JP2010126856A - Iodine-containing microfiber - Google Patents
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Abstract
Description
本発明はヨウ素含有微細繊維および当該繊維からなる不織布に関する。 The present invention relates to an iodine-containing fine fiber and a nonwoven fabric comprising the fiber.
従来、殺菌・抗菌剤としては、トリアゾール系、アルコール系、フェノール系、アルデヒド系、カルボン酸系、エステル系、エーテル系、ハロゲン系、トリアジン系、イミダゾール系、チアゾール系、ジスルフィド系、チオカーバメート系等の所謂有機合成で得られる有機系の殺菌・抗菌剤と、銀などの金属イオン系、ホウ酸系、イオウ系、ヨウ素系等の無機系の殺菌・抗菌剤が良く知られている。 Conventional bactericidal / antibacterial agents include triazole, alcohol, phenol, aldehyde, carboxylic acid, ester, ether, halogen, triazine, imidazole, thiazole, disulfide, thiocarbamate, etc. Well-known are organic disinfecting / antibacterial agents obtained by so-called organic synthesis, and inorganic disinfecting / antibacterial agents such as metal ions such as silver, boric acid, sulfur and iodine.
中でも、ヨウ素は古くから殺菌・抗菌効果があることがよく知られており、人体に対して比較的安全であることから、各種の用途に用いられている。このようなヨウ素系の殺菌・抗菌剤としては、ポリビニルピロリドンに分子ヨウ素が錯体を形成したポビドンヨードが広く知られている。 Above all, iodine has been well known for its antibacterial and antibacterial effects and has been used for various purposes because it is relatively safe for the human body. As such an iodine-based disinfectant / antibacterial agent, povidone iodine in which molecular iodine is complexed with polyvinylpyrrolidone is widely known.
ポビドンヨードは、通常は１０質量％程度の水溶液として使用されている。ポピドンヨードを用いた抗菌素材としては、繊維基材の表面にポビドンヨードを担持した抗菌性のシート（特許文献１参照）、ヨウ素が複合化された水溶性樹脂含有成分を静電紡糸したヨウ素含有微細繊維（特許文献２参照）等が検討されている。 Povidone iodine is usually used as an aqueous solution of about 10% by mass. Antibacterial materials using popidone iodine include an antibacterial sheet carrying povidone iodine on the surface of a fiber substrate (see Patent Document 1), and iodine-containing fine fibers obtained by electrostatic spinning of water-soluble resin-containing components combined with iodine. (See Patent Document 2) and the like have been studied.
特許文献１に記載のシートは、繊維の表面にポビドンヨードを、水溶性ポリマー等を介して担持させるため、ヨウ素が繊維表面から脱落するといった問題がある。また、特許文献２に記載のヨウ素含有微細繊維は、耐湿性、耐水性が不充分であることから、フィルター素材等として用いた場合に、使用条件が制限されるといった問題がある。
The sheet described in
本発明の目的は、例えばフィルター素材等に使用した場合であっても、優れた殺菌・抗菌機能を有し、かつ、耐湿性、耐水性に優れたヨウ素含有微細繊維を提供することにある。 An object of the present invention is to provide an iodine-containing fine fiber having an excellent sterilizing and antibacterial function and excellent in moisture resistance and water resistance even when used for a filter material, for example.
本発明は、
項１． ヨウ素が複合化された水溶性樹脂含有成分を静電紡糸して得られるヨウ素含有微細繊維であって、架橋構造を有することを特徴とするヨウ素含有微細繊維、
項２． ヨウ素が複合化された水溶性樹脂含有成分を静電紡糸した後、架橋処理して得られる項１に記載のヨウ素含有微細繊維、
項３． 架橋処理が、架橋剤を用いて架橋する処理である項２に記載のヨウ素含有微細繊維、
項４． 架橋剤が、グリオキサルおよび／またはメチロール化メラミンである項３に記載のヨウ素含有微細繊維、
項５． 水溶性樹脂が、ポリビニルピロリドンである項１〜４のいずれか１項に記載のヨウ素含有微細繊維、
項６． ヨウ素が複合化された水溶性樹脂含有成分に、他の水溶性樹脂をさらに含む項１〜５のいずれか１項に記載のヨウ素含有微細繊維、
項７． 他の水溶性樹脂が、ポリビニルアルコールおよび／またはアセトアセチル化ポリビニルアルコールである項６に記載のヨウ素含有微細繊維、
項８． 平均繊維径が、０．０１〜１０μｍである項１〜７のいずれか１項に記載のヨウ素含有微細繊維、
項９． 項１〜８のいずれか１項に記載のヨウ素含有微細繊維からなる不織布、
に関する。
The present invention
Item 6. Item 6. The iodine-containing fine fiber according to any one of
Item 7. Item 7. The iodine-containing fine fiber according to Item 6, wherein the other water-soluble resin is polyvinyl alcohol and / or acetoacetylated polyvinyl alcohol.
Item 8. Item 8. The iodine-containing fine fiber according to any one of
Item 9. The nonwoven fabric which consists of an iodine containing fine fiber of any one of claim | item 1 -8,
About.
本発明により、優れた殺菌・抗菌機能を有し、かつ、耐湿性、耐水性に優れたヨウ素含有微細繊維を提供することができる。 According to the present invention, it is possible to provide an iodine-containing fine fiber having an excellent sterilizing / antibacterial function and having excellent moisture resistance and water resistance.
本発明にかかるヨウ素含有微細繊維は、ヨウ素が複合化された水溶性樹脂含有成分を静電紡糸して得られるものであって、架橋構造を有することから、ヨウ素が繊維表面から脱落することなく繊維の構造中に保持された微細繊維を、安全で、かつ低コストで製造することができ、また、耐湿性、耐水性に優れたものである。なお、本明細書において、「複合化」とは、ヨウ素が水溶性樹脂と一体化していることを意味する。 The iodine-containing fine fiber according to the present invention is obtained by electrostatic spinning of a water-soluble resin-containing component combined with iodine, and has a crosslinked structure, so that iodine does not fall off from the fiber surface. The fine fiber held in the fiber structure can be produced safely and at low cost, and is excellent in moisture resistance and water resistance. In the present specification, “composite” means that iodine is integrated with the water-soluble resin.
本発明において、ヨウ素が複合化する水溶性樹脂としては、例えば、ポリアクリル酸等のアクリル系樹脂；ポリアクリルアミド、ポリアリルアミン等のポリアミド系樹脂；ポリエチレンオキシド、ポリプロピレンオキシド等のポリアルキレンオキシド系樹脂；ポリビニルアルコール、アセトアセチル化ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、アクリルニトリル変性ポリビニルアルコール、エポキシ変性ポリビニルアルコール、アクリルアミド変性ポリビニルアルコール等のポリビニルアルコール系樹脂；ポリエーテルグリコール系樹脂；ポリビニルピロリドン系樹脂；澱粉類；水溶性になるように分子量を小さくしたキチン・キトサン等が挙げられる。これらの中でも、より安定的にヨウ素を複合化できる観点から、ポリビニルピロリドン系樹脂、分子量調整を行ったキチン・キトサンが好ましく、ポリビニルピロリドンがより好ましい。 In the present invention, examples of water-soluble resins with which iodine is complexed include acrylic resins such as polyacrylic acid; polyamide resins such as polyacrylamide and polyallylamine; polyalkylene oxide resins such as polyethylene oxide and polypropylene oxide; Polyvinyl alcohol resins such as polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acrylonitrile-modified polyvinyl alcohol, epoxy-modified polyvinyl alcohol, and acrylamide-modified polyvinyl alcohol; polyether glycol resins; polyvinyl pyrrolidone resins; starches; Examples thereof include chitin and chitosan having a molecular weight reduced so as to be water-soluble. Among these, polyvinylpyrrolidone resins and chitin / chitosan having a molecular weight adjusted are preferable, and polyvinylpyrrolidone is more preferable from the viewpoint of more stably complexing iodine.
ヨウ素が複合化する水溶性樹脂の分子量は、水溶性樹脂を一度水に溶解し、その後繊維化する際に効率よく製造するという観点から、３，０００〜３，０００，０００が好ましく、５，０００〜１，５００，０００がより好ましく、６，０００〜１，３００，０００がさらに好ましい。なお、本明細書において、樹脂の分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）により測定される。 The molecular weight of the water-soluble resin with which iodine is complexed is preferably 3,000 to 3,000,000 from the viewpoint of efficiently producing the water-soluble resin once dissolved in water and then fiberized. 000 to 1,500,000 is more preferable, and 6,000 to 1,300,000 is more preferable. In the present specification, the molecular weight of the resin is measured by gel permeation chromatography (GPC).
水溶性樹脂とヨウ素を複合化する方法については特に限定されない。例えば、水溶性樹脂を水に溶解した後、これと、ヨウ素を溶解させた水とを混合し複合化させる方法、水溶性樹脂とヨウ素を密閉容器で混合、加熱することにより、昇華したヨウ素を水溶性樹脂に吸着、複合化させる方法等が挙げられる。また、水に溶解した水溶性樹脂とヨウ素を混合する際にヨウ素を予めシクロデキストリン等に包接させておいてもよい。 The method for combining the water-soluble resin and iodine is not particularly limited. For example, after dissolving a water-soluble resin in water, this is mixed with water in which iodine is dissolved to form a composite, and the water-soluble resin and iodine are mixed and heated in a sealed container to heat the sublimated iodine. Examples include a method of adsorbing and complexing with a water-soluble resin. Further, when mixing iodine with a water-soluble resin dissolved in water, iodine may be previously included in cyclodextrin or the like.
ヨウ素が複合化された水溶性樹脂の具体例としては、ポリビニルピロリドンに分子ヨウ素が錯体を形成したポビドンヨードが挙げられ、例えば、米国Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｓｐｅｃｉａｌｔｙ Ｐｒｏｄｕｃｔｓ（ＩＰＳ）社から「ＰＶＰ−ＩＯＤＩＮＥ」として市販されているものが利用できる。 Specific examples of water-soluble resins in which iodine is complexed include povidone iodine in which molecular iodine is complexed with polyvinylpyrrolidone. For example, it is commercially available as “PVP-IODINE” from International Specialty Products (IPS). You can use what you have.
本発明において、ヨウ素が複合化された水溶性樹脂含有成分は、ヨウ素が複合化された水溶性樹脂を含有するものであるが、微細繊維の繊維径を調整する観点、後述する架橋処理を容易にする観点から、他の水溶性樹脂や水溶性物質を含んでもよい。ヨウ素が複合化された水溶性樹脂の含有量は、前記成分中、０．１〜１００質量％であることが好ましく、０．５〜１００質量％であることがより好ましい。 In the present invention, the water-soluble resin-containing component complexed with iodine contains a water-soluble resin complexed with iodine. However, from the viewpoint of adjusting the fiber diameter of the fine fibers, the crosslinking treatment described later is easy. From the viewpoint of making it, other water-soluble resins and water-soluble substances may be included. The content of the water-soluble resin combined with iodine is preferably 0.1 to 100% by mass, and more preferably 0.5 to 100% by mass in the components.
前記他の水溶性樹脂や水溶性物質の具体例としては、澱粉類、天然物から採取精製されたグァーガム、ローカストビーンガム等の各種ガム類；アルギン酸ナトリウム、アルギン酸アンモニウム、アルギン酸プロピレングリコールエステル等のアルギン酸類；ゼラチン類；カルボキシメチルセルロース、ヒドロキシエチルルロース等のセルロース誘導体；ポリアクリル酸、ポリアクリル酸ナトリウム、アクリル酸エステル共重合体、ポリアクリルアミド等のアクリル系樹脂；ポリビニルアルコール、アセトアセチル化ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、アクリルニトリル変性ポリビニルアルコール、エポキシ変性ポリビニルアルコール、アクリルアミド変性ポリビニルアルコール等のポリビニルアルコール系樹脂；ポリビニルピロリドン、ビニルピロリドンと酢酸ビニル等との共重合体等のビニルピロリドン系重合体；イソブチレン−無水マレイン酸共重合体、メチルビニルエーテル−無水マレイン酸共重合体、スチレン−マレイン酸エステル共重合体等の無水マレイン酸共重合体およびそのアルカリ溶解液；ポリエチレンオキサイド；ポリアリルアミン等が挙げられる。これらの他の水溶性樹脂や水溶性物質は、それぞれ１種単独で、あるいは２種以上を組み合わせて用いることができる。これらの中でも、他の水溶性樹脂が好ましく、ポリビニルアルコール系樹脂、アクリル系樹脂がより好ましく、ポリビニルアルコール、アセトアセチル化ポリビニルアルコールがさらに好ましい。 Specific examples of the other water-soluble resins and water-soluble substances include starches, various gums such as guar gum and locust bean gum collected and purified from natural products; alginic acid such as sodium alginate, ammonium alginate, propylene glycol alginate, etc. Gelatins; Cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose; Acrylic resins such as polyacrylic acid, sodium polyacrylate, acrylate copolymer, polyacrylamide; Polyvinyl alcohol, acetoacetylated polyvinyl alcohol, carboxy Polyvinyl alcohol resins such as modified polyvinyl alcohol, acrylonitrile modified polyvinyl alcohol, epoxy modified polyvinyl alcohol, acrylamide modified polyvinyl alcohol; Vinyl pyrrolidone polymers such as revinyl pyrrolidone, vinyl pyrrolidone and vinyl acetate copolymer; isobutylene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, styrene-maleic acid ester copolymer And maleic anhydride copolymers and alkali solution thereof; polyethylene oxide; polyallylamine and the like. These other water-soluble resins and water-soluble substances can be used singly or in combination of two or more. Among these, other water-soluble resins are preferable, polyvinyl alcohol resins and acrylic resins are more preferable, and polyvinyl alcohol and acetoacetylated polyvinyl alcohol are more preferable.
他の水溶性樹脂の分子量は、後述する樹脂溶液中の水分が蒸発したときに繊維として得られる範囲のものであればよい。具体的には、所望の樹脂溶液粘度を確保する観点から、３，０００〜３，０００，０００が好ましく、５，０００〜１，５００，０００がより好ましい。分子量が３，０００未満では繊維強度が確保しにくく、３，０００，０００を超えると水への溶解性が悪くなり、後述の樹脂溶液濃度範囲での粘度の確保が難しくなる。 The molecular weight of the other water-soluble resin may be in a range that can be obtained as a fiber when water in the resin solution described later evaporates. Specifically, from the viewpoint of ensuring a desired resin solution viscosity, 3,000 to 3,000,000 is preferable, and 5,000 to 1,500,000 is more preferable. If the molecular weight is less than 3,000, the fiber strength is difficult to ensure, and if it exceeds 3,000,000, the solubility in water is deteriorated, making it difficult to ensure the viscosity in the resin solution concentration range described below.
本発明にかかるヨウ素含有微細繊維は、ヨウ素が複合化された水溶性樹脂含有成分を含む樹脂溶液を、静電紡糸法により紡糸して得られるものである。静電紡糸法はエレクトロスピニング法とも呼ばれ、１μｍ以下の径を持つ繊維の製造方法として数十年以上前に発見された方法であるが、最近になっていわゆるナノスケールの微細繊維が有機ＥＬ素子、電池セパレーター、電子ペーパー、電磁波シールド材等への用途のニーズが拡大したこともあり再度注目を集めている。 The iodine-containing fine fiber according to the present invention is obtained by spinning a resin solution containing a water-soluble resin-containing component combined with iodine by an electrostatic spinning method. The electrospinning method is also called an electrospinning method, which was discovered several decades ago as a method for producing fibers having a diameter of 1 μm or less. Recently, so-called nanoscale fine fibers have become organic EL. It has been attracting attention again due to the expansion of needs for applications such as elements, battery separators, electronic paper, and electromagnetic shielding materials.
静電紡糸法では、２〜１００ｋＶ、多くの場合５〜５０ｋＶに設定された電極の一方にセットされた細いノズルより樹脂溶液を他方の電極に向けて放出することにより、他方の電極上に通常は積層された形で微細繊維を得ることができる。
In the electrospinning method, the resin solution is discharged toward the other electrode from a thin nozzle set on one of the electrodes set to 2 to 100 kV, and in
本発明における樹脂溶液としては、ヨウ素が複合化された水溶性樹脂含有成分を水に溶解した水溶液が用いられる。前記樹脂溶液では樹脂の溶解溶剤として水を使用しているため、製造時の引火・爆発の危険が無く、また溶剤の回収が必要ないため、製造コストの低減を図ることができる。得られる微細繊維の繊維径は、水溶性樹脂の特性にもよるが、水溶性樹脂の分子量、樹脂溶液の粘度、樹脂溶液の濃度、樹脂溶液を供給するノズル径、樹脂溶液の供給速度、２極間の電圧、２極間の距離等種々の要因により変えることができる。これらの要因は、得られるヨウ素含有微細繊維の繊維径を決定するのに各々独立して影響を与えるものではなく、それぞれの要因がお互いに影響を及ぼしあっている。 As the resin solution in the present invention, an aqueous solution in which a water-soluble resin-containing component combined with iodine is dissolved in water is used. Since the resin solution uses water as a solvent for dissolving the resin, there is no risk of ignition or explosion during production, and no solvent recovery is required, so that the production cost can be reduced. Although the fiber diameter of the fine fiber obtained depends on the characteristics of the water-soluble resin, the molecular weight of the water-soluble resin, the viscosity of the resin solution, the concentration of the resin solution, the nozzle diameter for supplying the resin solution, the supply speed of the resin solution, 2 It can be changed by various factors such as the voltage between the electrodes and the distance between the electrodes. These factors do not influence each other independently in determining the fiber diameter of the obtained iodine-containing fine fibers, but the respective factors influence each other.
樹脂溶液から繊維化に至るのは、電極にセットされたノズルから放出された樹脂溶液が積層側の他の電極に至るまでの間に、溶媒である水を蒸発させながら静電反発等により微細液滴化・微細繊維化が進むことによるものと考えられるが、この遷移している状態を好適化させるために樹脂溶液の粘度は１つの要因となる。本発明で使用可能な樹脂溶液の粘度範囲としては５〜１００００ｍＰａ・ｓが好ましく、５〜６０００ｍＰａ・ｓがより好ましい。樹脂溶液粘度が５ｍＰａ・ｓ未満では積層側の電極に至る前に繊維化することなく液滴の分散が起こる。また粘度が１００００ｍＰａ・ｓより大きいとノズルからの供給が難しいだけでなく繊維径の調整が難しくなる。なお、本明細書において、樹脂溶液の粘度は、２５℃における粘度のことであり、Ｂ型粘度計により測定される。 From the resin solution to the fiberization, the resin solution discharged from the nozzle set on the electrode reaches the other electrode on the lamination side, and it is fine by electrostatic repulsion while evaporating water as the solvent. It is thought that this is due to the progress of droplet formation and fine fiberization, but the viscosity of the resin solution is one factor for optimizing this transition state. The viscosity range of the resin solution usable in the present invention is preferably 5 to 10,000 mPa · s, more preferably 5 to 6000 mPa · s. When the resin solution viscosity is less than 5 mPa · s, the droplets are dispersed without being fiberized before reaching the electrode on the lamination side. If the viscosity is greater than 10,000 mPa · s, it is difficult not only to supply from the nozzle but also to adjust the fiber diameter. In addition, in this specification, the viscosity of a resin solution is a viscosity in 25 degreeC, and is measured with a B-type viscometer.
樹脂溶液の樹脂濃度は、繊維化が可能である範囲で出来る限り濃い濃度が好ましい。具体的には０．５〜７０質量％が好ましく、０．５〜５０質量％がより好ましい。樹脂濃度が０．５質量％未満では電極間移動中での乾燥が進まず、それが静電反発にも影響するためか繊維の微細化がうまく行われない。樹脂濃度が７０質量％を超える場合には樹脂溶液の粘度を確保するために水溶性樹脂の分子量を小さくする必要などが生じ、分子量の低下が繊維化を難しくするため好ましくない。 The resin concentration of the resin solution is preferably as high as possible within the range where fiberization is possible. Specifically, 0.5 to 70% by mass is preferable, and 0.5 to 50% by mass is more preferable. If the resin concentration is less than 0.5% by mass, drying during movement between the electrodes does not proceed, and the fineness of the fibers is not performed well because it also affects electrostatic repulsion. When the resin concentration exceeds 70% by mass, it is necessary to reduce the molecular weight of the water-soluble resin in order to ensure the viscosity of the resin solution, and a decrease in molecular weight is not preferable because it makes fiberization difficult.
静電紡糸法において、樹脂溶液を供給するノズルの径は、目的とする微細繊維の繊維径、使用する水溶性樹脂の種類、樹脂溶液濃度、粘度等により選択され、通常０．０５〜３ｍｍのものが好ましく使用される。また繊維径の細いものを得るためには、ノズル径が細いほうが良好な結果が得られる場合がある。この場合のノズル径は、好ましくは０．０５〜０．５ｍｍ、より好ましくは０．１〜０．２５ｍｍのノズルが使用される。 In the electrostatic spinning method, the diameter of the nozzle for supplying the resin solution is selected depending on the fiber diameter of the target fine fiber, the type of the water-soluble resin to be used, the concentration of the resin solution, the viscosity, and the like, and usually 0.05 to 3 mm. Those are preferably used. In order to obtain a thin fiber diameter, a finer nozzle diameter may give better results. In this case, the nozzle diameter is preferably 0.05 to 0.5 mm, more preferably 0.1 to 0.25 mm.
微細繊維を製造するために与える２極間の電圧は、目的とする微細繊維の径により上述の各種要因を変更させながら適切に設定すればよく、通常５〜５０ｋＶの範囲で選択される。 What is necessary is just to set suitably the voltage between two poles given in order to manufacture a fine fiber, changing the above-mentioned various factors with the diameter of the target fine fiber, and is normally selected in the range of 5-50 kV.
電極間の距離、すなわちノズル先端と積層させる電極（巻き取り機）との距離は、微細繊維の繊維径、微細繊維の含水率に影響を与えるが、本発明においては、５〜３０ｃｍに設定することが好ましい。なお、本明細書において、ノズルと巻き取り機との間の距離とは、ノズルから樹脂溶液が放出される方向に対して垂直に巻き取り機が設置された場合の、ノズルと巻き取り機との間の最短距離のことを意味する。 The distance between the electrodes, that is, the distance between the nozzle tip and the electrode to be laminated (winding machine) affects the fiber diameter of the fine fibers and the moisture content of the fine fibers, but in the present invention, it is set to 5 to 30 cm. It is preferable. In this specification, the distance between the nozzle and the winder refers to the nozzle and winder when the winder is installed perpendicular to the direction in which the resin solution is discharged from the nozzle. It means the shortest distance between.
樹脂溶液の供給速度は、目的とする微細繊維の繊維径により、各種要因を変更させながら適切な値、例えば、１個のノズル当たり０．００５〜０．３ｍＬ／ｍｉｎに設定にすればよい。供給速度が速すぎると、溶媒である水の蒸発が十分に行われず、液滴の静電反発が十分に進行しない等の影響で、所望の微細繊維が得られない。逆に供給速度が遅すぎると微細繊維の生産性が悪くなるため好ましくない。 The supply speed of the resin solution may be set to an appropriate value, for example, 0.005 to 0.3 mL / min per nozzle, while changing various factors depending on the fiber diameter of the target fine fiber. If the supply speed is too high, the solvent water is not sufficiently evaporated, and the desired fine fibers cannot be obtained due to the effect that the electrostatic repulsion of the droplets does not proceed sufficiently. On the other hand, if the supply rate is too slow, the productivity of fine fibers is deteriorated, which is not preferable.
本発明においては、上記条件を適宜設定することにより微細繊維が得られる。本発明における「微細繊維」とは、平均繊維径が１０μｍ以下の繊維を意味し、本発明により平均繊維径が好ましくは０．０１〜１０μｍ、より好ましくは０．０３〜５μｍの範囲の微細繊維が得られる。本明細書において、平均繊維径は、後述の実施例に記載の方法により測定される。 In the present invention, fine fibers can be obtained by appropriately setting the above conditions. The “fine fiber” in the present invention means a fiber having an average fiber diameter of 10 μm or less, and the fine fiber having an average fiber diameter of preferably 0.01 to 10 μm, more preferably 0.03 to 5 μm according to the present invention. Is obtained. In this specification, an average fiber diameter is measured by the method as described in the below-mentioned Example.
本発明にかかるヨウ素含有微細繊維は、架橋構造を有するものであり、例えば、前記静電紡糸後の微細繊維を架橋処理することにより得ることができる。 The iodine-containing fine fiber according to the present invention has a crosslinked structure, and can be obtained, for example, by subjecting the fine fiber after electrospinning to a crosslinking treatment.
静電紡糸後の微細繊維を架橋処理する方法としては、得られるヨウ素含有微細繊維に架橋構造を付与できる方法であれば、特に限定されない。例えば、前記静電紡糸後の微細繊維に、紫外線、電子線等を照射して架橋処理する方法や、静電紡糸後の微細繊維に含まれるヨウ素が複合化された水溶性樹脂および／または前記他の水溶性樹脂が含有する官能基と反応可能な官能基を有する架橋剤を用いて架橋処理する方法等が挙げられる。 The method for crosslinking the microfiber after electrostatic spinning is not particularly limited as long as it can provide a crosslinked structure to the obtained iodine-containing fine fiber. For example, a method of irradiating the fine fiber after the electrospinning with an ultraviolet ray, an electron beam, or the like, a water-soluble resin in which iodine contained in the fine fiber after the electrospinning is combined and / or the above Examples of the method include a crosslinking treatment using a crosslinking agent having a functional group capable of reacting with a functional group contained in another water-soluble resin.
本明細書においては、実施形態の一例として、ヨウ素が複合化された水溶性樹脂および／または前記他の水溶性樹脂が含有する官能基と反応可能な官能基を有する架橋剤を用いて架橋処理する方法についてより詳しく説明する。 In this specification, as an example of the embodiment, a crosslinking treatment is performed using a crosslinking agent having a functional group capable of reacting with a functional group contained in the water-soluble resin combined with iodine and / or the other water-soluble resin. The method of performing will be described in more detail.
前記架橋剤は、ヨウ素が複合化された水溶性樹脂および／または前記他の水溶性樹脂が含有する官能基と反応可能な官能基を有する化合物であれば、特に限定されない。架橋剤としては、例えば、前記他の水溶性樹脂としてポリビニルアルコール、アセトアセチル化ポリビニルアルコール等のポリビニルアルコール系樹脂を使用した場合、アルデヒド化合物類、アミン化合物類、メチロール化合物類、エポキシ化合物類、イソシアネート化合物類、多価金属化合物等が挙げられる。これらの中でも、架橋反応の容易さの観点から、アルデヒド化合物類、メチロール化合物類が好ましく用いられ、グリオキサル、メチロール化メラミンがより好ましく用いられる。 The crosslinking agent is not particularly limited as long as it is a compound having a functional group capable of reacting with a functional group contained in a water-soluble resin in which iodine is combined and / or the other water-soluble resin. Examples of the crosslinking agent include aldehyde compounds, amine compounds, methylol compounds, epoxy compounds, isocyanates when polyvinyl alcohol resins such as polyvinyl alcohol and acetoacetylated polyvinyl alcohol are used as the other water-soluble resins. Examples thereof include compounds and polyvalent metal compounds. Among these, from the viewpoint of easy crosslinking reaction, aldehyde compounds and methylol compounds are preferably used, and glyoxal and methylolated melamine are more preferably used.
架橋剤の使用量は、ヨウ素が複合化された水溶性樹脂含有成分１００質量部に対して、０．０１〜１０質量部であることが好ましく、０．０２〜５質量部であることがより好ましく、０．０５〜５質量部であることがさらに好ましい。架橋剤の使用量が、０．０１質量部未満の場合、得られるヨウ素含有微細繊維の耐湿性、耐水性が充分でないおそれがある。また、架橋剤の使用量が、１０質量部を超える場合、使用量に見合う架橋効果が得られず、また、経済的でなくなるおそれがある。 The amount of the crosslinking agent used is preferably 0.01 to 10 parts by mass and more preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the water-soluble resin-containing component combined with iodine. Preferably, it is 0.05-5 mass parts. When the usage-amount of a crosslinking agent is less than 0.01 mass part, there exists a possibility that the moisture resistance of the obtained iodine containing fine fiber and water resistance may not be enough. Moreover, when the usage-amount of a crosslinking agent exceeds 10 mass parts, there exists a possibility that the crosslinking effect corresponding to a usage-amount will not be acquired, and it may become economical.
架橋処理する方法としては、前記樹脂溶液にあらかじめ架橋剤を添加しておき、静電紡糸後に加熱処理する方法；静電紡糸後の微細繊維に架橋剤を、塗布、噴霧等の方法により添加し、加熱処理する方法等が挙げられる。これらの中でも、得られるヨウ素含有微細繊維において架橋反応が均一に進行する観点から、樹脂溶液にあらかじめ架橋剤を添加しておき、静電紡糸後に加熱処理する方法が好適に用いられる。 As a crosslinking method, a crosslinking agent is added to the resin solution in advance and heat-treated after electrostatic spinning; a crosslinking agent is added to the fine fibers after electrostatic spinning by a method such as coating or spraying. And a heat treatment method. Among these, from the viewpoint that the crosslinking reaction proceeds uniformly in the iodine-containing fine fibers obtained, a method in which a crosslinking agent is added to the resin solution in advance and heat treatment is performed after electrostatic spinning is preferably used.
加熱処理の温度条件としては、使用する水溶性樹脂の種類、使用する架橋剤種、架橋剤の使用量等により異なるので、一概には言えないが、通常、５０℃〜２００℃である。また、処理時間は、通常、１０分〜３００分である。 The temperature conditions for the heat treatment vary depending on the type of water-soluble resin used, the type of cross-linking agent used, the amount of cross-linking agent used, and the like. Moreover, processing time is 10 minutes-300 minutes normally.
上記の架橋処理によれば、得られるヨウ素含有微細繊維の平均繊維径は、当該処理前の平均繊維径と実質上変化するものではない。 According to said bridge | crosslinking process, the average fiber diameter of the iodine containing fine fiber obtained does not change substantially with the average fiber diameter before the said process.
静電紡糸法においては、通常、微細繊維が電極上に積層された形で得られるため、本発明にかかる不織布は、これを前記架橋処理することにより、容易に得ることができる。したがって、これを用いることにより、殺菌・抗菌機能に優れているだけでなく、耐湿性や耐水性に優れたフィルター素材等として利用することができる。 In the electrospinning method, since the fine fibers are usually obtained in the form of being laminated on the electrode, the nonwoven fabric according to the present invention can be easily obtained by carrying out the crosslinking treatment. Therefore, by using this, it is not only excellent in sterilization and antibacterial functions, but also can be used as a filter material excellent in moisture resistance and water resistance.
以下に、本発明を実施例、比較例に基づいてさらに詳細に説明するが、本発明はかかる実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the present invention is not limited to such examples.
［実施例１］
攪拌機、冷却管を備えた３００ｍＬ容のフラスコに、水１１５ｇを仕込み、９０℃に維持しながら、他の水溶性樹脂としてポリビニルアルコール（株式会社クラレ製、商品名：クラレポバールＰＶＡ−１１７）１０ｇを加えて２時間攪拌し、ポリビニルアルコールが溶解したことを確認した後、２５℃に冷却して８質量％ポリビニルアルコール水溶液を得た。これに、ポピドンヨード（ＩＳＰ社製、商品名：ＰＶＰ−ＩＯＤＩＮＥ、分子量５０，０００、ヨウ素含有量：約１０質量％）０．１ｇを加え攪拌して溶解したことを確認した後、架橋剤として４０質量％グリオキサル水溶液（関東化学社製）０．０２５ｇを添加し、さらに水４３ｇを加えて、樹脂濃度が６質量％、粘度２３０ｍＰａ・ｓの樹脂溶液を得た。
[Example 1]
Into a 300 mL flask equipped with a stirrer and a condenser tube, 115 g of water was charged and maintained at 90 ° C., while 10 g of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: Kuraray Poval PVA-117) was added as another water-soluble resin. In addition, the mixture was stirred for 2 hours to confirm that the polyvinyl alcohol was dissolved, and then cooled to 25 ° C. to obtain an 8% by mass aqueous polyvinyl alcohol solution. To this was added 0.1 g of popidone iodine (trade name: PVP-IODINE, molecular weight 50,000, iodine content: about 10% by mass) manufactured by ISP Co., Ltd. 0.025 g of a mass% glyoxal aqueous solution (manufactured by Kanto Chemical Co., Inc.) was added, and 43 g of water was further added to obtain a resin solution having a resin concentration of 6 mass% and a viscosity of 230 mPa · s.
得られた樹脂溶液適当量を、図１に示した静電紡糸装置（カトーテック社製、ナノファイバーエレクトロスピニングユニット）のシリンジに仕込み、シリンジ針先端（ノズル、ノズル径０．２ｍｍ）と巻き取り機との距離を１００ｍｍとして、２極間に電圧を印加（２０ｋＶ）し、平均繊維径２００〜３００ｎｍの微細繊維からなる不織布を得た。なお、平均繊維径は、電子顕微鏡（日本電子社製、ＪＳＭ−６３９０ＬＡ型）を用いて、任意に３０本の繊維の繊維径を計測して、平均を算出することにより求めた。 An appropriate amount of the obtained resin solution is charged into a syringe of the electrostatic spinning apparatus (manufactured by Kato Tech, nanofiber electrospinning unit) shown in FIG. 1, and the tip of the syringe needle (nozzle, nozzle diameter 0.2 mm) and wound up The distance from the machine was set to 100 mm, and a voltage was applied between the two electrodes (20 kV) to obtain a nonwoven fabric composed of fine fibers having an average fiber diameter of 200 to 300 nm. In addition, the average fiber diameter was calculated | required by measuring the fiber diameter of 30 fibers arbitrarily using an electron microscope (The JEOL Co., Ltd. make, JSM-6390LA type | mold), and calculating an average.
得られた不織布を、１５０℃に設定した恒温槽に２０分間入れて熱処理を行なうことにより、目付量が５ｇ／ｍ２のヨウ素含有微細繊維からなる不織布を得た。 The obtained nonwoven fabric was put in a thermostat set at 150 ° C. for 20 minutes and heat treated to obtain a nonwoven fabric composed of iodine-containing fine fibers having a basis weight of 5 g / m 2 .
［実施例２］
実施例１において、他の水溶性樹脂としてのポリビニルアルコール１０ｇに代えて、アセトアセチル化ポリビニルアルコール（日本合成化学製、商品名：ゴーセファイマーＺ−４１０）１０ｇを用いた以外は実施例１と同様にして、平均繊維径２００〜３００ｎｍの微細繊維からなる不織布を得た。
[Example 2]
In Example 1, in place of 10 g of polyvinyl alcohol as another water-soluble resin, 10 g of acetoacetylated polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Goosefimer Z-410) was used. Similarly, the nonwoven fabric which consists of a fine fiber with an average fiber diameter of 200-300 nm was obtained.
得られた不織布を、１５０℃に設定した恒温槽に２０分間入れて熱処理を行なうことにより、目付量が５ｇ／ｍ２のヨウ素含有微細繊維からなる不織布を得た。 The obtained nonwoven fabric was put in a thermostat set at 150 ° C. for 20 minutes and heat treated to obtain a nonwoven fabric composed of iodine-containing fine fibers having a basis weight of 5 g / m 2 .
［実施例３］
実施例１において、架橋剤としての４０質量％グリオキサル水溶液０．０２５ｇに代えて、メチロール化メラミン（関東化学社製、Ｎ，Ｎ’−ビス（ヒドロキシメチル）尿素）０．０１ｇを用いた以外は実施例１と同様にして、平均繊維径２００〜３００ｎｍの微細繊維からなる不織布を得た。
[Example 3]
In Example 1, instead of 0.025 g of 40 mass% glyoxal aqueous solution as a crosslinking agent, 0.01 g of methylolated melamine (manufactured by Kanto Chemical Co., Inc., N, N′-bis (hydroxymethyl) urea) was used. In the same manner as in Example 1, a nonwoven fabric composed of fine fibers having an average fiber diameter of 200 to 300 nm was obtained.
得られた不織布を、１５０℃に設定した恒温槽に２０分間入れて熱処理を行なうことにより、目付量が５ｇ／ｍ２のヨウ素含有微細繊維からなる不織布を得た。 The obtained nonwoven fabric was put in a thermostat set at 150 ° C. for 20 minutes and heat treated to obtain a nonwoven fabric composed of iodine-containing fine fibers having a basis weight of 5 g / m 2 .
［比較例１］
実施例１において、４０質量％グリオキサル水溶液０．０２５ｇを使用しなかった以外は実施例１と同様にして、平均繊維径２００〜３００ｎｍの微細繊維からなる不織布を得た。
[Comparative Example 1]
In Example 1, the nonwoven fabric which consists of a fine fiber with an average fiber diameter of 200-300 nm was obtained like Example 1 except not having used 0.025g of 40 mass% glyoxal aqueous solution.
得られた不織布を、１５０℃に設定した恒温槽に２０分間入れて熱処理を行なうことにより、目付量が５ｇ／ｍ２のヨウ素含有微細繊維からなる不織布を得た。 The obtained nonwoven fabric was put in a thermostat set at 150 ° C. for 20 minutes and heat treated to obtain a nonwoven fabric composed of iodine-containing fine fibers having a basis weight of 5 g / m 2 .
［評価］
実施例１〜３および比較例１で得られた熱処理後の不織布について、それぞれ抗菌性および耐水性を評価した。
[Evaluation]
About the nonwoven fabric after the heat processing obtained in Examples 1-3 and Comparative Example 1, antibacterial property and water resistance were evaluated, respectively.
（１）抗菌性
抗菌加工製品−抗菌性試験方法・抗菌効果、ＪＩＳ Ｚ ２８０１：２０００に準じて試験を行なった。大腸菌ＩＦＯ３９７２を前培養し、１白金耳の菌を採取して１／５００栄養培地に分散稀釈し、試験菌液とした。この菌液０．４ｍｌを直径９０ｍｍの滅菌シャーレ中に置いた５０ｍｍ角の評価用不織布に滴下し、その上に４０ｍｍのストマッカーフィルムを密着させて載せ、シャーレの蓋を被せた後、プラスチック製容器に入れた。
(1) Antibacterial Antibacterial processed product-antibacterial test method / antibacterial effect, tested according to JIS Z 2801: 2000. Escherichia coli IFO 3972 was pre-cultured, and one platinum loop of fungus was collected and dispersed and diluted in 1/500 nutrient medium to obtain a test bacterial solution. 0.4 ml of this bacterial solution is dropped on a 50 mm square non-woven fabric for evaluation placed in a sterilized petri dish with a diameter of 90 mm, a 40 mm stomacher film is placed on top of it, and the petri dish is covered with a plastic container. Put it in.
３５℃で２４時間培養した後、不織布を滅菌ストマッカー袋に移して、滅菌水１０ｍｌを加えて接種した試験菌の洗い出しを行なった。この液について標準寒天稀釈法により３５℃、４８時間培養し、１検体当りの生菌数を測定した。 After culturing at 35 ° C. for 24 hours, the nonwoven fabric was transferred to a sterile stomacher bag, and 10 ml of sterile water was added to inoculate the inoculated test bacteria. This solution was cultured at 35 ° C. for 48 hours by the standard agar dilution method, and the number of viable bacteria per specimen was measured.
抗菌性の判定は、初期濃度と３５℃、２４時間培養後の生菌数測定した。培養前の生菌数は、４．２×１０４であった。なお、培養後の生菌数が１／１００未満に減少していれば『抗菌性あり』と判断できる。評価結果を表１に示す。 The antibacterial property was determined by measuring the initial concentration and the viable cell count after culturing at 35 ° C. for 24 hours. The number of viable bacteria before the culture was 4.2 × 10 4 . In addition, if the viable cell count after the culture is reduced to less than 1/100, it can be determined that “there is antibacterial”. The evaluation results are shown in Table 1.
（２）耐水性
溶出試験による質量減少率を測定することにより評価した。まず、温度２５℃のイオン交換水１００ｍｌに、秤量した１００ｍｍ角の評価用不織布を浸漬させて１時間攪拌し、取り出した。
(2) Water resistance It evaluated by measuring the mass decreasing rate by a dissolution test. First, a weighed 100 mm square nonwoven fabric for evaluation was immersed in 100 ml of ion-exchanged water at a temperature of 25 ° C., stirred for 1 hour, and taken out.
その後、熱風乾燥機により１００℃で３０分間乾燥させた後、再秤量し、質量減少率を以下の式から算出した。なお、質量減少率が１０質量％未満であれば『耐水性あり』と判断できる。また、このとき、耐湿性についても充分優れたものであると判断できる。評価結果を表１に示す。
質量減少率（質量％）＝（試験前の不織布質量−試験後の不織布質量）
÷試験前の不織布質量×１００
Then, after drying at 100 degreeC for 30 minute (s) with a hot air dryer, it reweighed and the mass reduction | decrease rate was computed from the following formula | equation. In addition, if the mass reduction rate is less than 10% by mass, it can be determined that “water resistance exists”. At this time, it can be determined that the moisture resistance is sufficiently excellent. The evaluation results are shown in Table 1.
Mass reduction rate (mass%) = (nonwoven mass before test−nonwoven mass after test)
÷ Non-woven mass before test x 100
表１より、実施例１〜３で得られたヨウ素含有微細繊維からなる不織布は、抗菌性に優れ、かつ、耐水性に優れていることがわかる。 From Table 1, it can be seen that the nonwoven fabric made of iodine-containing fine fibers obtained in Examples 1 to 3 is excellent in antibacterial properties and water resistance.
本発明にかかるヨウ素含有微細繊維は、殺菌・抗菌機能を有し、かつ、耐湿性、耐水性に優れているため、例えばフィルター、シート等の素材に好適に使用することができる。 The iodine-containing fine fiber according to the present invention has a bactericidal / antibacterial function and is excellent in moisture resistance and water resistance, and therefore can be suitably used for materials such as filters and sheets.
１ シリンジ
２ 樹脂溶液
３ ノズル（シリンジ針）
４ 加電圧器
５ 巻き取り機
1
4
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| CN102134762A (en) * | 2011-04-22 | 2011-07-27 | 东华大学 | Method for preparing polyvinyl pyrrolidone/Fe3O4 composite fibers |
| CN102251305A (en) * | 2011-06-28 | 2011-11-23 | 东华大学 | Preparation of cobalt nickel ferrite/ polyvinyl pyrrolidone composite magnetic nano fibers |
| CN102776707A (en) * | 2012-07-10 | 2012-11-14 | 东华大学 | Method for preparing PVP (polyvinyl pyrroloidone)/FF composite nano-fiber film by static spinning preparation |
| JP2015036411A (en) * | 2013-08-16 | 2015-02-23 | 第一工業製薬株式会社 | Aqueous composition and fiber treatment agent |
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| US11944693B2 (en) | 2010-07-02 | 2024-04-02 | The Procter & Gamble Company | Method for delivering an active agent |
| US11970789B2 (en) | 2010-07-02 | 2024-04-30 | The Procter & Gamble Company | Filaments comprising an active agent nonwoven webs and methods for making same |
| US11944696B2 (en) | 2010-07-02 | 2024-04-02 | The Procter & Gamble Company | Detergent product and method for making same |
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| CN102251305A (en) * | 2011-06-28 | 2011-11-23 | 东华大学 | Preparation of cobalt nickel ferrite/ polyvinyl pyrrolidone composite magnetic nano fibers |
| CN102776707A (en) * | 2012-07-10 | 2012-11-14 | 东华大学 | Method for preparing PVP (polyvinyl pyrroloidone)/FF composite nano-fiber film by static spinning preparation |
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| WO2015164159A1 (en) * | 2014-04-22 | 2015-10-29 | The Procter & Gamble Company | Filaments and fibrous structures employing same |
| US11951194B2 (en) | 2017-01-27 | 2024-04-09 | The Procter & Gamble Company | Compositions in the form of dissolvable solid structures comprising effervescent agglomerated particles |
| US12029799B2 (en) | 2017-05-16 | 2024-07-09 | The Procter & Gamble Company | Conditioning hair care compositions in the form of dissolvable solid structures |
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