JPH10140418A - Chitosan-containing yarn and its production - Google Patents
Chitosan-containing yarn and its productionInfo
- Publication number
- JPH10140418A JPH10140418A JP29909996A JP29909996A JPH10140418A JP H10140418 A JPH10140418 A JP H10140418A JP 29909996 A JP29909996 A JP 29909996A JP 29909996 A JP29909996 A JP 29909996A JP H10140418 A JPH10140418 A JP H10140418A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- fiber
- yarn
- antibacterial
- fine particles
- 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.)
- Granted
Links
Landscapes
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、衣料、インテリア
及び資材用途等として用いることのできる抗菌防臭性繊
維、特に繊維中にキトサン微粒子が分散している抗菌防
臭性を有するキトサン含有繊維に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial and deodorant fiber which can be used for clothing, interior and material applications, and particularly to a chitosan-containing fiber having antibacterial and deodorant properties in which chitosan fine particles are dispersed in the fiber.
【０００２】[0002]
【従来の技術】抗菌防臭性繊維は、雑菌の増殖を抑制
し、不快な異臭の発生を防止する目的で近年広く使用さ
れており、医療用、幼児、老人向け繊維製品として、ま
た最近では健康と快適を強く求める消費者ニ−ズを受
け、一般消費者向け製品として市中に広く流通してい
る。2. Description of the Related Art Antibacterial and deodorant fibers have been widely used in recent years for the purpose of suppressing the growth of various bacteria and preventing the generation of unpleasant off-flavors. It has been widely distributed throughout the market as a product for general consumers in response to consumer needs that strongly demand comfort.
【０００３】このような抗菌防臭性繊維には、種々の抗
菌剤が用いられており、繊維製品への抗菌剤の複合処理
方法も様々である。例えば、抗菌剤としては、銀−ゼオ
ライト系を代表とする無機金属系物質を用いる技術（特
開平５−２７２００８号公報等）、銅化合物または銅や
亜鉛などの金属微粉末を繊維中に添加する方法（特開昭
５５−１１５４４０号公報等）、４級アンモニウム塩誘
導体を用いる方法（特開昭５９−１３０３７１号公報
等）、トリクロロカルバニリド等のハロジアリル尿素化
合物を用いる方法（特開平２−２５９１６９号公報）、
その他の化合物としてサイアベンダゾ−ル系化合物（特
開昭６１−６１６号公報等）、フェノ−ル系化合物（特
開昭６０−２５２７１３号公報等）、脂肪酸エステル系
化合物を用いる方法（特開昭６３−６１７３号公報等）
などが知られている。[0003] Various antibacterial agents are used in such antibacterial and deodorant fibers, and there are various methods of compounding antibacterial agents into textile products. For example, as an antibacterial agent, a technique using an inorganic metal material represented by silver-zeolite (JP-A-5-272008, etc.), or a copper compound or a metal fine powder such as copper or zinc is added to the fiber. (Japanese Unexamined Patent Publication No. Sho 55-115440), a method using a quaternary ammonium salt derivative (Japanese Unexamined Patent Publication No. Sho 59-130371), a method using a halodiallyl urea compound such as trichlorocarbanilide (Japanese Unexamined Patent Publication No. 259169),
As other compounds, a method using a siabendazole-based compound (JP-A-61-616, etc.), a phenol-based compound (JP-A-60-252713, etc.), or a fatty acid ester-based compound (JP-A-63) No.-6173)
Etc. are known.
【０００４】しかしながら、銀、銅化合物を複合化した
繊維は、晒し処理を行うと銀、銅化合物が化学分解し抗
菌性が失われるという問題がある。また、一部の有機系
化合物を複合化した繊維は、後加工から廃棄まで含めた
使用環境の条件下で有害物質が生じる可能性を完全に否
定できないという問題点がある。However, there is a problem that a fiber obtained by compounding a silver and a copper compound is subjected to a bleaching treatment, whereby the silver and the copper compound are chemically decomposed and the antibacterial property is lost. In addition, there is a problem that a fiber in which some organic compounds are complexed cannot completely deny the possibility of generating harmful substances under the conditions of use environment including post-processing to disposal.
【０００５】こうした背景のもと、最近天然物由来の機
能性付与剤が注目されている。[0005] Against this background, attention has recently been paid to functionalizers derived from natural products.
【０００６】例えば、ヒノキから抽出されるヒノキチオ
−ルは抗菌、防カビ性、防虫等の機能を持ち、甲殻類か
ら得られる天然多糖類キチンの脱アセチル化物であるキ
トサンは、抗菌防臭、ＭＲＳＡに対する増殖抑制効果、
高保湿性、アトピ−性皮膚炎の予防、改善その他多くの
機能を持ち、繊維に含有して衣類に使用すると快適な感
触が得られることが知られている。For example, hinokitiol extracted from hinoki has antibacterial, antifungal and insect repellent functions, and chitosan, a deacetylated product of natural polysaccharide chitin obtained from crustaceans, has antibacterial and deodorant properties against MRSA. Growth inhibitory effect,
It is known that it has a high moisturizing property, prevents and ameliorates atopic dermatitis, and has many other functions, and that when contained in fibers and used in clothing, a comfortable feel can be obtained.
【０００７】しかしながら、抗菌防臭機能の発現、その
効果の持続性、さらには繊維が本来有する繊維性能、例
えば風合いの保持といった点から総合的に判断して、十
分とは言い得ないのが現状である。即ち、接着剤を用い
てキトサンを含有した繊維は洗濯に耐えるものとはなら
ない。キトサンを微粉末状に粉砕して紡糸用重合体原
液、例えば溶液あるいは融液に均一分散し公知の方法で
紡糸しようとしても紡糸口金の紡糸孔に詰まって生産性
よく紡糸することは困難であるし、繊維の風合いが異な
ったものとなってしまう。さらに、繊維をキトサン酸性
溶液に浸漬し、引き続いてアルカリ浴で中和し繊維表面
に析出させる方法で得られたキトサン含有繊維の抗菌性
能は、染色等の後加工や洗濯により比較的簡単に失わ
れ、実用的耐久性の更なる向上が求められている。However, in view of the manifestation of the antibacterial and deodorant function, the persistence of the effect, and the fiber performance inherent in the fiber, for example, maintaining the texture, it cannot be said that it is sufficient. is there. That is, fibers containing chitosan using an adhesive do not withstand washing. Even if chitosan is pulverized to a fine powder form and uniformly dispersed in a polymer solution for spinning, for example, a solution or a melt, and spinning is performed by a known method, it is difficult to spin with good productivity due to clogging in a spinning hole of a spinneret. Then, the texture of the fiber becomes different. Furthermore, the antibacterial performance of the chitosan-containing fiber obtained by immersing the fiber in a chitosan acidic solution, subsequently neutralizing the fiber with an alkaline bath, and precipitating the fiber surface is relatively easily lost by post-processing such as dyeing or washing. Therefore, further improvement in practical durability is required.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、上記従来の
問題点を解消し、抗菌防臭繊維製品に求められる、あら
ゆる細菌に対して効果があり、繊維の染色、さらし、柔
軟処理等の後加工や洗濯、アイロン等の繊維製品が使用
環境で受ける処理により抗菌防臭性能が失活せず、生産
から廃棄まで含めた全過程で有害な物質を生じない抗菌
防臭性繊維及び抗菌防臭性アクリル繊維の製造方法の提
供を課題とする。The present invention solves the above-mentioned conventional problems and is effective against all kinds of bacteria required for antibacterial and deodorant fiber products. Antibacterial and deodorant fibers and antibacterial and deodorant acrylic fibers that do not deactivate the antibacterial and deodorant performance due to processing received by the textile products such as processing, washing and ironing in the use environment, and do not produce harmful substances in all processes from production to disposal It is an object of the present invention to provide a method for manufacturing the same.
【０００９】[0009]
【課題を解決するための手段】本発明者等は上記課題を
解決するために鋭意検討した結果、以下の発明に到達し
た。即ち、本発明は、繊維中にキトサンを０．０２〜
２．０重量％含有し、かつキトサンが繊維中に微粒子状
で分散しており、繊維横断面に存在する任意の１００〜
２００個の微粒子の円換算平均直径が１〜１００ｎｍ、
その標準偏差が１００ｎｍ以下であることを特徴とする
キトサン含有繊維を第１の要旨とし、又、アクリロニト
リル系重合体溶液を湿式紡糸した乾燥緻密化する以前
の、膨潤度が３０〜２００％の糸条を、キトサン濃度が
０．０３〜２．５重量％で、温度が２５〜９０℃のキト
サン酸性水溶液に浸漬し、続いてアルカリ性水溶液によ
り中和した後、乾燥緻密化することを特徴とするキトサ
ン含有アクリル繊維の製造方法を第２の要旨とする。Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the following invention. That is, the present invention provides a chitosan of 0.02-
2.0% by weight, and chitosan is dispersed in fine particles in the fiber, and any of 100 to
The average circle-converted diameter of 200 fine particles is 1 to 100 nm,
A first aspect is a chitosan-containing fiber having a standard deviation of 100 nm or less, and a yarn having an swelling degree of 30 to 200% before wet-spinning and drying and densifying an acrylonitrile-based polymer solution. The strip is immersed in an aqueous chitosan solution having a chitosan concentration of 0.03 to 2.5% by weight and a temperature of 25 to 90 ° C., then neutralized with an alkaline aqueous solution, and then dried and densified. A second aspect of the present invention is a method for producing chitosan-containing acrylic fibers.
【００１０】[0010]
【発明の実施の形態】以下、本発明をさらに詳しく説明
する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.
【００１１】本発明において、繊維の種類は特に限定さ
れないが、いわゆる湿式紡糸法によって製造される繊維
が好ましく、特にアクリロニトリル系ポリマ−からなる
繊維が特に好ましい。In the present invention, the type of fiber is not particularly limited, but a fiber produced by a so-called wet spinning method is preferable, and a fiber composed of an acrylonitrile polymer is particularly preferable.
【００１２】本発明に用いるキトサンは、カニ、エビ等
の甲殻類の外骨格を形成するキチン質から炭酸カルシウ
ム、蛋白質等の夾雑物を酸及びアルカリ処理で除去して
得られるキチンを濃アルカリと加熱して脱アセチル化し
た塩基性多糖類である。キトサン含有量は、含有するこ
とにより期待される抗菌、防臭効果を得るには、先ず、
その含有量が重要であり、繊維に対して０．０２〜２．
０重量％である。０．０２重量％よりも少ないと効果は
不十分であり、２．０％よりも多くてもそれ以上の効果
の増加は望めないだけでなく、繊維の風合いが変化した
り、機械的強度を損なうという障害が現れるために好ま
しくない。The chitosan used in the present invention is obtained by removing contaminants such as calcium carbonate and protein from chitin forming an exoskeleton of a crustacean such as crab and shrimp by acid and alkali treatment, and converting chitin into a concentrated alkali. It is a basic polysaccharide that has been deacetylated by heating. To obtain the antibacterial and deodorant effects expected by containing chitosan content, first,
Its content is important and is between 0.02 and 2.
0% by weight. If the amount is less than 0.02% by weight, the effect is insufficient. If the amount is more than 2.0%, not only the effect cannot be increased any more, but also the texture of the fiber changes and the mechanical strength decreases. It is not preferable because an obstacle of impairment appears.
【００１３】かかるキトサンを繊維に含有する方法とし
ては、多数の方法があるが、抗菌防臭機能の発現、その
効果の持続性、さらには繊維が本来有する繊維の性能、
例えば風合いの保持といった点を満足するには、キトサ
ンの繊維中の存在状態、換言するとキトサンが繊維中に
凝集することなく、かつできるだけ微細な粒子として分
散していることが重要である。[0013] There are many methods for containing such chitosan in the fiber, and there are many methods. The expression of the antibacterial and deodorant function, the persistence of the effect, and the performance of the fiber which the fiber originally has,
For example, in order to satisfy the point of maintaining the texture, it is important that the state of chitosan present in the fiber, in other words, the chitosan is not aggregated in the fiber and is dispersed as fine particles as possible.
【００１４】つまり、キトサンが大きな粒子として分散
する場合には、キトサンに期待される抗菌、防臭効果を
発現するためのキトサン表面積が小さく、その効果は小
さくなってしまう。更に、晒し、染色といった後加工工
程や洗濯によって、場合によってはキトサン粒子として
溶解又は機械的に脱落するために、その効果の持続性が
損なわれるのであるが、その場合脱落の程度は、キトサ
ンの分散粒子の大きさにより決まる。つまり、その粒子
を単位としては溶解又は機械的脱落をするために、大き
い粒子で存在する場合には、脱落が比較的大きくなる。That is, when chitosan is dispersed as large particles, the surface area of chitosan for exhibiting the antibacterial and deodorant effects expected of chitosan is small, and the effect is reduced. In addition, post-processing steps such as bleaching and dyeing, and washing may dissolve or mechanically fall off as chitosan particles in some cases, thereby impairing the sustainability of the effect. It is determined by the size of the dispersed particles. That is, in order to dissolve or mechanically drop the particles as a unit, when the particles exist as large particles, the drop is relatively large.
【００１５】したがって、できるだけ小さな粒子として
分散することが好ましい。つまり、繊維中に微粒子状で
分散しており、繊維横断面に存在する任意の１００〜２
００個の微粒子の円換算平均直径が１〜１００ｎｍ、そ
の標準偏差が１００ｎｍ以下であることが好ましい。Therefore, it is preferable to disperse the particles as small as possible. That is, any 100 to 2 particles dispersed in the fiber in the form of fine particles and existing in the fiber cross section.
It is preferable that the average diameter of the 00 particles in terms of circle is 1 to 100 nm and the standard deviation is 100 nm or less.
【００１６】かかる分散状態は、繊維を四酸化ルテニウ
ムで染色した後、厚さ約８０ｎｍの横断面超薄切片と
し、透過型電子顕微鏡（日本電子（株）ＪＥＭ−１００
ＣＸ）により得られたキトサン分布図を画像解析装置
（ニコレ（株）Ｌｕｚｅｘ３）により解析することで得
ることができる。Such a dispersion state is obtained by dyeing the fiber with ruthenium tetroxide, forming an ultra-thin section of about 80 nm in cross section, and using a transmission electron microscope (JEM-100, JEOL Ltd.).
CX) can be obtained by analyzing the chitosan distribution map obtained by the CX) using an image analyzer (Luzex3, Nicole Co., Ltd.).
【００１７】分散微粒子の大きさを表す指標としては、
円換算直径を用いることができる。これは、各分散粒子
の画像における占有面積に相当する円の直径を示す。ま
た、その微粒子の大きさが均一である方が好ましい。そ
のため、円換算直径の標準偏差が小さい程よい。これら
の指標を効率的に得るためには、測定微粒子の数は１０
０個以上であることが好ましいが、２００個よりも多く
ても、実際上は何らの影響も与えることがなく、デ−タ
処理が煩雑になるので、現実的ではない。As an index indicating the size of the dispersed fine particles,
The circle equivalent diameter can be used. This indicates the diameter of a circle corresponding to the occupied area of each dispersed particle in the image. Further, it is preferable that the size of the fine particles is uniform. Therefore, the smaller the standard deviation of the circle-converted diameter, the better. In order to obtain these indices efficiently, the number of particles to be measured must be 10
It is preferable that the number is 0 or more. However, if the number is more than 200, it has no practical effect and the data processing becomes complicated, which is not practical.
【００１８】円換算平均直径が１〜１００ｎｍであるこ
とが好ましく、１００ｎｍよりも大きいと本発明の課題
を解決できない。他方１ｎｍよりも小さいと、却って溶
出しやすくなる。The average diameter in terms of a circle is preferably 1 to 100 nm, and if it is larger than 100 nm, the problem of the present invention cannot be solved. On the other hand, when it is smaller than 1 nm, elution is rather easy.
【００１９】また、円換算平均直径が１００ｎｍ以下で
あれば、円換算平均直径の標準偏差は小さく、粒子の大
きさは実質的に本発明の課題を解決し得る程度に均一で
本発明の課題の解決を阻害する程度の大粒子は存在しな
い。他方、円換算平均直径が１００ｎｍよりも大きい
と、円換算平均直径の標準偏差は大きく、少数ではある
が極端な大粒子が存在し、抗菌防臭機能の発現と効果の
持続性が低下するので好ましくない。If the circle-converted average diameter is 100 nm or less, the standard deviation of the circle-converted average diameter is small, and the size of the particles is uniform enough to substantially solve the problem of the present invention. There are no large particles that hinder the solution of the above. On the other hand, when the circle-equivalent average diameter is larger than 100 nm, the standard deviation of the circle-equivalent average diameter is large, and although a small number of extremely large particles are present, the expression of the antibacterial deodorant function and the persistence of the effect are preferably reduced. Absent.
【００２０】更に好ましい態様は、キトサン分散微粒子
が、凝集することなく、均一な形状の一次粒子として分
散していることがキトサンの利用効率の点で好ましい。
かかる観点から、該繊維の横断面に存在する任意の１０
０〜２００個のキトサン微粒子において、前に述べた式
（１）で定義されるシェ−プファクタ−ＳＦが１００〜
３００、その標準偏差が１５０以下であるアクリロニト
リル系繊維である事が好ましい。In a more preferred embodiment, the chitosan-dispersed fine particles are preferably dispersed as uniform primary particles without agglomeration from the viewpoint of chitosan utilization efficiency.
From this viewpoint, any 10 present in the cross section of the fiber
In the 0 to 200 chitosan fine particles, the shape factor SF defined by the above-mentioned formula (1) is 100 to 100.
Acrylonitrile fiber having a standard deviation of 300 or less and 150 or less is preferable.
【００２１】該式（１）で定義されるシェ−プファクタ
−ＳＦは、真円において１００となるような指標であ
る。該ＳＦが１００〜３００であれば、実質的に画像上
は円で分散し、現実には球状で分散していることにな
り、凝集状態にはない事を表している。しかも、その標
準偏差が１５０ｎｍ以下であれば、実質的に均一な形状
であることを表している。The shape factor SF defined by the equation (1) is an index that becomes 100 in a perfect circle. If the SF is 100 to 300, the image is substantially dispersed in a circle on the image, and is actually dispersed in a spherical shape, indicating that the image is not in an aggregated state. Moreover, if the standard deviation is 150 nm or less, it indicates that the shape is substantially uniform.
【００２２】本発明の繊維を製造する方法は幾つか挙げ
られるが、本発明の繊維を製造するためには、湿式紡糸
法において製造される凝固糸もしくはウエット糸をキト
サンを含有する溶液中に浸漬通過させる方法が最もよ
い。つまり、凝固糸もしくはウエット糸はその製造過程
におけるポリマ−の相分離過程で生成するミクロボイド
を有しており、これをキトサンを存在せしめるスペ−ス
として利用する事で、本発明の繊維を製造する事ができ
る。There are several methods for producing the fiber of the present invention. In order to produce the fiber of the present invention, a coagulated yarn or a wet yarn produced by a wet spinning method is immersed in a solution containing chitosan. The best way is to let it pass. In other words, the coagulated yarn or the wet yarn has microvoids generated in the phase separation process of the polymer in the production process, and the fiber of the present invention is produced by utilizing the microvoids as a space for allowing chitosan to exist. Can do things.
【００２３】かかる繊維の例としては、アクリロニトリ
ル系ポリマ−からなる繊維が最も効果的である。これを
例にとって、詳しく説明する。As an example of such a fiber, a fiber made of an acrylonitrile polymer is most effective. This will be described in detail with reference to an example.
【００２４】ここに、アクリロニトリル系繊維とは、ア
クリロニトリルを５０重量％以上含有し、これと共重合
可能な不飽和単量体であるビニル重合体からなる繊維で
ある。アクリロニトリル系重合体中のアクリロニトリル
量が５０重量％未満の場合は、アクリル繊維の特徴であ
る染色鮮明性、発色性が悪化すると共に、熱特性をはじ
めとする他の物性も低下する傾向にある。Here, the acrylonitrile fiber is a fiber containing 50% by weight or more of acrylonitrile and made of a vinyl polymer which is an unsaturated monomer copolymerizable therewith. When the amount of acrylonitrile in the acrylonitrile-based polymer is less than 50% by weight, the clarity of dyeing and coloring, which are the characteristics of acrylic fibers, are deteriorated, and other physical properties such as thermal properties also tend to be reduced.
【００２５】アクリロニトリルと共重合可能な不飽和単
量体としては、アクリル酸、メタクリル酸、又は、これ
らのアルキルエステル類、酢酸ビニル、アクリルアミ
ド、塩化ビニル、塩化ビニリデン、更に目的によっては
ビニルベンゼンスルホン酸ソ−ダ、メタリルスルホン酸
ソ−ダ、アクリルアミドジメチルプロパンスルホン酸ソ
−ダ等のイオン性不飽和単量体を用いることができる。Examples of the unsaturated monomer copolymerizable with acrylonitrile include acrylic acid, methacrylic acid or alkyl esters thereof, vinyl acetate, acrylamide, vinyl chloride, vinylidene chloride, and, depending on the purpose, vinyl benzene sulfonic acid. An ionic unsaturated monomer such as soda, soda methallylsulfonate, and soda acrylamidodimethylpropanesulfonate can be used.
【００２６】アクリル繊維にキトサンを含有する方法と
しては、例えば、湿式アクリル繊維製造工程の凝固糸に
含まれる溶剤を洗浄した洗浄糸条に対して、キトサン酸
性水溶液を含有後、中和しキトサンを析出する方法が挙
げられる。As a method of containing chitosan in an acrylic fiber, for example, a washing fiber obtained by washing a solvent contained in a coagulated yarn in a wet acrylic fiber production process is neutralized by containing a chitosan acidic aqueous solution and then neutralizing it. A method of depositing is exemplified.
【００２７】キトサン酸性水溶液中のキトサン濃度とし
ては、０．０３〜２．５重量％とするのが好ましい。つ
まり、０．０３重量％よりも少ないと結果的に繊維のキ
トサン含有量が少なく、十分な抗菌性を示さない。逆
に、２．５重量％よりも多い場合でも抗菌性の増加は殆
ど無い。つまり、キトサン量がミクロボイド内への析出
吸着容量を超え、キトサンの一部は繊維に取り込まれな
いで過剰になる。The concentration of chitosan in the chitosan acidic aqueous solution is preferably from 0.03 to 2.5% by weight. That is, if the content is less than 0.03% by weight, the chitosan content of the fiber is low, resulting in insufficient antibacterial properties. Conversely, there is almost no increase in antibacterial properties even when it is more than 2.5% by weight. That is, the amount of chitosan exceeds the adsorption capacity for precipitation in the microvoids, and a portion of chitosan becomes excessive without being taken into fibers.
【００２８】酸の種類は特に限定しないが、塩酸、乳
酸、酢酸、蟻酸等が好適に使用可能である。また、酸の
濃度はキトサンが溶解する範囲で低いほどアクリル繊維
の着色が抑えられ好ましく、具体的には２．５重量％以
下の濃度が好ましい。ここで、キトサンを含有する際の
ウエット糸の膨潤度と温度を制御する事は重要であり、
膨潤度は３０〜２００％、温度は２５〜９０℃とするこ
とで、本発明の繊維を製造することができる。膨潤度が
３０％よりも低いと、キトサンは繊維断面の表面近傍に
のみ分布し、耐久性に劣る。逆に、膨潤度が２００％よ
りも高いと、キトサン分散粒子径が１００ｎｍよりも大
きくなり、やはり耐久性に劣る。また、温度が２５℃よ
りも低いと、キトサンは繊維内部には分布せず、逆に温
度が９０℃よりも高いと、キトサンが分解する危険性が
ある。The type of the acid is not particularly limited, but hydrochloric acid, lactic acid, acetic acid, formic acid and the like can be suitably used. The lower the concentration of the acid in the range in which the chitosan is dissolved, the more the coloring of the acrylic fiber is suppressed, and the more preferable the concentration is, specifically, a concentration of 2.5% by weight or less. Here, it is important to control the swelling degree and temperature of the wet yarn when containing chitosan,
By setting the degree of swelling to 30 to 200% and the temperature to 25 to 90 ° C, the fiber of the present invention can be produced. If the degree of swelling is lower than 30%, chitosan is distributed only in the vicinity of the surface of the fiber cross section, resulting in poor durability. Conversely, when the degree of swelling is higher than 200%, the particle diameter of the chitosan dispersion becomes larger than 100 nm, and the durability is also poor. When the temperature is lower than 25 ° C., chitosan is not distributed inside the fiber, and when the temperature is higher than 90 ° C., there is a risk that the chitosan is decomposed.
【００２９】本発明の繊維の他の好ましい例としては、
ビニルアルコ−ル系ポリマ−からなる繊維を挙げること
ができる。つまり、かかるポリマ−を約１５％水溶液と
して、口金を通して約４０％のボウ硝を含む約ｐＨ５の
水溶液中に押し出して凝固糸を得る。かかる凝固糸を更
に洗浄しウエット糸を得る事ができる。該凝固糸かウエ
ット糸を前記のキトサンを含有する酢酸水溶液中に通過
させることで本発明に係るキトサン含有繊維を得る事が
できる。その後必要に応じて、中和、洗浄すればよい。Other preferred examples of the fiber of the present invention include:
Fibers composed of vinyl alcohol-based polymers can be mentioned. That is, such a polymer is extruded as an aqueous solution of about 15% through a mouthpiece into an aqueous solution of about pH 5 containing about 40% of borate to obtain a coagulated yarn. The coagulated yarn can be further washed to obtain a wet yarn. The chitosan-containing fiber according to the present invention can be obtained by passing the coagulated yarn or wet yarn through the above-mentioned acetic acid aqueous solution containing chitosan. Thereafter, neutralization and washing may be performed as necessary.
【００３０】本発明の繊維のもう一つの好ましい例とし
ては、セルロ−ス繊維を挙げる事ができる。セルロ−ス
繊維を製造する方法としては、溶解方法により幾つかあ
る。その一つとしていわゆるキュプラレ−ヨン法があ
る。この場合、常法に従って銅アンモニア水にセルロ−
スを、銅が３．６％、アンモニアが７．３％、セルロ−
スが９．０％になるように溶解し、口金を通して約５％
の硫酸水溶液中に押し出し凝固糸を得る。かかる凝固糸
を更に洗浄しウエット糸を得る事ができる。該凝固糸か
ウエット糸を前記のキトサンを含有する酢酸水溶液中に
通過させることで本発明に係るキトサン含有繊維を得る
事ができる。その後必要に応じて、中和、洗浄すればよ
い。Another preferred example of the fiber of the present invention is cellulose fiber. There are several methods for producing cellulose fibers depending on the dissolution method. One of them is the so-called cupra rayon method. In this case, cellulosic water is added to copper ammonia water according to a conventional method.
Copper, 3.6% ammonia, 7.3% ammonia,
Dissolve so that the volume becomes 9.0%, and about 5%
To obtain a coagulated yarn. The coagulated yarn can be further washed to obtain a wet yarn. The chitosan-containing fiber according to the present invention can be obtained by passing the coagulated yarn or wet yarn through the above-mentioned acetic acid aqueous solution containing chitosan. Thereafter, neutralization and washing may be performed as necessary.
【００３１】更にセルロ−ス繊維を製造する他の方法と
しては、Ｎ−メチルモルホリン−Ｎ−オキサイドに溶解
する方法がある。この場合は、セルロ−スを該溶媒に約
１０％溶解し、口金を通して水中に押し出し、更に洗浄
しウエット糸を得る事ができる。該ウエット糸を前記の
キトサンを含有する酢酸水溶液中に通過させることで本
発明に係るキトサン含有繊維を得ることができる。その
後必要に応じて、中和、洗浄すればよい。As another method for producing cellulose fibers, there is a method of dissolving in N-methylmorpholine-N-oxide. In this case, about 10% of cellulose is dissolved in the solvent, extruded into water through a mouthpiece, and further washed to obtain a wet yarn. The chitosan-containing fiber according to the present invention can be obtained by passing the wet yarn through the above-mentioned acetic acid aqueous solution containing chitosan. Thereafter, neutralization and washing may be performed as necessary.
【００３２】更にセルロ−スアセテ−ト繊維を例示する
事ができる。この場合には、セルロ−スアセテ−トをジ
メチルアセトアマイドに溶解し、前記のアクリル繊維の
場合と同様にして、本発明の繊維を製造する事ができ
る。Further, cellulose acetate fibers can be exemplified. In this case, the cellulose of the present invention can be produced in the same manner as in the case of the above-mentioned acrylic fiber by dissolving cellulose acetate in dimethylacetamide.
【００３３】本発明のキトサン含有繊維を紡績糸、布
帛、不織布等の繊維複合体として用いる場合、抗菌防臭
性能を得るためには、キトサン含有繊維が２０重量％以
上混合されていることが好ましい。キトサン含有繊維と
混合する繊維としては、使用目的にあわせて選択すれば
よく特に限定しないが、通常のアクリル繊維、綿、ウ−
ル、麻、絹、ポリエステル等公知の繊維が挙げられる。When the chitosan-containing fiber of the present invention is used as a fiber composite such as spun yarn, cloth, non-woven fabric, etc., it is preferable that the chitosan-containing fiber is mixed in an amount of 20% by weight or more in order to obtain antibacterial and deodorant performance. The fiber to be mixed with the chitosan-containing fiber is not particularly limited as long as it is selected according to the purpose of use.
And known fibers such as cotton, hemp, silk, and polyester.
【００３４】[0034]
【実施例】以下、本発明を実施例により、更に具体的に
説明する。なお、アクリル繊維中のキトサン含有量の測
定は、比較例５を除いて、次のようにして行った。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The measurement of the chitosan content in the acrylic fiber was performed as follows, except for Comparative Example 5.
【００３５】（アクリル繊維中のキトサン含有量の測
定） １）秤量したキトサン含有アクリル繊維５ｇを６Ｍ塩酸
１００ｍｌに浸漬し、沸騰水中で８時間加熱する。 ２）アクリル繊維を取り除き、得られたキトサン抽出塩
酸溶液２５ｍｌに蒸留水１５０ｍｌを加えながら減圧下
で濃縮乾固する。 ３）乾固物を１０％酢酸溶液１０ｍｌに溶解し、これに
エ−リッヒ試薬（ｐ−ジメチルアミノベンズアルデヒド
の１％エタノ−ル溶液）１ｍｌを添加し、５℃で１２時
間静置する。 ４）波長４３５ｎｍで３）溶液の吸光度を測定する。 ５）検量線から濃縮液中のキトサン濃度を求め、アクリ
ル繊維中に含有する量に換算した。(Measurement of Chitosan Content in Acrylic Fiber) 1) 5 g of the weighed chitosan-containing acrylic fiber is immersed in 100 ml of 6M hydrochloric acid and heated in boiling water for 8 hours. 2) The acrylic fiber is removed, and concentrated to dryness under reduced pressure while adding 150 ml of distilled water to 25 ml of the obtained chitosan-extracted hydrochloric acid solution. 3) The dried product was dissolved in 10 ml of a 10% acetic acid solution, and 1 ml of Erich reagent (a 1% solution of p-dimethylaminobenzaldehyde in ethanol) was added thereto, followed by standing at 5 ° C. for 12 hours. 4) Measure the absorbance of the solution at a wavelength of 435 nm. 5) The concentration of chitosan in the concentrated solution was determined from the calibration curve and converted to the amount contained in the acrylic fiber.
【００３６】（乾燥緻密化前のアクリル繊維糸条の膨潤
度の測定）紡糸工程より採取した乾燥緻密化前のアクリ
ル繊維糸条を１０００Ｇの加速度の下で１０分間脱水し
た後の重量Ｗ1、その後、１１０℃で３時間熱風乾燥し
た後の重量Ｗ2から下式を用いて算出した。 （膨潤度）＝［（Ｗ1−Ｗ2）／Ｗ2］×１００（％）(Measurement of Swelling Degree of Acrylic Fiber Yarn Before Dry Densification) The weight W 1 after dewatering the acrylic fiber yarn before drying and densification obtained from the spinning step at an acceleration of 1000 G for 10 minutes, It was then calculated using the following equation from 3 hours hot dry weight W 2 after at 110 ° C.. (Swelling degree) = [(W 1 −W 2 ) / W 2 ] × 100 (%)
【００３７】（重合体の還元粘度）還元粘度ηredは、
ジメチルホルムアミドを溶剤とした濃度０．５重量％の
重合体溶液の粘度を２５℃においてキャノンフェンスケ
粘度計を用いて測定した。(Reduced Viscosity of Polymer) The reduced viscosity η red is
The viscosity of a 0.5% by weight polymer solution using dimethylformamide as a solvent was measured at 25 ° C. using a Cannon-Fenske viscometer.
【００３８】（抗菌性能測定）繊維製品衛生加工協議会
で定めた菌数測定法により、黄色ブドウ状球菌による菌
数増減値差を求めた。菌数増減値差１．６以上を抗菌性
有効の基準とした。尚、洗濯方法は同協議会で定めた方
法に従った。(Measurement of antibacterial performance) The difference in the increase or decrease in the number of bacteria caused by Staphylococcus aureus was determined by the method of measuring the number of bacteria determined by the Textile Sanitary Processing Council. A difference of 1.6 or more of the increase and decrease values of the number of bacteria was used as a standard for antibacterial activity. In addition, the washing method followed the method determined by the council.
【００３９】〔実施例１〜４〕水系懸濁重合法により、
アクリロニトリル／酢酸ビニル＝９３／７重量比である
還元粘度１．９５のアクリロニトリル系共重合体を得
た。これをジメチルアセトアミドに共重合体濃度が２５
重量％となるように溶解し紡糸原液とした。この紡糸原
液を４０℃、３０重量％ジメチルアセトアミド水溶液を
満たした紡糸浴中に湿式紡糸し、沸水中で溶剤を洗浄し
ながら５倍延伸を施した後の膨潤度７５〜９０％の延伸
糸を引き続き、表１に示したキトサン浴濃度、キトサン
浴温度のキトサン（共和テクノス株式会社フロ−ナック
Ｃ）と酢酸０．１重量％の水溶液を満たした浴に導き、
繊維重量に対する付着水分量が１００％となるように脱
水した後、０．１重量％水酸化ナトリウム水溶液中で中
和（ｐＨ８．３）した。Examples 1 to 4 By an aqueous suspension polymerization method,
An acrylonitrile copolymer having a reduced viscosity of 1.95 with an acrylonitrile / vinyl acetate = 93/7 weight ratio was obtained. This was added to dimethylacetamide at a copolymer concentration of 25.
The solution was dissolved so as to be a weight percent to obtain a spinning stock solution. This spinning solution is wet-spun in a spinning bath filled with a 30% by weight aqueous solution of dimethylacetamide at 40 ° C., stretched 5 times while washing the solvent in boiling water to obtain a drawn yarn having a swelling degree of 75 to 90%. Subsequently, the solution was led to a bath filled with chitosan (Kyowa Technos Co., Ltd., Flownac C) and an aqueous solution of 0.1% by weight of acetic acid at a chitosan bath concentration and a chitosan bath temperature shown in Table 1,
After dehydration so that the amount of water adhering to the fiber weight became 100%, it was neutralized (pH 8.3) in a 0.1% by weight aqueous sodium hydroxide solution.
【００４０】その後、過剰の水酸化ナトリウムを洗浄、
油剤を付着せしめた後１５０℃の熱ロ−ラ−で乾燥緻密
化を行った。さらに２．５ｋｇ／ｃｍ2の加圧スチ−ム
中で緩和延伸処理を行い、単繊維繊度２ｄ、キトサン含
有量０．０６重量％のキトサン含有アクリル繊維を得
た。Thereafter, the excess sodium hydroxide is washed,
After adhering the oil agent, it was dried and densified by a hot roller at 150 ° C. Further, relaxation stretching treatment was performed in a 2.5 kg / cm 2 pressure steam to obtain chitosan-containing acrylic fibers having a single fiber fineness of 2d and a chitosan content of 0.06% by weight.
【００４１】既に述べた方法で、繊維中のキトサン分散
状態に関する指標を測定し、更に洗濯前、洗濯１０回後
の抗菌性と風合いを評価した。その評価結果を表２に示
した。In accordance with the method already described, an index relating to the state of dispersion of chitosan in the fiber was measured, and the antibacterial properties and texture before and after washing 10 times were evaluated. Table 2 shows the evaluation results.
【００４２】〔比較例１〜３〕沸水中で溶剤を洗浄しな
がら５倍延伸を施した後の延伸糸の膨潤度及びキトサン
浴温度を表１に示すように変更した以外は実施例１と同
様に実施し、単繊維繊度２ｄのアクリル繊維を得て、繊
維中のキトサン分散状態及び洗濯前、洗濯１０回後の抗
菌性と風合いを評価した。その評価結果を表２に示し
た。[Comparative Examples 1 to 3] The same procedures as in Example 1 were carried out except that the swelling degree of the drawn yarn and the chitosan bath temperature after performing 5-fold drawing while washing the solvent in boiling water were changed as shown in Table 1. The same operation was performed to obtain an acrylic fiber having a fineness of single fiber of 2d, and the state of dispersion of chitosan in the fiber, and the antibacterial property and texture before and after washing 10 times were evaluated. Table 2 shows the evaluation results.
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【表２】 [Table 2]
【００４５】〔実施例５〜８、比較例４〕共重合体濃
度、紡糸浴温度、及び膨潤度の一部をそれぞれ表３の如
く変更する以外は実施例１と同様に実施して、繊維中の
キトサンの分散状態、抗菌性を評価した。その評価結果
を表４に示した。Examples 5 to 8, Comparative Example 4 The same procedure as in Example 1 was carried out except that the copolymer concentration, spinning bath temperature, and part of the swelling degree were changed as shown in Table 3, respectively. The dispersion state and antibacterial property of chitosan in the inside were evaluated. Table 4 shows the evaluation results.
【００４６】[0046]
【表３】 [Table 3]
【００４７】[0047]
【表４】 [Table 4]
【００４８】〔比較例５〕アクリロニトリル／酢酸ビニ
ル＝９３／７重量比のアクリロニトリル系共重合体から
なる単繊維繊度２ｄのアクリル繊維を繊維重量の３００
倍のキトサン（共和テクノス株式会社フロ−ナックＣ）
０．１重量％酢酸０．１重量％水溶液に１分間浸漬し、
次にマングルで絞り率１００％で絞った後に、０．２Ｎ
水酸化ナトリウム水溶液中を通してキトサンを凝固さ
せ、再びマングルで絞り、１１０℃で５分間熱処理し、
更に水洗、乾燥した。かくして得られた繊維は、当該処
理前後の重量増加率よりキトサンを０．０２％含有して
いることが判明した。しかしその繊維中には、キトサン
微粒子は存在せず、もっぱら繊維表面に薄膜状態で存在
していた。また、この繊維の抗菌性能は洗濯前は５．３
であったが、洗濯１０回後は２．１であった。Comparative Example 5 Acrylnitrile / vinyl acetate = 93/7 weight ratio acrylonitrile-based copolymer was used to prepare an acrylic fiber having a fineness of 2d and a fiber weight of 300.
Double Chitosan (Kyowa Technos Co., Ltd. Flownac C)
Immersed in a 0.1 wt% acetic acid 0.1 wt% aqueous solution for 1 minute,
Next, after squeezing with a mangle at a squeezing ratio of 100%, 0.2N
The chitosan is coagulated by passing through an aqueous sodium hydroxide solution, squeezed again with a mangle, and heat-treated at 110 ° C. for 5 minutes,
Further, it was washed with water and dried. The fiber thus obtained was found to contain 0.02% chitosan from the weight increase before and after the treatment. However, the chitosan fine particles did not exist in the fiber, but existed in a thin film state on the fiber surface. The antibacterial performance of this fiber was 5.3 before washing.
However, it was 2.1 after 10 washes.
【００４９】〔実施例９、１０、比較例６〕水系懸濁重
合法により還元粘度１．８５のアクリロニトリル系共重
合体（アクリロニトリル／酢酸ビニル／メタリルスルホ
ン酸ソ−ダ＝９２／７／１重量比）を得た。この重合体
を用い、共重合体濃度（比較例６のみ）及び膨潤度をそ
れぞれ表５に示されている条件に変更する以外は、実施
例１と同様に実施し、繊維中のキトサンの分散状態と抗
菌性を調べた。その評価結果を表６に示した。Examples 9, 10 and Comparative Example 6 An acrylonitrile copolymer having a reduced viscosity of 1.85 by an aqueous suspension polymerization method (acrylonitrile / vinyl acetate / sodium methallylsulfonate = 92/7/1) Weight ratio). Using this polymer, the same procedure as in Example 1 was carried out except that the copolymer concentration (only in Comparative Example 6) and the degree of swelling were changed to the conditions shown in Table 5, respectively, to disperse chitosan in the fiber. The condition and antibacterial properties were investigated. Table 6 shows the evaluation results.
【００５０】[0050]
【表５】 [Table 5]
【００５１】[0051]
【表６】 [Table 6]
【００５２】[0052]
【発明の効果】本発明によるキトサン含有繊維は、抗菌
防臭繊維製品に求められる、あらゆる細菌に対して効果
があり、繊維の染色、さらし、柔軟処理等の後加工や洗
濯等の繊維製品が使用環境で受ける処理により抗菌防臭
性能が失活せず、生産から廃棄まで含めた全過程で有害
な物質を生じない。又、本発明のキトサン含有アクリル
繊維の製造方法によれば、該繊維を効率よく安定に製造
することができる。The fiber containing chitosan according to the present invention is effective against all kinds of bacteria required for antibacterial and deodorant fiber products, and is used in post-processing such as dyeing, bleaching, and softening of the fiber, and in textile products such as washing. Antibacterial and deodorant performance is not deactivated by environmental treatment, and no harmful substances are generated in all processes from production to disposal. Further, according to the method for producing chitosan-containing acrylic fiber of the present invention, the fiber can be efficiently and stably produced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ａ６１Ｋ 31/73 ＡＤＺ Ａ６１Ｋ 31/73 ＡＤＺ Ｃ０８Ｂ 37/08 Ｃ０８Ｂ 37/08 Ａ Ｄ０１Ｆ 2/08 Ｄ０１Ｆ 2/08 6/14 6/14 Ｚ 6/18 6/18 Ｚ Ｄ０６Ｍ 15/03 Ｄ０６Ｍ 15/03 (72)発明者 西原 良浩 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社大竹事業所内 (72)発明者 細川 宏 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社大竹事業所内 (72)発明者 伊藤 元 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社中央技術研究所内──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI A61K 31/73 ADZ A61K 31/73 ADZ C08B 37/08 C08B 37/08 A D01F 2/08 D01F 2/08 6/14 6 / 14 Z 6/18 6/18 Z D06M 15/03 D06M 15/03 (72) Inventor Yoshihiro Nishihara 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Otake Works (72) Inventor Hiroshi Hosokawa Hiroshima 20-1 Miyuki-cho, Otake-shi, Japan Mitsubishi Rayon Co., Ltd. Otake Works (72) Inventor Gen Ito 20-1 Miyuki-cho, Otake-shi, Hiroshima Pref. Mitsubishi Central Research Institute Co., Ltd.
Claims (4)
％含有し、かつキトサンが繊維中に微粒子状で分散して
おり、繊維横断面に存在する任意の１００〜２００個の
微粒子の円換算平均直径が１〜１００ｎｍ、その標準偏
差が１００ｎｍ以下であることを特徴とするキトサン含
有繊維。1. A fiber containing 0.02 to 2.0% by weight of chitosan, wherein the chitosan is dispersed in the form of fine particles, and 100 to 200 arbitrary fine particles present in the cross section of the fiber. A chitosan-containing fiber having an average circle-converted diameter of 1 to 100 nm and a standard deviation of 100 nm or less.
ビニルアルコ−ル、セルロ−ス或いはそのエステル系誘
導体からなる請求項１記載の繊維。2. The fiber according to claim 1, wherein the fiber comprises an acrylonitrile-based polymer, polyvinyl alcohol, cellulose or an ester-based derivative thereof.
り、かつ該繊維の横断面に存在する任意の１００〜２０
０個のキトサン微粒子において、下式（１）で定義され
るシェ−プファクタ−ＳＦが１００〜３００、その標準
偏差が１５０以下である請求項１記載のキトサン含有繊
維。 ＳＦ＝ＭＬ2×π×１００／（４×Ａ）．．．．．（１） （ここで、ＭＬは繊維の横断面におけるキトサン微粒子
の最大長、Ａは繊維の横断面におけるキトサン微粒子の
面積である。）3. The fiber according to claim 1, wherein the fiber comprises an acrylonitrile-based polymer,
The chitosan-containing fiber according to claim 1, wherein the shape factor-SF defined by the following formula (1) is 100 to 300, and the standard deviation thereof is 150 or less. SF = ML 2 × π × 100 / (4 × A). . . . . (1) (where ML is the maximum length of the chitosan fine particles in the cross section of the fiber, and A is the area of the chitosan fine particles in the cross section of the fiber.)
した乾燥緻密化する以前の膨潤度が３０〜２００％の糸
条を、キトサン濃度が０．０３〜２．５重量％で、温度
が２５〜９０℃のキトサン酸性水溶液に浸漬し、続いて
アルカリ性水溶液により中和した後、乾燥緻密化するこ
とを特徴とするキトサン含有アクリル繊維の製造方法。4. A yarn obtained by wet spinning an acrylonitrile polymer solution and having a degree of swelling of 30 to 200% before dry densification, a chitosan concentration of 0.03 to 2.5% by weight and a temperature of 25 to 200%. A method for producing a chitosan-containing acrylic fiber, comprising immersing in an aqueous solution of chitosan at 90 ° C., subsequently neutralizing with an alkaline aqueous solution, and then drying and densifying.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29909996A JP3450137B2 (en) | 1996-11-11 | 1996-11-11 | Chitosan-containing fiber and method for producing the same |
| PCT/JP1997/002725 WO1998012369A1 (en) | 1996-09-17 | 1997-08-06 | Chitosan-containing acrylic fibers and process for preparing the same |
| CNB2004100325936A CN1276147C (en) | 1996-09-17 | 1997-08-06 | Preparation method of acrylonitrile fiber containing deacetyl chitin |
| KR10-1999-7002195A KR100441358B1 (en) | 1996-09-17 | 1997-08-06 | Chitosan-containing acrylic fibers and process for preparing the same |
| GB9905546A GB2339717B (en) | 1996-09-17 | 1997-08-06 | Chitosan-containing acrylic fibers and process for preparing the same |
| CNB971987823A CN1168861C (en) | 1996-09-17 | 1997-08-06 | Chitosan-containing acrylic fibers and process for preparing the same |
| TW086111551A TW369571B (en) | 1996-09-17 | 1997-08-08 | Chitosan-containing acrylonitrile fibers and process |
| US09/271,272 US6551705B1 (en) | 1996-09-17 | 1999-03-17 | Chitosan-containing acrylic fibers and process for preparing the same |
| US09/605,707 US6524508B1 (en) | 1996-09-17 | 2000-06-27 | Process of making chitosan-containing acrylic fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29909996A JP3450137B2 (en) | 1996-11-11 | 1996-11-11 | Chitosan-containing fiber and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10140418A true JPH10140418A (en) | 1998-05-26 |
| JP3450137B2 JP3450137B2 (en) | 2003-09-22 |
Family
ID=17868144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29909996A Expired - Lifetime JP3450137B2 (en) | 1996-09-17 | 1996-11-11 | Chitosan-containing fiber and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3450137B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001070191A1 (en) * | 2000-03-23 | 2001-09-27 | Cognis Deutschland Gmbh & Co. Kg | Deodorizing preparations containing nanoscale chitosans and/or chitosan derivatives |
| KR20020044890A (en) * | 2000-12-07 | 2002-06-19 | 김순기 | Method of weaving thread with chitosan |
| CN115595789A (en) * | 2022-09-15 | 2023-01-13 | 深圳市歌中歌服饰有限公司（Cn） | Wear-resistant high-elasticity fabric and preparation method thereof |
-
1996
- 1996-11-11 JP JP29909996A patent/JP3450137B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001070191A1 (en) * | 2000-03-23 | 2001-09-27 | Cognis Deutschland Gmbh & Co. Kg | Deodorizing preparations containing nanoscale chitosans and/or chitosan derivatives |
| US6916465B2 (en) | 2000-03-23 | 2005-07-12 | Cognis Deutschland Gmbh & Co. Kg | Deodorizing preparations containing nanosacle chitosans and/or chitosan derivatives |
| KR20020044890A (en) * | 2000-12-07 | 2002-06-19 | 김순기 | Method of weaving thread with chitosan |
| CN115595789A (en) * | 2022-09-15 | 2023-01-13 | 深圳市歌中歌服饰有限公司（Cn） | Wear-resistant high-elasticity fabric and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3450137B2 (en) | 2003-09-22 |
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