JP3413631B2 - Antibacterial cellulose regenerated fiber - Google Patents
Antibacterial cellulose regenerated fiberInfo
- Publication number
- JP3413631B2 JP3413631B2 JP20521296A JP20521296A JP3413631B2 JP 3413631 B2 JP3413631 B2 JP 3413631B2 JP 20521296 A JP20521296 A JP 20521296A JP 20521296 A JP20521296 A JP 20521296A JP 3413631 B2 JP3413631 B2 JP 3413631B2
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- regenerated
- chitosan
- fine particles
- antifungal
- 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.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、セルロース再生繊維が
本来有する吸水性を損なうことなく、優れた保湿性を有
し、抗菌性、抗カビ性、防ダニ性を同時に具備するセル
ロース再生繊維に関し、糸、編織物、不織布、抄紙等の
原料に供され、衣料分野、衛生材料分野、包装資材分
野、産業資材分野、農業分野等に広く利用される繊維を
提供するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a regenerated cellulose fiber having excellent moisture retention without impairing the water absorption originally possessed by the regenerated cellulose fiber, and having antibacterial property, antifungal property and anti-mite property at the same time. The present invention provides a fiber that is used as a raw material for yarns, knitted fabrics, nonwoven fabrics, papermaking, and the like, and is widely used in the fields of clothing, sanitary materials, packaging materials, industrial materials, agriculture, and the like.
【０００２】[0002]
【従来の技術】繊維に対して抗菌性、抗カビ性、防ダニ
性を付与する方法としては、繊維製造時に原料中に薬剤
を混合し紡糸する方法、あるいは繊維に加工処理する方
法等が提案されている。従来より用いられていた抗菌性
を与える物質としては、例えば、銀、銅、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
ナイド塩酸塩等があり、また、抗カビ性を与える物質と
しては、有機チアゾリル化合物、ベンズイミダゾリル化
合物等の有機芳香族型化合物等があり、防ダニ性を与え
る物質としては、殺ダニ剤、忌避剤等がある。そして個
々の薬品を繊維に練込んだり、表面の官能基に化学結合
で固定させること等により、抗菌性、抗カビ性、防ダニ
性を付与した繊維を得ていた。2. Description of the Related Art As a method of imparting antibacterial, antifungal, and tick-proof properties to fibers, a method of mixing a chemical in a raw material at the time of fiber production and spinning, or a method of processing into fibers is proposed. Has been done. Examples of conventionally used substances that impart antibacterial properties include those having metal ions such as silver, copper and zinc, benzalkonium chloride, organic silicon-based quaternary ammonium salts, hexamethylene biguanide hydrochloride and the like. In addition, as the substance that imparts antifungal properties, there are organic thiazolyl compounds, organic aromatic compounds such as benzimidazolyl compounds, and the like, and as the substances that provide acaricide properties, there are acaricides, repellents, and the like. . Then, by kneading the individual chemicals into the fiber, or by fixing the chemical bond to the functional group on the surface, a fiber having an antibacterial property, an antifungal property and an anti-mite property was obtained.
【０００３】しかし、抗菌性、抗カビ性、防ダニ性の対
象となる細菌、カビ、ダニは、生物学的に見ても全く異
なるものであり、それらに抵抗性を有する物質は基本的
に違うものである。従って、抗菌性繊維、抗カビ性繊
維、防ダニ性繊維の如く、細菌、カビ、ダニ、それぞれ
に抵抗性を有する繊維は開発されているが、細菌、カ
ビ、ダニに対して同時に抵抗性を有する繊維は開発され
ていない。However, bacteria, molds and mites, which are targeted for antibacterial properties, antifungal properties and mite-proof properties, are completely different biologically, and substances having resistance to them are basically It ’s different. Therefore, although fibers having resistance to bacteria, fungi, mites, such as antibacterial fibers, antifungal fibers, and mites-proof fibers, have been developed, they are resistant to bacteria, fungi, and mites at the same time. No fibers have been developed.
【０００４】本出願人は特開平４−２８９２１１号公報
で、セルロース再生繊維中に粒子径１０μｍ以下の再生
キトサン微小粒状体又は再生アセチル化キトサン微小粒
状体をビスコース中に混合紡糸して繊維中に０．５重量
％以上２．０重量％以下含有させることによって、再生
繊維本来の強度を損なうことなく、染色性を向上させる
と共に耐久性に富む抗菌・脱臭性能を具備した再生セル
ロース繊維を、また、特願平６−３０８１０９号で、粒
子径１０μｍ以下の第４級アンモニウム塩化キトサン微
小粒状体をビスコース中に混合紡糸し繊維中に０．３〜
１．６重量％含有させることにより、幅広い抗菌スペク
トルを具備する再生セルロース繊維が得られることを開
示した。これらは、キトサン系の微小粒状体のみをビス
コース中に混合し、紡糸した再生セルロース繊維で、抗
菌性を主たる目的としたものであり、抗カビ性、防ダニ
性を目的としたものではなく、また、カニ、エビ、昆虫
類の外骨格から得られるキトサンに抗菌性や抗カビ性が
あることは既に知られているが、セルース分解性を有す
るカビに対する抵抗性は十分とは言えず、防ダニ性は期
待できない。The applicant of the present invention discloses in JP-A-4-289211 that the regenerated chitosan fine particles having a particle diameter of 10 μm or less or the regenerated acetylated chitosan fine particles are mixed and spun in viscose into the fibers. In an amount of 0.5% by weight or more and 2.0% by weight or less, the regenerated cellulose fiber having antibacterial / deodorant performance with improved dyeability and excellent durability without impairing the original strength of the regenerated fiber, Further, in Japanese Patent Application No. 6-308109, quaternary ammonium chloride chitosan fine particles having a particle size of 10 μm or less are mixed and spun in viscose, and 0.3 to 0.3% is added to the fiber.
It has been disclosed that by containing 1.6% by weight, regenerated cellulose fiber having a broad antibacterial spectrum can be obtained. These are regenerated cellulose fibers obtained by mixing only chitosan-based fine particles in viscose and spinning them, with the main purpose being antibacterial properties, not antifungal properties and mites-proof properties. , Crab, shrimp, it is already known that chitosan obtained from the exoskeleton of insects has antibacterial and antifungal properties, but it cannot be said that the resistance to fungi having decomposing ability is sufficient. Anti-mite property cannot be expected.
【０００５】抗カビ性に関しては、有機チアゾリル化合
物、ベンズイミダゾリル化合物等の有機芳香族系化合物
等の抗カビ性能を有する薬剤を繊維原料中に混合し紡糸
したものはなかった。また，これらの抗カビ剤を繊維上
に固着させることにより該性能を発現させることはでき
るが、繊維上に固着させる方法では繊維本来の吸水性、
保湿性、風合いを損なう結果となり、実用的に欠点があ
る。Regarding the antifungal property, there has been no one in which a drug having an antifungal property such as an organic aromatic compound such as an organic thiazolyl compound or a benzimidazolyl compound is mixed in a fiber raw material and spun. Further, although it is possible to develop the performance by fixing these antifungal agents on the fiber, the method of fixing the antifungal agent on the fiber,
This results in impaired moisturizing properties and texture, which is a practical drawback.
【０００６】また、防ダニ性に関しては、殺ダニ剤、忌
避剤を繊維に固着加工することが行われているが、効果
の耐久性、人体に対する安全性の面が指摘されている。
従って、上述の如き抗カビ性、防ダニ性を繊維に付与
し、繊維本来の吸水性、保湿性、風合いを保持し実用上
充分な性能と安全性を有する繊維は開発されていないの
が現状である。Regarding the mites-proofing property, an acaricide or repellent is fixedly processed on the fiber, but it is pointed out that the effect is durable and the human body is safe.
Therefore, it is the present situation that a fiber having the above-described antifungal properties and mite-proof properties is imparted to the fiber, and the water absorbency of the fiber, the moisture retention property, and the texture are maintained and which has practically sufficient performance and safety have not been developed. Is.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、繊維自体が
本来有する吸水性、風合い等の性能を損なうことなく、
優れた保湿性を有し、抗菌性、抗カビ性、防ダニ性を併
せ具備する抗菌性セルロース再生繊維を提供するもので
ある。DISCLOSURE OF THE INVENTION The present invention is directed to the fiber itself without impairing its inherent properties such as water absorption and texture.
It is intended to provide an antibacterial regenerated cellulose fiber having excellent moisturizing properties, antibacterial properties, antifungal properties and anti-mite properties.
【０００８】[0008]
【課題を解決するための手段】本発明者等はかかる課題
を解決すべく鋭意検討した結果、本発明に到達した。即
ち本発明は、粒子径１０μｍ以下の再生キトサン微小粒
状体、又は再生アセチル化キトサン微小粒状体、ニトリ
ル系抗菌剤、ピリジン系抗菌剤、ハロアルキルチオ系抗
菌剤、有機ヨード系抗菌剤、チアゾール系抗菌剤、及び
ベンツイミダゾール系抗菌剤をセルロースビスコースに
添加し、該ビスコースを紡糸した抗菌性セルロース再生
繊維である。本発明の繊維は、これら複数の薬剤を同時
に混合含有していることで抗菌、抗カビ効果の相乗効果
が認められ、それぞれの薬剤が有している単独の効果以
上に幅広い抗菌スペクトル、幅広い抗カビスペクトル、
防ダニ性を発現することが可能である。The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides regenerated chitosan fine particles having a particle diameter of 10 μm or less, or regenerated acetylated chitosan fine particles, nitrile antibacterial agents, pyridine antibacterial agents, haloalkylthio antibacterial agents, organic iodine antibacterial agents, thiazole antibacterial agents. It is an antibacterial cellulose regenerated fiber obtained by adding an agent and a benzimidazole antibacterial agent to cellulose viscose and spinning the viscose. The fiber of the present invention is found to have a synergistic effect of antibacterial and antifungal effects by simultaneously containing a plurality of these drugs, and has a broader antibacterial spectrum and a broader antibacterial spectrum than the single effect of each drug. Mold spectrum,
It is possible to express anti-mite property.
【０００９】[0009]
【発明の実施の形態】本発明に用いられる粒子径が１０
μｍ以下の再生キトサン微小粒状体、又は再生アセチル
化キトサン微小粒状体を得るには、本出願人が特開昭６
２ー６２８２７号公報及び特開昭６２−１００５３４号
公報に開示した方法によって作ることが好ましい。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、該水溶液を塩基性水溶液中に落下等の手段で加
え凝固再生させ再生キトサンとし、又は、該再生キトサ
ンをメタノール、エタノール等の極性溶媒中で無水酢酸
等でアセチル化した再生アセチル化キトサンを、それぞ
れ中性になるまで十分水洗した後、該再生キトサン又は
再生アセチル化キトサンを更に微粒化することによっ
て、再生キトサン微小粒状体又は再生アセチル化キトサ
ン微小粒状体が効率よく得られる。BEST MODE FOR CARRYING OUT THE INVENTION The particle size used in the present invention is 10
In order to obtain regenerated chitosan fine particles having a size of less than or equal to μm, or regenerated acetylated chitosan fine particles, the applicant of the present invention disclosed in Japanese Patent Application Laid-Open No.
It is preferably produced by the method disclosed in JP-A-2-62827 and JP-A-62-100534. That is, chitosan is dissolved in an acidic aqueous solution to give an acidic aqueous solution of chitosan, and the aqueous solution is added to a basic aqueous solution by means such as dropping to coagulate and regenerate to regenerate chitosan, or the regenerated chitosan is dissolved in a polar solvent such as methanol or ethanol. Regenerated acetylated chitosan acetylated with acetic anhydride, etc., is thoroughly washed with water until it becomes neutral, and then the regenerated chitosan or regenerated acetylated chitosan is further atomized to obtain regenerated chitosan fine particles or regenerated acetylated chitosan. Chitosan fine particles can be efficiently obtained.
【００１０】抗菌性の発現、繊維の保湿性の向上には、
キトサンの分子内アミノ基が大きく寄与するため、再生
キトサンをアセチル化して再生アセチル化キトサンにす
る際のアセチル化の程度は、アミノ基を２０％程度残
す、即ち脱アセチル化度が２０％を下らないようにする
ことが好ましい。In order to develop antibacterial properties and improve the moisturizing properties of fibers,
Since the amino group in the molecule of chitosan greatly contributes, the degree of acetylation when acetylating regenerated chitosan to regenerated acetylated chitosan leaves about 20% of the amino group, that is, the degree of deacetylation does not fall below 20%. It is preferable to do so.
【００１１】尚、微粒化には、通常の噴霧乾燥機を使用
することが出来る。噴霧乾燥して微粒化するには、ホモ
ジナイザー等通常の湿式粉砕機で予め粉砕分散せしめ
て、平均粒径を５０μｍ以下にした乳状の懸濁液として
用いるのがよい。このようにして得た懸濁液は、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
出乾燥されるが、この際収縮により更に微粒化される。
高温雰囲気中の温度は、被乾燥物が乾燥されるに充分な
温度であればよく１００〜１８０℃の範囲で自由に選択
できる。得られる微粒子の粒子径は、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ことに
よって、任意に調整することが出来るが、確実に所望の
均一な粒子径の乾燥物を得るためには更に分級すること
が好ましい。A normal spray dryer can be used for atomization. For spray drying and atomization, it is preferable to pulverize and disperse in advance with an ordinary wet pulverizer such as a homogenizer to use as a milky suspension having an average particle diameter of 50 μm or less. The suspension thus obtained is discharged and dried in a high temperature atmosphere together with the pressurized air discharged from the periphery of the nozzle, but at this time, it is further atomized due to contraction.
The temperature in the high temperature atmosphere may be a temperature sufficient to dry the material to be dried, and can be freely selected in the range of 100 to 180 ° C. The particle size of the obtained fine particles can be arbitrarily adjusted by appropriately adjusting the discharge amount and the added air pressure when discharging in a high temperature atmosphere, but it is possible to reliably obtain a dried product having a desired uniform particle size. Further classification is preferable for obtaining.
【００１２】本発明に用いられるニトリル系抗菌剤とし
て好ましくは、ハロアリールニトリル化合物、より好ま
しくはハロイソフタロニトリル化合物が挙げられる。ハ
ロイソフタロニトリル化合物としては、２、４、５、６
−テトラクロロイソフタロニトリル、５−クロロ−２、
４、６−トリフロロイソフタロニトリル等を挙げること
が出来る。The nitrile antibacterial agent used in the present invention is preferably a haloaryl nitrile compound, more preferably a haloisophthalonitrile compound. The haloisophthalonitrile compound is 2, 4, 5, 6
-Tetrachloroisophthalonitrile, 5-chloro-2,
4,6-trifluoroisophthalonitrile and the like can be mentioned.
【００１３】本発明に用いられるピリジン系抗菌剤とし
て好ましくは、ハロゲン化されたピリジン誘導体、ピリ
ジンチオール−１−オキシド化合物等が挙げられ、より
好ましくは、スルフォニルハロピリジン化合物、ピリジ
ンチオール−１−オキシド化合物等が挙げられる。The pyridine antibacterial agent used in the present invention is preferably a halogenated pyridine derivative, a pyridinethiol-1-oxide compound or the like, and more preferably a sulfonylhalopyridine compound or a pyridinethiol-1-oxide. A compound etc. are mentioned.
【００１４】上記ハロゲン化されたピリジン誘導体とし
ては、２−クロロ−６−トリクロロメチルピリジン、２
−クロロ−４−トリクロロメチル−６−メトキシピリジ
ン、２−クロロ−４−トリクロロメチル−６−（２−フ
リルメトキシ）ピリジン、ジ（４−クロロフェニル）ピ
リジルメタノールや、スルフォニルハロピリジン化合物
に分類される、２、３、５、６−テトラクロロ−４−メ
チルスルフォニルピリジン、２、３、５−トリクロロ−
４−（ｎ−プロピルスルフォニル）ピリジン等が挙げら
れ、ピリジンチオール−１−オキシド化合物としては、
２−ピリジンチオール−１−オキシドナトリウム、２−
ピリジンチオール−１−オキシド亜鉛、ジ（２−ピリジ
ンチオール−１−オキシド）等が挙げられる。Examples of the halogenated pyridine derivative include 2-chloro-6-trichloromethylpyridine and 2
-Chloro-4-trichloromethyl-6-methoxypyridine, 2-chloro-4-trichloromethyl-6- (2-furylmethoxy) pyridine, di (4-chlorophenyl) pyridylmethanol and sulfonylhalopyridine compounds. 2,3,5,6-tetrachloro-4-methylsulfonylpyridine, 2,3,5-trichloro-
4- (n-propyl sulfonyl) pyridine etc. are mentioned, As a pyridine thiol 1-oxide compound,
2-Pyridinethiol-1-oxide sodium, 2-
Pyridinethiol-1-oxide zinc, di (2-pyridinethiol-1-oxide) and the like can be mentioned.
【００１５】本発明に用いられるハロアルキルチオ系抗
菌剤として好ましくは、ハロアルキルチオフタルイミド
化合物、ハロアルキルチオテトラヒドロフタルイミド化
合物、ハロアルキルチオスルファミド化合物、ハロアル
キルチオスルフィミド化合物等を挙げることが出来る。Preferred examples of the haloalkylthio type antibacterial agent used in the present invention include haloalkylthiophthalimide compounds, haloalkylthiotetrahydrophthalimide compounds, haloalkylthiosulfamide compounds and haloalkylthiosulfimide compounds.
【００１６】上記ハロアルキルチオフタルイミド化合物
としては、Ｎ−フロロジクロロメチルチオフタルイミ
ド、Ｎ−トリクロロメチルチオフタルイミド等が挙げら
れ、ハロアルキルチオテトラヒドロフタルイミド化合物
としては、Ｎ−１、１、２、２−テトラクロロエチルチ
オテトラヒドロフタルイミド、Ｎ−トリクロロメチルチ
オテトラヒドロフタルイミド等を挙げることが出来る。Examples of the haloalkylthiophthalimide compound include N-florodichloromethylthiophthalimide and N-trichloromethylthiophthalimide, and examples of the haloalkylthiotetrahydrophthalimide compound include N-1,1,2,2-tetrachloroethylthiotetrahydrophthalimide. , N-trichloromethylthiotetrahydrophthalimide and the like.
【００１７】また、ハロアルキルチオスルファミド化合
物としては、Ｎ−トリクロロメチルチオ−Ｎ−（フェニ
ル）メチルスルファミド、Ｎ−トリクロロメチルチオ−
Ｎ−（４−クロロフェニル）メチルスルファミド、Ｎ−
（１−フロロ−１、１、２、２−テトラクロロエチルチ
オ）−Ｎ−（フェニル）メチルスルファミド、Ｎ−
（１、１−ジフロロ−１、２、２−トリクロロエチルチ
オ）−Ｎ−（フェニル）メチルスルファミド等が挙げら
れ、ハロアルキルチオスルフィミド化合物としては、
Ｎ、Ｎ−ジメチル−Ｎ´−フェニル−Ｎ´−（フロロジ
クロロメチルチオ）スルフィミド、Ｎ、Ｎ−ジクロロフ
ロロメチルチオ−Ｎ´−フェニルスルフィミド、Ｎ、Ｎ
−ジメチル−Ｎ´−（ｐ−トリル）−Ｎ´−（フロロジ
クロロメチルチオ）スルフィミド等を挙げることが出来
る。The haloalkylthiosulfamide compounds include N-trichloromethylthio-N- (phenyl) methylsulfamide and N-trichloromethylthio-.
N- (4-chlorophenyl) methylsulfamide, N-
(1-Fluoro-1,1,2,2-tetrachloroethylthio) -N- (phenyl) methylsulfamide, N-
(1,1-difluoro-1,2,2-trichloroethylthio) -N- (phenyl) methylsulfamide and the like can be mentioned. As the haloalkylthiosulfimide compound,
N, N-dimethyl-N'-phenyl-N '-(florodichloromethylthio) sulfimide, N, N-dichlorofluoromethylthio-N'-phenylsulfimide, N, N
-Dimethyl-N '-(p-tolyl) -N'-(florodichloromethylthio) sulfimide and the like can be mentioned.
【００１８】本発明に用いられる有機ヨード系抗菌剤と
しては好ましくは、ヨードスルフォン化合物、ヨウ化不
飽和脂肪族化合物等が挙げられ、より好ましくは、ヨー
ドスルフォニルベンゼン化合物を挙げることが出来る。The organic iodine antibacterial agent used in the present invention is preferably an iodosulfone compound, an iodinated unsaturated aliphatic compound or the like, and more preferably an iodosulfonylbenzene compound.
【００１９】上記ヨードスルフォニル化合物としては、
ヨードスルフォニルベンゼン化合物である、ジヨードメ
チル−ｐ−トリルスルフォン、１−ジヨードメチルスル
フォニル−４−メチルベンゼン、１−ジヨードメチルス
ルフォニル−４−クロロベンゼン等が挙げられ、また、
ヨウ化不飽和脂肪族化合物としては、３−ヨード−２−
プロパルギルブチルカルバミン酸、４−クロロフェニル
−３−ヨードプロパルギルホルマール、３−エトキシカ
ルボニルオキシ−１−ブロム−１、２−ジヨード−１−
プロペン、２、３、３−トリヨードアリルアルコール等
を挙げることが出来る。The above-mentioned iodosulfonyl compound is
Examples of the iodosulfonylbenzene compound include diiodomethyl-p-tolylsulfone, 1-diiodomethylsulfonyl-4-methylbenzene, 1-diiodomethylsulfonyl-4-chlorobenzene, and the like.
As the iodinated unsaturated aliphatic compound, 3-iodo-2-
Propargyl butylcarbamic acid, 4-chlorophenyl-3-iodopropargyl formal, 3-ethoxycarbonyloxy-1-bromo-1,2-diiodo-1-
Examples include propene, 2,3,3-triiodoallyl alcohol and the like.
【００２０】本発明に用いられるチアゾール系抗菌剤と
して好ましくは、イソチアゾリン−３−オン化合物、ベ
ンツチアゾール化合物等が挙げられ、より好ましくは、
イソチアゾリン−３−オン化合物等を挙げることが出来
る。The thiazole antibacterial agent used in the present invention is preferably an isothiazolin-3-one compound, a benzthiazole compound or the like, and more preferably,
An isothiazolin-3-one compound etc. can be mentioned.
【００２１】上記イソチアゾリン−３−オン化合物とし
ては、１、２−ベンツイソチアゾリン−３−オン、２−
（ｎ−オクチル）−４−イソチアゾリン−３−オン、５
−クロロ−２−メチル−４−イソチアゾリン−３−オ
ン、２−メチル−４−イソチアゾリン−３−オン、４、
５−ジクロロ−２−シクロヘキシル−４−イソチアゾリ
ン−３−オン等が挙げられ、ベンツチアゾール化合物と
しては、２−（４−チオシアノメチルチオ）ベンツチア
ゾール、２−メルカプトベンツチアゾールナトリウム、
２−メルカプトベンツチアゾール亜鉛等を挙げることが
出来る。Examples of the above isothiazolin-3-one compounds include 1,2-benzisothiazolin-3-one and 2-
(N-octyl) -4-isothiazolin-3-one, 5
-Chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,
5-dichloro-2-cyclohexyl-4-isothiazolin-3-one and the like can be mentioned, and as the benzthiazole compound, 2- (4-thiocyanomethylthio) benzthiazole, 2-mercaptobenzthiazole sodium,
Examples thereof include 2-mercaptobenzthiazole zinc.
【００２２】本発明に用いられるベンツイミダゾール系
抗菌剤として好ましくは、ベンツイミダゾールカルバミ
ン酸化合物、イオウ原子含有ベンツイミダゾール化合
物、ベンツイミダゾールの環式化合物誘導体等を挙げる
ことが出来、より好ましくは、ベンツイミダゾールカル
バミン酸化合物、チアゾリルベンツイミダゾール化合物
等が挙げられる。The benzimidazole antibacterial agent used in the present invention is preferably a benzimidazolecarbamic acid compound, a sulfur atom-containing benzimidazole compound, a cyclic compound derivative of benzimidazole, or the like, and more preferably benzimidazole. Examples thereof include carbamic acid compounds and thiazolylbenzimidazole compounds.
【００２３】上記ベンツイミダゾールカルバミン酸化合
物としては、１Ｈ−２−ベンツイミダゾールカルバミン
酸メチル、１−ブチルカルバモイル−２−ベンツイミダ
ゾールカルバミン酸メチル、６−ベンゾイル−１Ｈ−２
−ベンツイミダゾールカルバミン酸メチル、６−（２−
チオフェンカルボニル）−１Ｈ−２−ベンツイミダゾー
ルカルバミン酸メチル等が挙げられる。As the above-mentioned benzimidazolecarbamic acid compound, 1H-2-benzimidazole carbamate methyl, 1-butylcarbamoyl-2-benzimidazole carbamate methyl, 6-benzoyl-1H-2.
-Methyl benzimidazole carbamate, 6- (2-
Thiophenecarbonyl) -1H-2-benzimidazole methyl carbamate and the like.
【００２４】また、イオウ原子含有ベンツイミダゾール
化合物としては、１Ｈ−２−チオシアノメチルチオベン
ツイミダゾール、１−ジメチルアミノスルフォニル−２
−シアノ−４−ブロモ−６−トリフロロメチルベンツイ
ミダゾール等を挙げることが出来る。The sulfur atom-containing benzimidazole compounds include 1H-2-thiocyanomethylthiobenzimidazole and 1-dimethylaminosulfonyl-2.
-Cyano-4-bromo-6-trifluoromethylbenzimidazole and the like can be mentioned.
【００２５】ベンツイミダゾールの環式化合物誘導体と
しては、２−（４−チアゾリル）−１Ｈ−ベンツイミダ
ゾール、２−（２−クロロフェニル）−１Ｈ−ベンツイ
ミダゾール、２−（１−（３、５−ジメチルピラゾリ
ル））−１Ｈ−ベンツイミダゾール、２−（２−フリ
ル）−１Ｈ−ベンツイミダゾール等が挙げられる。Examples of cyclic compound derivatives of benzimidazole include 2- (4-thiazolyl) -1H-benzimidazole, 2- (2-chlorophenyl) -1H-benzimidazole and 2- (1- (3,5-dimethyl). Pyrazolyl))-1H-benzimidazole, 2- (2-furyl) -1H-benzimidazole and the like.
【００２６】上記ニトリル系抗菌剤、ピリジン系抗菌
剤、ハロアルキルチオ系抗菌剤、有機ヨード系抗菌剤、
チアゾール系抗菌剤、ベンツイミダゾール系抗菌剤は、
それぞれの抗菌剤より１種又は２種以上を選択し混合し
て用いても良い。また、上述に記載の６種類の抗菌剤の
１種類でも欠けていると期待される効果が発揮されな
い。選ばれた抗菌剤を混合した混合物の粒子径は再生キ
トサン微小粒状体又は再生アセチル化キトサン微小粒状
体と同様に紡糸時の口金詰まりを防止するために１０μ
ｍ以下が好ましい。１０μｍ以下に調整する方法として
は、１０μｍ以下に粉砕機等により微粉砕した個々の抗
菌剤粒子を混合する方法、それぞれの抗菌剤を混合した
後に微粉砕する方法等があるが、何れの方法を用いても
良い。The above nitrile antibacterial agents, pyridine antibacterial agents, haloalkylthio antibacterial agents, organic iodine antibacterial agents,
The thiazole antibacterial agents and benzimidazole antibacterial agents are
One kind or two or more kinds may be selected from the respective antibacterial agents and mixed and used. In addition, even one of the above-mentioned six kinds of antibacterial agents does not exhibit the effect expected to be lacking. The particle size of the mixture obtained by mixing the selected antibacterial agent is 10 μ in order to prevent clogging of the spinneret during spinning as in the case of the regenerated chitosan fine particles or the regenerated acetylated chitosan fine particles.
m or less is preferable. As a method of adjusting to 10 μm or less, there are a method of mixing individual antibacterial agent particles finely crushed to 10 μm or less with a pulverizer, a method of mixing each antibacterial agent and then finely pulverizing. You may use.
【００２７】次に、このようにして得た粒子径１０μｍ
以下の再生キトサン微小粒状体又は再生アセチル化キト
サン微小粒状体とニトリル系抗菌剤、ピリジン系抗菌
剤、ハロアルキルチオ系抗菌剤、有機ヨード系抗菌剤、
チアゾール系抗菌剤、ベンツイミダゾール系抗菌剤をセ
ルロース再生繊維に同時に含有させるには、そのままか
又は、予め水又はアルカリ水溶液に分散させて添加溶液
とするか、ある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よい。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。また、本発明で用いられる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
スがあり、本発明の抗菌性セルロース再生繊維は、ステ
ープル、フィラメント等の如何なる形状でもよく、繊度
にも制限なくまた、ダル化等のため酸化チタン等の無機
顔料を共に用いることもできる。Next, the particle size thus obtained is 10 μm.
The following regenerated chitosan fine particles or regenerated acetylated chitosan fine particles and nitrile antibacterial agents, pyridine antibacterial agents, haloalkylthio antibacterial agents, organic iodine antibacterial agents,
To contain the thiazole type antibacterial agent and the benzimidazole type antibacterial agent in the regenerated cellulose fibers at the same time, as it is, or by dispersing them in water or an alkaline aqueous solution in advance to form an addition solution, or in an appropriate amount of cellulose viscose to be added. It may be dispersed into an additive solution, which may be mixed with cellulose viscose immediately before spinning and spinning. As the spinning conditions and the like at this time, the usual conditions for producing regenerated cellulose fibers are applied. Further, the cellulose viscose used in the present invention, there are usually rayon viscose and polynosic viscose, the antibacterial cellulose regenerated fiber of the present invention may be any shape such as staple, filament, without any limitation in fineness, An inorganic pigment such as titanium oxide may be used together for the purpose of forming a dulled state.
【００２８】粒子形１０μｍ以下の再生キトサン微小粒
状体又は再生アセチル化キトサン微小粒状体とニトリル
系抗菌剤、ピリジン系抗菌剤、ハロアルキルチオ系抗菌
剤、有機ヨード系抗菌剤、チアゾール系抗菌剤、ベンツ
イミダゾール系抗菌剤の合計の対セルロース添加量は、
０．３〜２．０重量％が好ましい。添加量が少ないと所
望の抗菌性や抗カビ性が得られず、添加量が多いと繊維
強度が低下し、実用上不適である。Regenerated chitosan fine particles having a particle size of 10 μm or less or regenerated acetylated chitosan fine particles and a nitrile antibacterial agent, a pyridine antibacterial agent, a haloalkylthio antibacterial agent, an organic iodine antibacterial agent, a thiazole antibacterial agent, and benz. The total amount of cellulose added to the imidazole antibacterial agent is
0.3 to 2.0% by weight is preferable. If the added amount is too small, desired antibacterial properties and antifungal properties cannot be obtained, and if the added amount is too large, the fiber strength decreases, which is not suitable for practical use.
【００２９】再生キトサン微小粒状体又は再生アセチル
化キトサン微小粒状体と抗菌剤を混合した混合物中に占
める再生キトサン微小粒状体又は再生アセチル化キトサ
ン微小粒状体の割合は、１０〜９０％が好ましい。１０
％より少ない場合には充分な抗菌性と繊維の保湿性が得
られず、９０％より多い場合には所望の抗カビ性、防ダ
ニ性が得られない。従ってより好ましくは再生キトサン
微小粒状体又は再生アセチル化キトサン微小粒状体の割
合は２０〜８０％である。実施例からも明らかな如く、
再生キトサン微小粒状体、又は再生アセチル化キトサン
微小粒状体を加えず抗菌剤の混合物のみを含有させたも
のでは本願発明の効果は期待できず、本発明の抗菌性セ
ルロース再生繊維では、上述の構成であることから繊維
本来の吸水性があり、優れた保湿性があり、従来の抗菌
性セルロース再生繊維には見られなかった抗菌性、抗カ
ビ性、防ダニ性を同時に具備している。The proportion of the regenerated chitosan fine particles or the regenerated acetylated chitosan fine particles and the antibacterial agent in the mixture of the regenerated chitosan fine particles or the regenerated acetylated chitosan fine particles is preferably 10 to 90%. 10
When it is less than 90%, sufficient antibacterial properties and moisturizing properties of the fiber cannot be obtained, and when it is more than 90%, desired antifungal properties and mite-proofing properties cannot be obtained. Therefore, more preferably, the ratio of the regenerated chitosan fine particles or the regenerated acetylated chitosan fine particles is 20 to 80%. As is clear from the examples,
The effect of the present invention cannot be expected with a regenerated chitosan fine granule or a mixture containing only a mixture of antibacterial agents without adding regenerated acetylated chitosan fine granules, and the antibacterial cellulose regenerated fiber of the present invention has the above-mentioned constitution. Therefore, it has water absorbency inherent to the fiber, has excellent moisturizing property, and simultaneously has antibacterial properties, antifungal properties, and mites-proof properties not found in conventional antibacterial cellulose regenerated fibers.
【００３０】[0030]
【実施例】以下、本発明の実施例について具体的に説明
するが、本発明はこの範囲に限定されるものではない。
また、繊度、乾強度、湿強度、結節強度、吸湿性、抗菌
性能、抗カビ性能、防ダニ性能等は以下の方法で試験し
た。
（１）繊度、乾強度、湿強度、結節強度
ＪＩＳ Ｌ １０１５ 「化学繊維のステープル試験
法」
（２）吸湿性
試料約１０ｇの絶乾重量を測定し、直ちに３５℃、相対
湿度９０％の環境下に６０分間放置し、その重量を測定
し、重量変化より水分率を求め吸湿性とした。
（３）抗菌性能
繊維製品衛生加工協議会の、抗菌加工製品加工効果試験
マニュアルの、菌数測定法に準じて抗菌性能を測定し
た。その方法は次の通りである。EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited to this range.
Further, fineness, dry strength, wet strength, knot strength, hygroscopicity, antibacterial performance, antifungal performance, mite prevention performance, etc. were tested by the following methods. (1) Fineness, dry strength, wet strength, knot strength JIS L 1015 "Stap test method for chemical fibers" (2) Absolute dry weight of a hygroscopic sample of about 10 g was measured, and an environment of 35 ° C and relative humidity of 90% was immediately measured. It was left to stand for 60 minutes, the weight was measured, and the moisture content was determined from the weight change to obtain the hygroscopicity. (3) Antibacterial performance The antibacterial performance was measured according to the bacteria count measuring method in the antibacterial processed product processing effect test manual of the Textile Products Sanitary Processing Council. The method is as follows.
【００３１】〈菌数測定法〉黄色ブドウ球菌（Staphylo
coccus aureus, IFO 12732，以下表中ではＳ．と示
す）、大腸菌（Escherichia coli, IFO 13168 ，以下表
中ではＥ．と示す）、緑膿菌（Pseudomonas aeruginos
a, IFO 3080，以下表中ではＰ．と示す）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を滅菌処理を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、容器中に滅菌緩衡生理食塩液を２０ｍｌ
加え、手で振幅約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、滅菌緩衡生理食塩
液で適当な希釈系列を作り、各段階の希釈液１ｍｌを各
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枚ずつ作成した。これを３５
〜３７℃で２４時間培養後、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。<Method of measuring the number of bacteria> Staphylococcus aureus (Staphylo
coccus aureus, IFO 12732, S. , Escherichia coli, IFO 13168, designated as E. in the table below, Pseudomonas aeruginos
a, IFO 3080, P. Is used as a test bacterium, and the bacterium is preliminarily cultured in a normal broth medium to a concentration of 5 to 30 × 10 5 cells / ml to give a test bacterium suspension. 0.2 ml of the suspension was uniformly inoculated into 0.2 g of a sample in a sterilized screw-equipped vial, and after static culture at 35 to 37 ° C. for 18 hours, sterile buffered saline was added to the container. 20 ml
In addition, after shaking vigorously by hand for 25 to 30 times with an amplitude of about 30 cm to disperse the live bacteria under test in the solution, make an appropriate dilution series with sterile buffered saline, and dilute 1 ml of each step. Each was placed in a sterilized petri dish and about 15 ml of a standard agar medium was poured into each plate to prepare two plates each with the same dilution. 35 this
After culturing at ~ 37 ° C for 24 hours, count the number of growing colonies,
The number of viable bacteria in the sample was calculated by multiplying the dilution ratio.
【００３２】そして、その効果の判定は、再生キトサン
微小粒状体又は再生アセチル化キトサン微小粒状体とニ
トリル系抗菌剤，ピリジン系抗菌剤，ハロアルキルチオ
系抗菌剤，有機ヨード系抗菌剤，チアゾール系抗菌剤，
ベンツイミダゾール系抗菌剤の無添加試料３検体と添加
試料３検体の平均菌数を基に次式で増減値差を求め、
１．６以上を抗菌効果ありと判定した。The effect is determined by the regenerated chitosan microparticles or regenerated acetylated chitosan microparticles and nitrile antibacterial agents, pyridine antibacterial agents, haloalkylthio antibacterial agents, organic iodine antibacterial agents, thiazole antibacterial agents. Agent,
Based on the average number of bacteria of three non-added samples of benzimidazole antibacterial agent and three added samples, the increase / decrease difference is calculated by the following formula,
It was judged that 1.6 or more had an antibacterial effect.
【００３３】[0033]
【数１】 [Equation 1]
【００３４】（４）抗カビ性能
ＪＩＳ Ｚ ２９１１ 「カビ抵抗性試験」 湿式試験
法
尚、試験菌体はアスペルギルス・ニゲル（Aspergillus
niger,IFO 4414，以下表中ではＡ．と示す）、ケトミウ
ム・グロボサム（Chaetomium globosum,IFO 6347，以下
表中ではＣ．と示す）、トリコデルマ・ビリデ（Tricho
derma viride,IFO 5720 ，以下表中ではＴ．と示す）の
３種類を用いた。結果は、次に示すカビ抵抗性の表示に
より判定した。(4) Antifungal performance JIS Z 2911 "Mold resistance test" Wet test method The test cells were Aspergillus niger.
niger, IFO 4414, A. in the table below. , Chaetomium globosum, IFO 6347, shown as C. in the table below, and Trichoderma viride.
derma viride, IFO 5720, T. Is used). The result was judged by the following indication of mold resistance.
【００３５】[0035]
【表１】 [Table 1]
【００３６】（５）防ダニ性能
直径４cm、高さ０．６cmのプラスチック製シャーレの底
面一面に均一に試料を敷き混みこの上にダニの入ってい
ない粉末飼料０．０５ｇを置く。これを直径９cm、高さ
１．５cmのプラスチック製シャーレの中央に置く。この
大小のシャーレの間に、良く繁殖したダニ培地を生存ダ
ニ数として約３，０００個体投入し、均一に広げる。こ
れを粘着シート上に置き、２７×１３×９cmの食品保存
用プラスチック製容器に粘着シートごと入れ、飽和食塩
水を入れて蓋をして容器内の湿度を約７５％に保ち、２
５℃±１℃の恒温器に格納して１昼夜飼育の後、試料か
ら水洗い法にてダニを回収の後計数し、次式に当てはめ
て忌避率を求めた。なお、試験はばらつきを考慮し、３
回の繰り返しを行った。(5) Acaricide-proof performance A sample is evenly spread over the entire bottom surface of a plastic petri dish having a diameter of 4 cm and a height of 0.6 cm, and 0.05 g of powder feed containing no mites is placed on this. This is placed in the center of a plastic petri dish having a diameter of 9 cm and a height of 1.5 cm. Between the large and small petri dishes, about 3,000 individuals of a well-propagated mite medium are added as the number of living mites and spread uniformly. Place this on an adhesive sheet, put the adhesive sheet in a 27 x 13 x 9 cm plastic container for food storage, add saturated saline solution and cover it to keep the humidity in the container at about 75%.
After storing in a thermostat of 5 ° C. ± 1 ° C. and raising for one day and night, mites were collected from the sample by the water washing method, counted, and applied to the following formula to determine the repellent rate. In addition, considering the variation, the test is 3
Repeated times.
【００３７】[0037]
【数２】 [Equation 2]
【００３８】〔実施例１〕脱アセチル化度８５％平均分
子量４２，０００のキトサン５００ｇを、酢酸２５０ｇ
を含む水７，７５０ｇ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、３，４００cps 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。Example 1 500 g of chitosan having a degree of deacetylation of 85% and an average molecular weight of 42,000 was added to 250 g of acetic acid.
Was added to and dissolved in water (7,750 g) to obtain a chitosan acetic acid aqueous solution. The viscosity of this solution at 20 ° C. was 3,400 cps when measured with a rotational viscometer. This chitosan acidic aqueous solution was dropped into a 5% caustic soda aqueous solution to coagulate and regenerate it into particles.
【００３９】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２〜２．５％になるよう
に水を加えて、１５，０００rpm の回転数で３分間ずつ
３回繰り返して粉砕分散させ乳状の懸濁液とした。これ
を１２０メッシュの篩で粗大片を濾別し、攪拌機で攪拌
しながら、濾液を３．０kg／cm2 の加圧空気と共に毎分
１８ｍｌの流量で、１７０〜１８０℃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（（株）セイシン企業製、
商品名スペディック２５０）を用いて、分級して粒子径
５μｍ以下の再生キトサン微小粒状体３００ｇを得た。The coagulated product was sufficiently washed with water until it became neutral, water was added in advance so that the final solid content concentration was 2 to 2.5%, and the solid matter was rotated at 15,000 rpm for 3 minutes each. It was pulverized and dispersed three times to obtain a milky suspension. Coarse pieces are filtered off with a 120-mesh sieve, and the filtrate is discharged into a high-temperature atmosphere of 170 to 180 ° C at a flow rate of 18 ml per minute together with 3.0 kg / cm 2 of pressurized air while stirring with a stirrer. Then, the dried product was collected in a cyclone collector. The dried product is a wind classifier (manufactured by Seishin Enterprise Co., Ltd.,
300 g of regenerated chitosan fine particles having a particle diameter of 5 μm or less were obtained by classification using a trade name Spedic 250).
【００４０】この再生キトサン微小粒状体に対して、ニ
トリル系抗菌剤，ピリジン系抗菌剤，ハロアキルチオ系
抗菌剤，有機ヨード系抗菌剤，チアゾール系抗菌剤，ベ
ンツイミダゾール系抗菌剤の混合物である市販の抗菌抗
黴剤（（株）センカワ製、商品名Ｋ・Ｂ・９ Ｅ，以下
抗菌抗黴剤Ａと略記する）を再生キトサン微小粒状体対
抗菌抗黴剤Ａが８０対２０（重量比）となるように添加
混合し、再生キトサン微小粒状体と抗菌抗黴剤Ａの混合
物３７５ｇを得た。A commercially available mixture of nitrile antibacterial agents, pyridine antibacterial agents, haloacylthio antibacterial agents, organic iodine antibacterial agents, thiazole antibacterial agents and benzimidazole antibacterial agents is added to the regenerated chitosan microparticulates. Antibacterial and antifungal agent (manufactured by SENKAWA Co., Ltd., trade name KB9E, hereinafter abbreviated as antibacterial and antifungal agent A) is regenerated chitosan microparticulate to antibacterial and antifungal agent A 80 to 20 (weight ratio) And mixed to obtain 375 g of a mixture of regenerated chitosan fine particles and antibacterial and antifungal agent A.
【００４１】この再生キトサン微小粒状体と抗菌抗黴剤
Ａの混合物を、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％、全アルカリ６．０％、全硫
黄２．５％）各１５リットルに、セルロースに対し、
０，０．３，０．５，２．０，３．０重量％の添加量に
なるように予め水に分散させておいた再生キトサン微小
粒状体と抗菌抗黴剤Ａ混合物分散液をそれぞれ添加し、
均一にレーヨンビスコースに混合し、脱泡後、直ちに
０．０９mmφ×１００Ｈのノズルを使用し、紡糸速度５
２ｍ／分で、硫酸１１５ｇ／ｌ、硫酸ナトリウム３１０
ｇ／ｌ、硫酸亜鉛１４ｇ／ｌ、温度５３℃の紡糸浴に紡
糸し、通常の二浴緊張紡糸法により延伸し３２mmに切断
後、通常の精練乾燥処理をして、３デニールの抗菌性セ
ルロース再生繊維をそれぞれ試料１〜５として糸切れな
く製造して得た。これらの試料１〜５の繊度，乾強度，
湿強度，結節強度，吸湿性を測定し、その結果を表２
に、抗菌性能，抗カビ性能，防ダニ性能の測定結果を表
３に示した。A mixture of the regenerated chitosan fine particles and the antibacterial and antifungal agent A was used to prepare rayon viscose (cellulose 9.0%, total alkali 6.0%, total sulfur 2.5%) obtained by a conventional method. To 15 liters of cellulose,
The regenerated chitosan microparticulates and the antibacterial and antifungal agent A mixture dispersion liquids, which have been previously dispersed in water so that the added amounts are 0, 0.3, 0.5, 2.0 and 3.0% by weight, respectively. Add
Mix uniformly with rayon viscose, and immediately after defoaming, use a nozzle of 0.09 mmφ x 100H and spin speed 5
Sulfuric acid 115 g / l, sodium sulfate 310 at 2 m / min
g / l, zinc sulfate 14 g / l, spinning in a spinning bath at a temperature of 53 ° C., stretched by a normal two-bath tension spinning method, cut to 32 mm, and then subjected to normal scouring and drying treatment to obtain 3 denier antibacterial cellulose Regenerated fibers were obtained as samples 1 to 5 without yarn breakage. Fineness, dry strength of these samples 1-5,
Wet strength, knot strength and hygroscopicity were measured and the results are shown in Table 2.
Table 3 shows the measurement results of the antibacterial performance, the antifungal performance, and the mite prevention performance.
【００４２】[0042]
【表２】 [Table 2]
【００４３】[0043]
【表３】 [Table 3]
【００４４】表２，表３から明らかなように、再生キト
サン微小粒状体と抗菌抗黴剤Ａを同時にレーヨンビスコ
ースに添加し紡糸して得た抗菌性セルロース再生繊維は
優れた吸湿性を有すると共に、抗菌性能，抗カビ性能，
防ダニ性能を併せ具備しているが、試料５は優れた抗菌
性能，抗カビ性能，防ダニ性能を発現するものの強力低
下が大きい。従って、実用上再生キトサン微小粒状体と
抗菌抗黴剤Ａの混合物の添加量はセルロースに対して
０．３〜２．０％が好ましい。As is clear from Tables 2 and 3, the regenerated chitosan fine particles and the antibacterial and antifungal agent A were simultaneously added to the rayon viscose and spun to obtain antibacterial regenerated cellulose fibers having excellent hygroscopicity. Along with antibacterial performance, antifungal performance,
Although it has both anti-mite performance, Sample 5 exhibits excellent anti-bacterial performance, anti-fungal performance, and anti-mite performance, but its strength is greatly reduced. Therefore, for practical use, the amount of the mixture of the regenerated chitosan fine particles and the antibacterial / antifungal agent A is preferably 0.3 to 2.0% with respect to the cellulose.
【００４５】〔実施例２〕脱アセチル化度９０％、平均
分子量５４，０００のキトサン５００ｇを２５０ｇの酢
酸を含む７，７５０ｇに溶解してキトサン酢酸水溶液を
得た。この溶液の２０℃における粘度は回転粘度計で測
定したところ４，３００cps であった。このキトサン酸
性溶液を５％のアンモニア水溶液中に落下させて、紐状
にキトサンを凝固再生させた。Example 2 500 g of chitosan having a deacetylation degree of 90% and an average molecular weight of 54,000 was dissolved in 7,750 g containing 250 g of acetic acid to obtain an aqueous chitosan acetic acid solution. The viscosity of this solution at 20 ° C. was 4,300 cps when measured with a rotary viscometer. The chitosan acidic solution was dropped into a 5% aqueous ammonia solution to coagulate and regenerate the chitosan in a string shape.
【００４６】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、１
５，０００rpm の回転数で３分間ずつ３回繰り返し粉砕
分散させ乳状の懸濁液とした。これを１００メッシュの
篩で濾過後、濾液を攪拌機で攪拌しで分散状態を保ちな
がら、４．０kg／cm2 の加圧空気と共に毎分１６ｍｌの
流量で、１７５℃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以下の再生キ
トサン微小粒状体３６０ｇを得た。The coagulated product was sufficiently washed with water until it became neutral, and then, using a homogenizer as in Example 1, 1
The mixture was pulverized and dispersed repeatedly three times for 3 minutes each at a rotation speed of 5,000 rpm to obtain a milky suspension. After filtering this through a 100-mesh sieve, stirring the filtrate with a stirrer and maintaining the dispersion state, it was discharged with a pressurized air of 4.0 kg / cm 2 at a flow rate of 16 ml per minute into a high temperature atmosphere of 175 ° C. Then, the dried product was collected in a cyclone collector. The dried product was classified in the same manner as in Example 1 to obtain 360 g of regenerated chitosan fine particles having a particle diameter of 5 μm or less.
【００４７】この再生キトサン微小粒状体に対して、実
施例１で用いた市販の抗菌抗黴剤Ａを再生キトサン微小
粒状体対抗菌抗黴剤Ａが８０対２０（重量比）となるよ
うに添加し、再生キトサン微小粒状体と抗菌抗黴剤Ａの
混合物４５０ｇを得た。The commercially available antibacterial and antifungal agent A used in Example 1 was added to the regenerated chitosan microparticulate so that the ratio of regenerated chitosan microparticulate to antibacterial and antifungal agent A was 80:20 (weight ratio). Then, 450 g of a mixture of regenerated chitosan fine particles and antibacterial and antifungal agent A was obtained.
【００４８】この再生キトサン微小粒状体と抗菌抗黴剤
Ａの混合物を、ポリノジックビスコース（セルロース
５．０％、、全アルカリ３．５％、全硫黄３％）各１５
リットルに、セルロースに対して、０，０．３，０．
５，２．０，３．０重量％の混合量になるように予め水
に分散させておいた再生キトサン微小粒状体と抗菌抗黴
剤Ａ混合物分散液を添加し均一に混合し、脱泡後、直ち
に０．０７mmφ×５００Ｈのノズルを使用し、紡糸速度
３２ｍ／分で硫黄２４ｇ／ｌ、硫酸亜鉛０．４ｇ／ｌ、
硫酸ナトリウム６０ｇ／ｌ、温度３５℃の紡糸浴に紡糸
し、次いで硫酸２ｇ／ｌ、硫酸亜鉛０．０５ｇ／ｌ、温
度２７℃の浴中で２倍延伸し３８mmに切断した後、炭酸
ナトリウム１ｇ／ｌ、硫酸ナトリウム２ｇ／ｌ、温度６
０℃の条件で処理を行なった後、再度硫酸５ｇ／ｌ、温
度６５℃で処理し、通常の精練、乾燥処理を行って、
１．２５デニールの抗菌性セルロース再生繊維を糸切れ
なくそれぞれ試料６〜１０として製造して得た。これら
の試料６〜１０の繊度，乾強度，湿強度，結節強度，吸
湿性を測定し、その結果を表４に、抗菌性能，抗カビ性
能，防ダニ性能の測定結果を表５に示した。A mixture of the regenerated chitosan fine particles and the antibacterial / antifungal agent A was added to polynosic viscose (5.0% cellulose, 3.5% total alkali, 3% total sulfur) for each 15
0, 0.3, 0.
The regenerated chitosan microparticulates and the antibacterial / antifungal agent A mixture dispersion liquid, which had been previously dispersed in water to a mixed amount of 5, 2.0, 3.0% by weight, were added and uniformly mixed, and defoamed. Immediately afterwards, using a nozzle of 0.07 mmφ × 500H, at a spinning speed of 32 m / min, 24 g / l of sulfur, 0.4 g / l of zinc sulfate,
It is spun in a spinning bath of sodium sulfate 60 g / l and temperature 35 ° C., and then it is twice stretched in a bath of sulfuric acid 2 g / l, zinc sulfate 0.05 g / l and temperature 27 ° C. and cut into 38 mm, and then sodium carbonate 1 g. / L, sodium sulfate 2g / l, temperature 6
After the treatment at 0 ° C., it is treated again at 5 g / l of sulfuric acid at a temperature of 65 ° C., and the usual scouring and drying treatments are carried out.
Antibacterial cellulose regenerated fibers having a denier of 1.25 were prepared and obtained as samples 6 to 10 without yarn breakage. The fineness, dry strength, wet strength, knot strength, and hygroscopicity of these samples 6 to 10 were measured. The results are shown in Table 4, and the results of the antibacterial performance, antifungal performance, and mite prevention performance are shown in Table 5. .
【００４９】[0049]
【表４】 [Table 4]
【００５０】[0050]
【表５】 [Table 5]
【００５１】表４，表５から明らかなように、キトサン
微小粒状体と抗菌抗黴剤Ａを同時にポリノジックビスコ
ースに添加し紡糸して得たポリノジックの抗菌性セルロ
ース再生繊維は優れた吸湿性を有すると共に、抗菌性
能，抗カビ性能，防ダニ性能を併せ具備しているが、試
料１０は優れた抗菌性能，抗カビ性能，防ダニ性能を発
現するものの強力低下が大きい。従って、実用上再生キ
トサン微小粒状体と抗菌抗黴剤Ａの混合物の添加量はセ
ルロースに対して０．３〜２．０％が好ましい。As is clear from Tables 4 and 5, the polynosic antibacterial cellulose regenerated fiber obtained by adding the chitosan microparticulates and the antibacterial antifungal agent A to the polynosic viscose at the same time and spinning it has excellent hygroscopicity. In addition to having the antibacterial performance, the antifungal performance, and the mitesproofing performance, the sample 10 exhibits excellent antibacterial performance, antifungal performance, and mitesproofing performance, but has a large decrease in strength. Therefore, for practical use, the amount of the mixture of the regenerated chitosan fine particles and the antibacterial / antifungal agent A is preferably 0.3 to 2.0% with respect to the cellulose.
【００５２】〔実施例３〕脱アセチル化度８２％、平均
分子量４５，０００のキトサン５００ｇを酢酸２５０ｇ
を含む７，７５０ｇ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℃における粘度は回転粘度計で
測定したところ３，４００cps であった。このキトサン
酸性溶液を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。Example 3 500 g of chitosan having a degree of deacetylation of 82% and an average molecular weight of 45,000 was added to 250 g of acetic acid.
Was added and dissolved to obtain an aqueous chitosan acetic acid solution. The viscosity of this solution at 20 ° C. was 3,400 cps when measured with a rotary viscometer. This chitosan acidic solution was dropped into a 5% aqueous solution of sodium hydroxide and coagulated and regenerated into particles.
【００５３】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、１５，０００rpm の回転数
で３分間ずつ３回繰り返し粉砕分散させ乳状の懸濁液と
した。これを１２０メッシュの篩で粗大片を濾別し、攪
拌機で攪拌しながら、濾液を３．０kg／cm2 の加圧空気
と共に毎分１６ｍｌの流量で１７０〜１８０℃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（（株）セイシン
企業製、商品名スペディック２５０）を用いて、分級し
て粒子径５μｍ以下の再生キトサン微小粒状体３００ｇ
を得た。The coagulated product was sufficiently washed with water until it became neutral, and then pulverized and dispersed 3 times for 3 minutes each at a rotation speed of 15,000 rpm in the same manner as in Example 1 to obtain a milky suspension. Coarse pieces are filtered off with a 120-mesh sieve, and the filtrate is discharged together with pressurized air of 3.0 kg / cm 2 at a flow rate of 16 ml per minute into a high temperature atmosphere of 170 to 180 ° C. while stirring with a stirrer. Then, the dried product was collected in a cyclone collector. 300 g of regenerated chitosan fine particles having a particle size of 5 μm or less are classified by classifying the dried product using an air classifier (manufactured by Seishin Enterprise Co., Ltd., trade name Spedic 250).
Got
【００５４】この再生キトサン微小粒状体に対して、実
施例１で用いた市販の抗菌抗黴剤Ａを添加し、再生キト
サン微小粒状体と抗菌抗黴剤Ａとの混合比（重量比）
（再生キトサン微小粒状体／抗菌抗黴剤Ａ）が０／１０
０，１０／９０，２０／８０，５０／５０，８０／２
０，９０／１０，１００／０となるように調整した。To the regenerated chitosan fine particles, the commercially available antibacterial and antifungal agent A used in Example 1 was added, and the mixture ratio (weight ratio) of the regenerated chitosan fine particles and the antibacterial and antifungal agent A was added.
(Recycled chitosan fine particles / antibacterial antifungal agent A) is 0/10
0, 10/90, 20/80, 50/50, 80/2
It was adjusted to be 0, 90/10, 100/0.
【００５５】これらの再生キトサン微小粒状体と抗菌抗
黴剤Ａの混合物を、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％、全アルカリ６．０％、
全硫黄２．５％）各１５リットルに、セルロースに対
し、２．０重量％の添加量になるように予め水に分散さ
せておいたそれぞれの再生キトサン微小粒状体と抗菌抗
黴剤Ａ混合物分散液を添加し、均一にレーヨンビスコー
スに混合し、脱泡後、実施例１と同様に紡糸し、通常の
二浴緊張紡糸法により延伸し３８mmに切断後、通常の精
練乾燥処理をして、３デニールの抗菌性セルロース再生
繊維をそれぞれ試料１１〜１７として糸切れなく製造し
て得た。これらの試料１１〜１７の繊度，乾強度，湿強
度，結節強度，吸湿性を測定し、その結果を表６に、抗
菌性能，抗カビ性能，防ダニ性能の測定結果を表７に示
した。A mixture of these regenerated chitosan fine particles and antibacterial and antifungal agent A was used to prepare rayon viscose (cellulose 9.0%, total alkali 6.0%,
Total sulfur 2.5%) Each mixture of regenerated chitosan fine particles and antibacterial / antifungal agent A mixture, which was previously dispersed in water so that the amount of addition was 2.0% by weight with respect to 15 liters of cellulose. The dispersion was added, uniformly mixed with rayon viscose, defoamed, spun in the same manner as in Example 1, stretched by the ordinary two-bath tension spinning method, cut to 38 mm, and then subjected to ordinary scouring and drying treatment. As a result, 3 denier antibacterial cellulose regenerated fibers were obtained as samples 11 to 17 without yarn breakage. The fineness, dry strength, wet strength, knot strength, and hygroscopicity of these samples 11 to 17 were measured, and the results are shown in Table 6 and the antibacterial performance, antifungal performance, and mite prevention performance are shown in Table 7. .
【００５６】[0056]
【表６】 [Table 6]
【００５７】[0057]
【表７】 [Table 7]
【００５８】表６，表７から明らかなように、再生キト
サン微小粒状体と抗菌抗黴剤Ａを同時にレーヨンビスコ
ースに添加し紡糸して得た抗菌性セルロース再生繊維は
優れた吸湿性を有すると共に、抗菌性能，抗カビ性能，
防ダニ性能を併せ具備しているが、試料１１は吸湿性が
小さく、試料１７は抗カビ性が劣っている。従って、実
用上再生キトサン微小粒状体と抗菌抗黴剤Ａの混合物中
の再生キトサン微小粒状体の割合は再生キトサン微小粒
状体と抗菌抗黴剤Ａの混合物をセルロース重量に対し
２．０％添加したときは１０〜９０％が好ましい。As is clear from Tables 6 and 7, the regenerated chitosan fine particles and the antibacterial and antifungal agent A were simultaneously added to rayon viscose and spun to obtain antibacterial regenerated cellulose fibers, which had excellent hygroscopicity. Along with antibacterial performance, antifungal performance,
Although the sample 11 also has anti-mite performance, the sample 11 has a small hygroscopic property, and the sample 17 has a poor antifungal property. Therefore, practically, the ratio of the regenerated chitosan fine particles in the mixture of the regenerated chitosan fine particles and the antibacterial and antifungal agent A is 2.0% of the mixture of the regenerated chitosan fine particles and the antibacterial and antifungal agent A based on the weight of cellulose. When it does, 10-90% is preferable.
【００５９】〔実施例４〕脱アセチル化度８７％、平均
分子量４５，０００のキトサン５００ｇを、酢酸２５０
ｇを含む水７，５００ｇに溶解して、２５℃における粘
度３，３００cpsのキトサン酢酸水溶液を得た。これを
１０％苛性ソーダ、２０％水からなる塩基性水溶液中
に、孔径０．２５mmの孔より圧力下で一定量ずつ落下さ
せ粒状に凝固再生させた。これを中性になるまで十分洗
浄し再生キトサン粒状物を得た。これをエタノールで４
回置換した後、等モルの無水酢酸を用いて、常温で２４
時間反応させた後、エタノールで洗浄後水洗し、０．５
Ｎ苛性ソーダでエステル結合を切断のため、室温で１時
間反応させ水洗し、脱アセチル化度２５％の再生アセチ
ル化キトサン５．０リットルを得た。Example 4 500 g of chitosan having a deacetylation degree of 87% and an average molecular weight of 45,000 was added to 250 g of acetic acid.
It was dissolved in 7,500 g of water containing g to obtain a chitosan acetic acid aqueous solution having a viscosity of 3,300 cps at 25 ° C. This was dropped into a basic aqueous solution consisting of 10% caustic soda and 20% water under pressure from a hole having a hole diameter of 0.25 mm, and was solidified and regenerated into particles. This was thoroughly washed until it became neutral to obtain regenerated chitosan granules. 4 this with ethanol
After substituting twice, use equimolar acetic anhydride at room temperature for 24 hours.
After reacting for a time, washed with ethanol and then with water to 0.5
In order to cleave the ester bond with N caustic soda, the mixture was reacted at room temperature for 1 hour and washed with water to obtain 5.0 liters of regenerated acetylated chitosan having a deacetylation degree of 25%.
【００６０】該再生アセチル化キトサン５．０リットル
に水４．７５リットルを加えてホモジナイザーで１７，
０００rpm で５分間２回繰り返し粉砕し、更に、水４．
７５リットルを加えて濃度３．４７％の分散液とした。
これを１４ml／分の流速で３．６kg／cm2 の加圧空気と
共に１８℃の高温雰囲気中に吐出乾燥させ、乾燥物をサ
イクロンコレクターに捕集し、該乾燥物を実施例１と同
様に分級機で分級して、粒子径５μｍ以下の再生アセチ
ル化キトサン微小粒状体２００ｇを得た。To the regenerated acetylated chitosan (5.0 liters) was added water (4.75 liters), and the mixture was homogenized with a homogenizer 17.
Repeatedly grind twice at 000 rpm for 5 minutes, and then water 4.
75 liters were added to obtain a dispersion having a concentration of 3.47%.
This was discharged and dried at a flow rate of 14 ml / min together with 3.6 kg / cm 2 of pressurized air in a high temperature atmosphere of 18 ° C., and the dried product was collected by a cyclone collector, and the dried product was treated in the same manner as in Example 1. The particles were classified by a classifier to obtain 200 g of regenerated acetylated chitosan fine particles having a particle diameter of 5 μm or less.
【００６１】この再生アセチル化キトサン微小粒状体に
対して、実施例１で用いた市販の抗菌抗黴剤Ａを再生ア
セチル化キトサン微小粒状体と抗菌抗黴剤Ａが８０対２
０（重量比）となるように添加し、再生アセチル化キト
サン微小粒状体と抗菌抗黴剤Ａの混合物２５０ｇを得
た。To the regenerated acetylated chitosan microparticulate, the commercially available antibacterial / antifungal agent A used in Example 1 was mixed with the regenerated acetylated chitosan microparticulate and the antibacterial / antifungal agent A at 80: 2.
0 (weight ratio) was added to obtain 250 g of a mixture of regenerated acetylated chitosan fine particles and antibacterial and antifungal agent A.
【００６２】これを実施例２と同様にしてポリノジック
ビスコースに添加混合して、紡糸し同様の処理をして、
１．２５デニール×３８mmの抗菌性セルロース再生繊維
を、糸切れなくそれぞれ試料１８〜２２として製造して
得た。試料１８〜２２の繊度，乾強度，湿強度，結節強
度，吸湿性を測定し、その結果を表８に、抗菌性能，抗
カビ性能，防ダニ性能の測定結果を表９に示した。This was added to and mixed with polynosic viscose in the same manner as in Example 2, spun and treated in the same manner.
Recycled antibacterial cellulose fibers of 1.25 denier x 38 mm were prepared and obtained as samples 18 to 22 without yarn breakage. The fineness, dry strength, wet strength, knot strength, and hygroscopicity of Samples 18 to 22 were measured. The results are shown in Table 8 and the results of the antibacterial performance, antifungal performance, and mite prevention performance are shown in Table 9.
【００６３】[0063]
【表８】 [Table 8]
【００６４】[0064]
【表９】 [Table 9]
【００６５】表８，表９から明らかなように、再生アセ
チル化キトサン微小粒状体と抗菌抗黴剤Ａを混合し同時
にポリノジックビスコースに添加し紡糸して得た抗菌性
セルロース再生繊維は優れた吸湿性を有すると共に、抗
菌性能，抗カビ性能，防ダニ性能を併せ具備している
が、試料２２は優れた抗菌性能，抗カビ性能，防ダニ性
能を発現するものの強力低下が大きい。従って、実用上
再生アセチル化キトサン微小粒状体と抗菌抗黴剤Ａの混
合物の添加量は再生アセチル化キトサン微小粒状体と抗
菌抗黴剤Ａの混合物の比率が８０対２０（重量比）のと
きにセルロースに対して０．３〜２．０％が好ましい。As is clear from Tables 8 and 9, the antibacterial cellulose regenerated fiber obtained by mixing the regenerated acetylated chitosan fine particles and the antibacterial and antifungal agent A and simultaneously adding them to polynosic viscose and spinning was excellent. While having hygroscopicity, it also has antibacterial, antifungal, and mite-proof properties, but Sample 22 exhibits excellent antibacterial, antifungal, and mite-proof properties, but its strength is greatly reduced. Therefore, the amount of the mixture of the regenerated acetylated chitosan fine particles and the antibacterial / antifungal agent A is practically added when the ratio of the mixture of the regenerated acetylated chitosan fine particles and the antibacterial / antifungal agent A is 80:20 (weight ratio). Moreover, 0.3 to 2.0% is preferable with respect to cellulose.
【００６６】[0066]
【発明の効果】上述の実施例から明らかなように、本発
明によれば、セルロース再生繊維中に粒子径１０μｍ以
下の再生キトサン微小粒状体又は再生アセチル化キトサ
ン微小粒状体，ニトリル系抗菌剤，ピリジン系抗菌剤，
ハロアルキルチオ系抗菌剤，有機ヨード系抗菌剤，チア
ゾール系抗菌剤及びベンツイミダゾール系抗菌剤を同時
に、セルロースに対して０．３〜２．０％（重量）含有
せしめ、また、再生キトサン微小粒状体又は再生アセチ
ル化キトサン微小粒状体が混合させる抗菌剤の合計に対
し１０〜９０％含有させることによって、セルロース再
生繊維が本来有する物性、風合い等の性能を損うことな
く、優れた吸湿性を有し、抗菌性能，抗カビ性能，防ダ
ニ性能を併せ具備する抗菌性セルロース再生繊維を提供
することが出来る。As is apparent from the above-mentioned examples, according to the present invention, regenerated chitosan fine particles or regenerated acetylated chitosan fine particles having a particle diameter of 10 μm or less, regenerated acetylated chitosan fine particles, nitrile antibacterial agent, Pyridine antibacterial agent,
A haloalkylthio antibacterial agent, an organic iodine antibacterial agent, a thiazole antibacterial agent and a benzimidazole antibacterial agent are simultaneously contained in cellulose in an amount of 0.3 to 2.0% (by weight), and regenerated chitosan microparticulates Alternatively, by containing 10 to 90% of the total amount of the antibacterial agent mixed with the regenerated acetylated chitosan fine particles, the regenerated cellulose has excellent hygroscopicity without impairing the properties such as physical properties and texture originally possessed by the regenerated cellulose. However, it is possible to provide an antibacterial cellulosic regenerated fiber having antibacterial performance, antifungal performance and mite prevention performance.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−289211（ＪＰ，Ａ) 特開 平８−144121（ＪＰ，Ａ) 特開 平４−65510（ＪＰ，Ａ) 特開 平７−207525（ＪＰ，Ａ) 特開 平８−134779（ＪＰ，Ａ) 特開 平４−126819（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) D01F 1/00 - 9/04 ─────────────────────────────────────────────────── --Continued front page (56) References JP-A-4-289211 (JP, A) JP-A-8-144121 (JP, A) JP-A-4-65510 (JP, A) JP-A-7- 207525 (JP, A) JP-A-8-134779 (JP, A) JP-A-4-126819 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) D01F 1 / 00-9 / 04
Claims (2)
以下の再生キトサン微小粒状体、ニトリル系抗菌剤、ピ
リジン系抗菌剤、ハロアルキルチオ系抗菌剤、有機ヨー
ド系抗菌剤、チアゾール系抗菌剤、及びベンツイミダゾ
ール系抗菌剤を含有していることを特徴とする抗菌性セ
ルロース再生繊維。1. A particle size of 10 μm in regenerated cellulose fibers.
Characterized by containing the following regenerated chitosan fine particles, nitrile antibacterial agents, pyridine antibacterial agents, haloalkylthio antibacterial agents, organic iodine antibacterial agents, thiazole antibacterial agents, and benzimidazole antibacterial agents Antibacterial regenerated cellulose fiber.
化キトサン微小粒状体である請求項１記載の抗菌性セル
ロース再生繊維。2. The regenerated antibacterial cellulose fiber according to claim 1, wherein the regenerated chitosan fine particles are regenerated acetylated chitosan fine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20521296A JP3413631B2 (en) | 1996-07-16 | 1996-07-16 | Antibacterial cellulose regenerated fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20521296A JP3413631B2 (en) | 1996-07-16 | 1996-07-16 | Antibacterial cellulose regenerated fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1037018A JPH1037018A (en) | 1998-02-10 |
| JP3413631B2 true JP3413631B2 (en) | 2003-06-03 |
Family
ID=16503267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20521296A Expired - Fee Related JP3413631B2 (en) | 1996-07-16 | 1996-07-16 | Antibacterial cellulose regenerated fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3413631B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT410806B (en) * | 1999-08-26 | 2003-08-25 | Chemiefaser Lenzing Ag | Viscose or lyocell cellulose fibers useful for making textiles comprise a deodorizing ceramic material and a bacteriostatic organic material |
| JP2001123367A (en) * | 1999-10-22 | 2001-05-08 | Toray Ind Inc | Fiber structure |
| CN1099477C (en) * | 2000-01-14 | 2003-01-22 | 东华大学 | Antibacterial fibres containing chitin and its derivatives, and preparing process thereof |
| EP1243688A1 (en) * | 2001-03-22 | 2002-09-25 | Cognis Iberia, S.L. | Use of chitosan nanoparticles |
| AT506334B1 (en) | 2008-01-22 | 2010-12-15 | Chemiefaser Lenzing Ag | METHOD FOR THE TREATMENT OF CELLULOSIC FORM BODIES |
| CN101935893A (en) * | 2010-08-27 | 2011-01-05 | 山东海龙股份有限公司 | Multifunctional aromatic antibiosis viscose fiber and preparation method thereof |
| CN107012525A (en) * | 2017-06-01 | 2017-08-04 | 合肥创沃科技有限公司 | A kind of preparation method of the composite regenerated cellulose tissue repair materials of chitosan |
-
1996
- 1996-07-16 JP JP20521296A patent/JP3413631B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1037018A (en) | 1998-02-10 |
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