrics of Samples 1 to 4 were measured.
【００２４】[0024]
【表１】 [Table 1]
【００２５】この結果から明らかなように、該セルロー
ス再生繊維に対する微小粒状再生キトサン含有量が、
0.4重量％に満たない試料１は、抗菌性能や抗カビ性能
が無く、脱臭性能についても低レベルのものであり、こ
れに対し、本発明にあたる試料２〜４については、抗菌
性能や抗カビ性能，脱臭性能に優れ、土壌中での分解に
ついても該セルロース再生繊維は完全に分解され、痕跡
すら残さなかった。As is apparent from the results, the content of the regenerated fine chitosan with respect to the regenerated cellulose fiber is as follows.
Sample 1 having less than 0.4% by weight has no antibacterial performance or antifungal performance, and has a low level of deodorizing performance, whereas Samples 2 to 4 according to the present invention have antibacterial performance and antifungal performance. The cellulose regenerated fiber was completely decomposed and did not leave any trace even when decomposed in soil.
【００２６】実施例２ 脱アセチル化度90％、平均分子量42,000のキトサン9.75
kgを、酢酸 4.875kgを含む水140.25kgに加えて溶解し、
キトサン酢酸水溶液を得た。この溶液の20℃に於ける粘
度は、回転粘度計で測定したところ、 3,300 cpsであっ
た。このキトサン酸性水溶液を、 5％苛性ソーダ水溶液
中に落下させて、粒状に凝固再生させた。この凝固物を
中性になるまで十分水で洗浄した後、実施例１と同様に
ホモジナイザーを用いて、10,000 rpmの回転数で 800ｌ
／ｈの流量で供給し、これを 8回繰り返して粉砕分散さ
せ乳状の懸濁液とした。これを攪拌機で攪拌しながら、
ろ液を 5.0kg／cm2 の加圧空気と共に毎時18ｌの流量
で、 230〜 250℃の高温雰囲気中に吐出して乾燥し、乾
燥物をサイクロンコレクターに捕集した。該乾燥物を実
施例１と同様にして分級し、粒子径 5μｍ以下の微小粒
状再生キトサン5.36kgを得た。Example 2 9.75 chitosan having a degree of deacetylation of 90% and an average molecular weight of 42,000
kg, dissolved in 140.25 kg of water containing 4.875 kg of acetic acid,
An aqueous solution of chitosan acetic acid was obtained. The viscosity of this solution at 20 ° C. was 3,300 cps as measured by a rotational viscometer. The chitosan acidic aqueous solution was dropped into a 5% aqueous solution of caustic soda, and solidified and regenerated in granular form. The coagulated product was sufficiently washed with water until it became neutral, and then 800 l at 10,000 rpm using a homogenizer in the same manner as in Example 1.
/ H, and this was repeated eight times to be pulverized and dispersed to obtain a milky suspension. While stirring this with a stirrer,
The filtrate was discharged at a flow rate of 18 l / h into a high temperature atmosphere of 230 to 250 ° C. together with 5.0 kg / cm 2 of pressurized air and dried, and the dried product was collected in a cyclone collector. The dried product was classified in the same manner as in Example 1 to obtain 5.36 kg of fine granular regenerated chitosan having a particle size of 5 μm or less.
【００２７】この微小粒状再生キトサンを、ポリノジッ
クビスコース（セルロース 5.0重量％，全アルカリ 3.5
重量％，全硫黄 3重量％）に、セルロースに対し、 0.5
重量％及び 3.0重量％の混合量になるように予め水に分
散させておいた微小粒状再生キトサン分散液を添加，均
一に混合し、脱泡後、直ちに0.07mm×3000Ｈのノズルを
使用し、紡糸速度30ｍ／分で、硫酸22ｇ／ｌ，硫酸ナト
リウム65ｇ／ｌ，硫酸亜鉛 0.5ｇ／ｌ，温度35℃の紡糸
浴中に紡糸し、次いで硫酸 2ｇ／ｌ，硫酸亜鉛0.05ｇ／
ｌ，温度25℃の浴中で 2倍延伸し、38mmに切断後、炭酸
ナトリウム 1ｇ／ｌ，硫酸ナトリウム 2ｇ／ｌ，温度60
℃の条件で処理を行った後、再度硫酸 5ｇ／ｌ，温度65
℃で処理し、通常の精練乾燥処理をして、1.25デニール
のセルロース再生繊維夫々30kgを製造した。これらのセ
ルロース再生繊維の微小粒状再生キトサンの含有量を測
定したところ、夫々0.40重量％（繊維４），2.70重量％
（繊維５）であった。This fine granular regenerated chitosan was mixed with polynosic viscose (cellulose 5.0% by weight, total alkali 3.5).
%, 3% by weight of total sulfur) and 0.5%
Add the fine-grained regenerated chitosan dispersion previously dispersed in water so that the mixing amount becomes 3.0% by weight, and mix uniformly. Immediately after defoaming, use a nozzle of 0.07mm × 3000H. At a spinning speed of 30 m / min, spinning is performed in a spinning bath of 22 g / l sulfuric acid, 65 g / l sodium sulfate, 0.5 g / l zinc sulfate, and a temperature of 35 ° C, and then 2 g / l sulfuric acid and 0.05 g / zinc sulfate.
1, stretched twice in a bath at a temperature of 25 ° C., cut into 38 mm, and then sodium carbonate 1 g / l, sodium sulfate 2 g / l, temperature 60
After treatment under the condition of ° C, sulfuric acid 5g / l, temperature 65
C., and ordinary scouring and drying treatment was performed to produce 30 kg of 1.25 denier regenerated cellulose fibers. When the content of fine granular regenerated chitosan of these regenerated cellulose fibers was measured, they were 0.40% by weight (fiber 4) and 2.70% by weight, respectively.
(Fiber 5).
【００２８】得られた繊維４のみを用いて、カード及び
クロスラッパのウェブ成形機でウェブとし、水流絡合さ
せ不織布（試料５）を得た。別に繊維５を20重量％と、
ポリノジックレーヨン1.25Ｄ×38mmを80重量％混繊し、
同様にウェブとし、95Ｐ／cm2 のニードリングを施して
不織布（試料６）を得た。別に繊維５を15重量％と、綿
を85重量％混繊し、試料５と同様な操作を施して不織布
（試料７）を得た。別に繊維５を30重量％と、ポリエス
テル繊維 3Ｄ×38mmを70重量％混繊し、試料５と同様な
操作を施して不織布（試料８）を得た。別に繊維５を20
重量％と、ポリエステル繊維 3Ｄ×51mmを50重量％，ポ
リプロピレン繊維 3Ｄ×64mm混繊し、加熱圧着と95Ｐ／
cm2 のニードリングを施して不織布（試料９）を得た。Using only the obtained fiber 4, a web was formed by a card and cross-wrapper web forming machine, and the web was hydroentangled to obtain a nonwoven fabric (sample 5). Separately, with fiber 5 at 20% by weight,
80% by weight of Polynosic rayon 1.25D x 38mm
Similarly, a web was formed and subjected to needling of 95 P / cm 2 to obtain a nonwoven fabric (sample 6). Separately, 15% by weight of fiber 5 and 85% by weight of cotton were mixed, and the same operation as in sample 5 was performed to obtain a nonwoven fabric (sample 7). Separately, 30% by weight of fiber 5 and 70% by weight of 3D × 38 mm polyester fiber were mixed, and the same operation as in sample 5 was performed to obtain a nonwoven fabric (sample 8). Separately, fiber 5 20
50% by weight of polyester fiber 3D × 51mm, polypropylene fiber 3D × 64mm, and heat compression and 95P /
A needling of cm 2 was performed to obtain a nonwoven fabric (sample 9).
【００２９】得られた試料５〜９の不織布について、目
付，厚み，破断時強度，抗菌性能，抗カビ性能，脱臭性
能及び分解性能を測定したところ、表２の通りであっ
た。The basis weight, thickness, strength at break, antibacterial performance, antifungal performance, deodorizing performance, and decomposition performance of the obtained nonwoven fabrics of Samples 5 to 9 were measured.
【００３０】[0030]
【表２】 [Table 2]
【００３１】この結果から明らかなように、不織布の全
重量に対する該セルロース再生繊維の構成比率が20重量
％に満たない試料７は、抗菌性能や抗カビ性能が無く、
脱臭性能についても低レベルのものであり、これに対
し、本発明にあたる試料５，６，８，９については、抗
菌性能や抗カビ性能，脱臭性能に優れ、土壌中での分解
についても、該セルロース再生繊維は完全に分解され、
痕跡すら残さなかった。As is apparent from the results, Sample 7 in which the composition ratio of the regenerated cellulose fibers to the total weight of the nonwoven fabric was less than 20% by weight had no antibacterial performance or antifungal performance,
On the other hand, the deodorizing performance is also at a low level. On the other hand, the samples 5, 6, 8, and 9 according to the present invention are excellent in antibacterial performance, antifungal performance, and deodorizing performance. Cellulose regenerated fiber is completely decomposed,
No traces were left.
【００３２】[0032]
【発明の効果】本発明の不織布は優れた抗菌性能や抗カ
ビ性能，脱臭性能，実用的に耐えられる物性を具備した
ものであり、また該セルロース再生繊維単独の不織布又
は、生分解性繊維と混繊した不織布は、土壌微生物によ
り完全に分解され、環境汚染防止の効果がある。The nonwoven fabric of the present invention has excellent antibacterial performance, antifungal performance, deodorizing performance, and physical properties that can be practically used. The mixed nonwoven fabric is completely decomposed by soil microorganisms and has an effect of preventing environmental pollution.
【００３３】また、本発明の不織布は、抗菌性能や抗カ
ビ性能，脱臭性能を与える微小粒状再生キトサンが繊維
の内部にまで存在しているためキトサンが脱落せず、風
合いも極めて良好な不織布である。Further, the nonwoven fabric of the present invention is a nonwoven fabric which does not fall off and has an extremely good texture because fine particulate regenerated chitosan which provides antibacterial performance, antifungal performance and deodorizing performance is present even inside the fiber. is there.
Claims (1)
ンを 0.4〜 2.7重量％含有するセルロース再生繊維を構
成要素とする不織布であって、該セルロース再生繊維の
構成比率が不織布を構成する繊維全体の20重量％以上で
あることを特徴とする不織布。1. A nonwoven fabric comprising regenerated cellulose fibers containing 0.4 to 2.7% by weight of regenerated chitosan having a particle diameter of 10 μm or less, wherein the composition ratio of the regenerated cellulose fibers is the entire fiber constituting the nonwoven fabric. Nonwoven fabric characterized by not less than 20% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4023146A JP2571738B2 (en) | 1992-01-13 | 1992-01-13 | Non-woven |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4023146A JP2571738B2 (en) | 1992-01-13 | 1992-01-13 | Non-woven |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05186945A JPH05186945A (en) | 1993-07-27 |
| JP2571738B2 true JP2571738B2 (en) | 1997-01-16 |
Family
ID=12102431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4023146A Expired - Fee Related JP2571738B2 (en) | 1992-01-13 | 1992-01-13 | Non-woven |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2571738B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07258972A (en) * | 1994-03-16 | 1995-10-09 | Rado Kikaku:Kk | Composite raw material comprising chitosan and protein material |
| JP2800094B2 (en) * | 1994-07-13 | 1998-09-21 | 富士紡績株式会社 | Method for improving strikethrough of polynosic fiber fabric |
| GB9613957D0 (en) * | 1996-07-03 | 1996-09-04 | British Textile Tech | Cellulose product |
| AU7456098A (en) * | 1997-05-13 | 1998-12-08 | Young Keun Hong | Aqueous cellulose solution and rayon fiber produced from the same |
| KR20010097226A (en) * | 2000-04-20 | 2001-11-08 | 이신희 | A method of preparing chitosan non-woven fabric of softness and flexibility for medical care |
| KR20020033123A (en) * | 2002-02-28 | 2002-05-04 | (주)케이트론 | Manufacturing processes of antibacterial dye and deodorant textile comprising chitosan oligomer |
| KR100476549B1 (en) * | 2002-11-22 | 2005-03-17 | 벤텍스 주식회사 | functional fabric for the skin |
| JP2005264370A (en) * | 2004-03-18 | 2005-09-29 | Fuji Spinning Co Ltd | Method for modifying and printing fabric |
| CN110894642B (en) * | 2019-12-16 | 2021-06-22 | 中科纺织研究院（青岛）有限公司 | Chitin modified PP spunbonded non-woven fabric |
| CN112176526B (en) * | 2020-09-15 | 2023-01-13 | 浙江优全护理用品科技股份有限公司 | Green antibacterial cleaning and nursing dry towel and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2884091B2 (en) * | 1989-06-20 | 1999-04-19 | 金井重要工業株式会社 | Degradable nonwoven fabric |
| JP2788961B2 (en) * | 1990-06-28 | 1998-08-20 | 工業技術院長 | Biodegradable nonwoven |
-
1992
- 1992-01-13 JP JP4023146A patent/JP2571738B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05186945A (en) | 1993-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8092732B2 (en) | Processing method of the natural cellulose fiber with feature for enhancing the capability of antifungi, antibacteria and deodorization | |
| US5985301A (en) | Antibacterial cellulose fiber and production process thereof | |
| CA2146549C (en) | Durable antimicrobial agents | |
| CA2399954C (en) | Polymer composition and molded articles produced therefrom | |
| US20110224637A1 (en) | LOW pH, OPTIMAL ORP, AND ODOR-REDUCING FIBERS, A PROCESS FOR MAKING THE FIBERS, AND ARTICLES MADE THEREFROM | |
| TWI392780B (en) | Wet melt with a mold, antibacterial and deodorant function of cellulose non-woven system | |
| JP2571738B2 (en) | Non-woven | |
| JP3018304B2 (en) | Sanitary absorbent products | |
| JPH04289211A (en) | Modified cellulosic regenerated fiber | |
| CN1600928A (en) | Non-woven fabrics of chitin, preparation method and usage | |
| EP2880206B1 (en) | Personal care products comprising algal biomass fibers laden with metal ions | |
| TW201437444A (en) | Manufacturing method of bamboo cellulose fiber with natural antimicrobial, deordorization, and negative ion functions | |
| JP5849378B2 (en) | Functional rayon fiber and method for producing the same | |
| CN111961251A (en) | Nano antibacterial material, preparation method thereof, antibacterial fiber material and application | |
| JP3413631B2 (en) | Antibacterial cellulose regenerated fiber | |
| JP3424114B2 (en) | Modified cellulose regenerated fiber and its production method | |
| JP2802988B2 (en) | Modified cellulose regenerated fiber | |
| JP2021031785A (en) | Paramylum-containing rayon fiber and method of producing paramylum-containing rayon fiber | |
| CN1292436A (en) | Bacteriostatic odour-resistant blended yarn, its preparation method and application | |
| JP4321335B2 (en) | Antibacterial / deodorant fiber, method for producing the same, and fiber molded article using the same | |
| He et al. | The spinning, structure, and properties of cellulose/chitin blend filaments through HWM method | |
| EP4177385A1 (en) | Spinning solution, and alginate fiber comprising cannabidiol, method for producing the same, and use thereof | |
| CN113481727A (en) | Organic-inorganic composite antibacterial powder and preparation method thereof | |
| Islam et al. | Wound dressing utilising nonwoven wool matrix | |
| JPH04194079A (en) | Antibacterial, mildew-proofing and deodorizing nonwoven fabric having hydrophilicity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081024 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091024 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091024 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101024 Year of fee payment: 14 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111024 Year of fee payment: 15 |
|
| LAPS | Cancellation because of no payment of annual fees |