JP4808381B2 - Chitosan-coated functional article and manufacturing method thereof - Google Patents
Chitosan-coated functional article and manufacturing method thereof Download PDFInfo
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この出願の発明は、キトサンが被覆固着された機能物品とその製造方法に関するものである。さらに詳しくは、この出願の発明は、キトサンが被覆固着され、高い抗菌効果を有し、さらに親水性をも付与することが可能とされた、キトサン被覆機能物品とその製造方法に関するものである。 The invention of this application relates to a functional article to which chitosan is coated and fixed, and a method for manufacturing the functional article. More specifically, the invention of this application relates to a chitosan-coated functional article, to which chitosan is coated and fixed, has a high antibacterial effect, and can be imparted with hydrophilicity, and a method for producing the same.
キトサンは、カニやエビ等の甲殻類や糸状菌等から得られるキチンの脱アセチル化物である。近年、キチンやキトサンは、保湿性を有し、抗菌作用や免疫賦活作用等、様々な有益な薬理効果を有することが判明するにつれて、その応用への期待が高まっている。 Chitosan is a deacetylated product of chitin obtained from crustaceans such as crabs and shrimps and filamentous fungi. In recent years, as chitin and chitosan have moisturizing properties and have various beneficial pharmacological effects such as antibacterial action and immunostimulatory action, expectations for their application are increasing.
一方、合成高分子の繊維からなる織物や、不織布は、従来から手拭タオル、ウエットティッシュ等のようなワイパー類やナプキン、あるいは紙オムツをはじめとする衛生用品等にも使用されているが、昨今の衛生・清潔志向の高まりから、これら各種製品に抗菌性や抗アレルギー性等の作用を付加した機能製品が数多く製造されてきてもいる。 On the other hand, woven fabrics and non-woven fabrics made of synthetic polymer fibers have been used in wipers and napkins such as hand towels and wet tissues, and sanitary goods such as paper diapers. Due to the increasing hygiene and cleanliness consciousness, many functional products with antibacterial and antiallergic effects added to these various products have been manufactured.
このような状況において、キトサンは、カチオン性の多糖であり、上記のとおりの、保湿性や抗菌性をはじめ、創傷治癒効果等の様々な効果を有することから、このキトサンを用いて合成繊維や不織布等を加工することができれば、上記のような有益な効果を発揮する付加価値の高い機能製品が提供されることになる。このようなことから、キトサンを繊維や不織布等に適用することが期待されていた。 In such a situation, chitosan is a cationic polysaccharide and has various effects such as moisturizing and antibacterial properties as described above, as well as wound healing effects. If a nonwoven fabric or the like can be processed, a high-value-added functional product that exhibits the beneficial effects as described above will be provided. For these reasons, it has been expected that chitosan is applied to fibers, nonwoven fabrics, and the like.
そこで、この出願の発明者らは、キトサンの水溶液を作製し、このものを用いることによって、従来では困難であって、疎水性物質であるポリエチレン（ＰＥ）やポリプロピレン（ＰＰ）等の合成高分子（合成樹脂）等へのキトサンの被覆を可能とする方法を開発した（特許文献１）。この方法では、キトサンをゲル化して水に懸濁し、これに炭酸ガスを通気させることにより作製されたキトサンの水溶液を用いて、表面がプラズマ処理されたＰＥやＰＰ等の合成高分子にキトサンを被覆している。 Therefore, the inventors of the present application made an aqueous solution of chitosan and used this to produce a synthetic polymer such as polyethylene (PE) or polypropylene (PP), which is difficult in the past and is a hydrophobic substance. A method enabling coating of (synthetic resin) etc. with chitosan was developed (Patent Document 1). In this method, chitosan is gelled and suspended in water, and an aqueous solution of chitosan prepared by aeration of carbon dioxide gas is used to apply chitosan to a synthetic polymer such as PE or PP whose surface is plasma-treated. It is covered.
この出願の発明は、上記の課題を解決するものとして、以下のキトサン被覆機能物品およびキトサン被覆機能性物品の製造方法を提供する。＜１＞疎水性物質に、少くとも１種の炭素数８〜１８の長鎖脂肪酸もしくはその酸無水物により部分アシル化された部分アシル化キトサンが被覆固着されているキトサン被覆機能物品。＜２＞部分アシル化キトサンが、両性またはアニオン性部分アシル化キトサンである前記第１の機能物品。＜３＞疎水性物質が、合成高分子体である前記第１または２の機能物品。＜４＞合成高分子が、ポリオレフィンの繊維、織布または不織布である前記第３の機能物品。＜５＞前記第１から４のいずれかの機能物品の製造方法であって、部分アシル化キトサン溶液に疎水性物質を浸漬させ、乾燥処理を施すことを特徴とするキトサン被覆機能物品の製造方法。 The invention of this application provides the following chitosan-covered functional article and a method for producing a chitosan-covered functional article as a solution to the above problems. <1> A chitosan-coated functional article in which a partially acylated chitosan partially acylated with at least one long-chain fatty acid having 8 to 18 carbon atoms or an acid anhydride thereof is coated and fixed to a hydrophobic substance . <2> The first functional article, wherein the partially acylated chitosan is an amphoteric or anionic partially acylated chitosan. < 3 > The first or second functional article, wherein the hydrophobic substance is a synthetic polymer. < 4 > The third functional article, wherein the synthetic polymer is a polyolefin fiber, woven fabric, or nonwoven fabric. < 5 > A method for producing a functional article according to any one of the first to fourth aspects, wherein a hydrophobic substance is immersed in a partially acylated chitosan solution and dried. .
しかしながら、以上のような従来の方法の場合には、キトサンを被覆するために、ＰＰやＰＥ等の合成高分子表面のプラズマ処理や紫外線照射という特殊処理を行う必要があり、そのための設備や工程の負担が大きいという問題があった。また、キトサンの被覆固着における密着性等の特性においても必ずしも充分ではなかった。
この出願の発明は、以上のとおりの背景から、従来技術の問題点を解消し、疎水性物質（合成高分子）でも、簡単にキトサンが被覆可能とされ、しかも表面改質とともに各種の生理活性効果や保湿性等の効果の発現が期待されるキトサンが被覆された新しい機能物品とその製造方法を提供することを課題としている。 The invention of this application solves the problems of the prior art based on the background as described above, and even a hydrophobic substance (synthetic polymer) can be easily coated with chitosan, and various physiological activities can be achieved along with surface modification. It is an object of the present invention to provide a new functional article coated with chitosan, which is expected to exhibit effects and effects such as moisture retention, and a method for producing the same.
この出願の発明は、上記の課題を解決するものとして、以下のキトサン被覆機能物品およびキトサン被覆機能性物品の製造方法を提供する。＜１＞疎水性物質に部分アシル化キトサンが被覆固着されているキトサン被覆機能物品。＜２＞部分アシル化キトサンが、少くとも１種の炭素数８〜１８の長鎖脂肪酸もしくはその酸無水物により部分アシル化されたものである前記第１の機能物品。＜３＞部分アシル化キトサンが、両性またはアニオン性部分アシル化キトサンである前記第１または２の機能物品。＜４＞疎水性物質が、合成高分子体である前記第１から３のいずれかの機能物品。＜５＞合成高分子が、ポリオレフィンの繊維、織布または不織布である前記第４の機能物品。＜６＞前記第１から５のいずれかの機能物品の製造方法であって、部分アシル化キトサン溶液に疎水性物質を浸漬させ、乾燥処理を施すことを特徴とするキトサン被覆機能物品の製造方法。 The invention of this application, as to solve the above problems, provides a method for producing the following key chitosan coated functional articles and chitosan coated functional articles. <1> A chitosan-coated functional article in which a partially acylated chitosan is coated and fixed to a hydrophobic substance. <2> The first functional article, wherein the partially acylated chitosan is partially acylated with at least one long-chain fatty acid having 8 to 18 carbon atoms or an acid anhydride thereof. <3> The first or second functional article, wherein the partially acylated chitosan is an amphoteric or anionic partially acylated chitosan. <4> The functional article according to any one of the first to third aspects, wherein the hydrophobic substance is a synthetic polymer. <5> The fourth functional article, wherein the synthetic polymer is a polyolefin fiber, woven fabric, or nonwoven fabric. <6> A method for producing a functional article according to any one of the first to fifth aspects, wherein a hydrophobic substance is immersed in a partially acylated chitosan solution and dried. .
以上のこの出願の第１の発明によって、疎水性物質（合成高分子）でも、簡便にキトサンが被覆固着され、表面改質とともに抗菌効果等の生理活性を発現し、親水性をも付与することのできる、機能物品が提供される。また、少くとも１種の炭素数８〜１８の長鎖脂肪酸もしくはその酸無水物により部分アシル化キトサンを調整されているため、より効率よく上記の効果を実現することができる。また、第２の発明によれば、両性またはアニオン性部分アシル化キトサンとすることで上記の効果はより顕著なものとなる。そして、第３の発明では、疎水性物質としての合成高分子に対しキトサンが被覆された機能物品が提供され、第４の発明によれば、繊維、フィルム等としても汎用のポリエチレン、ポリプロピレン等のポリオレフィン系の機能物品が提供されることになる。さらに第５の発明によれば、簡便な手段で、密着性に優れ、生理活性等の発現も良好なキトサン被覆物品の製造が可能とされる。 According to the first invention of this application, chitosan is easily coated and fixed even with a hydrophobic substance (synthetic polymer), exhibits surface modification and physiological activity such as antibacterial effect, and imparts hydrophilicity. can, functional articles Ru are provided. Moreover, since the partially acylated chitosan is adjusted with at least one kind of long-chain fatty acid having 8 to 18 carbon atoms or an acid anhydride thereof, the above-described effects can be realized more efficiently. Further, according to the second invention, the above-described effect becomes more remarkable by using an amphoteric or anionic partially acylated chitosan. And in 3rd invention, the functional article by which chitosan was coat | covered with respect to the synthetic polymer as a hydrophobic substance is provided, According to 4th invention, general-purpose polyethylene, a polypropylene, etc. also as a fiber, a film, etc. A functional product of polyolefin type will be provided. Furthermore, according to the fifth invention, it is possible to produce a chitosan-coated article that is excellent in adhesion and excellent in physiological activity and the like by simple means.
この出願の発明は、上記のとおりの特徴をもつものであるが、以下にその実施の形態について詳しく説明する。 The invention of this application has the features as described above, and the embodiments thereof will be described in detail below.
この出願では、カニやエビ等の甲殻類等からのキトサン、あるいはその部分アセチル化物を対象として考慮することができる。そして、これらのキトサンは、この出願の発明において部分アシル化されたものとして使用される。この場合の部分アシル化は、キトサンのヒドロキシル基、そしてアミノ基の部分アシル化として実現される。 In this application, chitosan from crustaceans such as crabs and shrimps, or partially acetylated products thereof can be considered. These chitosans are used as partially acylated in the invention of this application. Partial acylation in this case is realized as partial acylation of the hydroxyl group and then the amino group of chitosan.
アシル化は、有機カルボン酸もしくはその酸ハロゲン化物あるいは無水カルボン酸を用いて行うことができる。 The acylation can be performed using an organic carboxylic acid or an acid halide thereof or a carboxylic anhydride.
そして、この部分アシル化においては、所定のアシル化反応の少くとも一部を長鎖脂肪酸あるいはその無水物を用いることが好適に考慮される。この場合の長鎖脂肪酸あるいはその無水物は、炭素数８〜１８程度のものが考慮されてよい。 In this partial acylation, it is preferable to use a long-chain fatty acid or an anhydride thereof for at least a part of the predetermined acylation reaction. In this case, the long-chain fatty acid or its anhydride may be one having about 8 to 18 carbon atoms.
より好適な場合として例示すると、まず、キトサンを長鎖脂肪酸と反応させて、キトサンのアミノ基の一部、具体的には１０−２０％をアシル化させる。ついで、一部のアミノ基がアシル化されたキトサンをピロリドンカルボン酸（ＰＣＡ）や乳酸等で中和させる。これにより得られた部分アシル化キトサン（Ｐ−Ｃｎ−キトサン）を水や、水と相溶性のあるアルコール等との混合水性溶液に溶解させ、部分アシル化キトサン水溶液を作製する。そして、この部分アシル化キトサン水溶液に疎水性物質を浸漬させ、乾燥処理を施すだけで、簡便にキトサンを被覆固着することができ、キトサンが被覆固着された機能物品を製造することができる。 As a more preferable case, first, chitosan is reacted with a long-chain fatty acid to acylate a part of the amino group of chitosan, specifically 10-20%. Next, chitosan having some amino groups acylated is neutralized with pyrrolidone carboxylic acid (PCA) or lactic acid. The partially acylated chitosan (P-Cn-chitosan) obtained in this manner is dissolved in a mixed aqueous solution of water or an alcohol compatible with water to prepare a partially acylated chitosan aqueous solution. Then, by simply immersing a hydrophobic substance in this partially acylated chitosan aqueous solution and subjecting it to a drying treatment, the chitosan can be simply coated and fixed, and a functional article coated and fixed with chitosan can be produced.
この場合の部分アシル化キトサンは、基本的にはカチオン性であることから、溶液のｐＨが中性からアルカリ性の場合は沈殿を生じることがある。このような場合には、電荷を調節して両性またはアニオン性の部分アシル化キトサンとすることで沈殿を防ぐことができる。 Since the partially acylated chitosan in this case is basically cationic, precipitation may occur when the pH of the solution is neutral to alkaline. In such a case, precipitation can be prevented by adjusting the charge to form an amphoteric or anionic partially acylated chitosan.
このような両性またはアニオン性部分アシル化キトサンは、上記のような長鎖脂肪酸やより低炭素数のカルボン酸あるいはそれらの酸無水物を用いて部分アシル化した部分アシル化キトサン溶液に無水コハク酸等のヒドロキシカルボン酸あるいはその酸無水物を添加し、また、その添加量を加減することにより、部分アシル化キトサンの電荷を調節し、任意の電荷を有する両性またはアニオン性の部分アシル化キトサンとすることができる。 Such amphoteric or anionic partially acylated chitosan is obtained by adding succinic anhydride to a partially acylated chitosan solution partially acylated using a long chain fatty acid, a carboxylic acid having a lower carbon number, or an acid anhydride thereof. By adding a hydroxycarboxylic acid or an acid anhydride thereof, and adjusting the amount added, the charge of the partially acylated chitosan is adjusted, and the amphoteric or anionic partially acylated chitosan having an arbitrary charge can do.
また、この出願の発明における疎水性物質としては、特にその種類は限定されないが、好適な機能物品としての実現のためには、天然高分子あるいは合成高分子体とすることが好ましい。この場合の合成高分子体は、たとえば、ポリエチレンやポリプロピレン等のポリオレフィン、ポリアクリル、ポリカーボネイト、ポリアセタール等が使用できる。特に、ポリエチレンおよびポリプロピレンは、手拭タオル、ウエットティッシュ等のようなワイパー類やナプキン、また、紙オムツをはじめとする衛生用品等に広く用いられる不織布の構成物の一つであるため、これら多くの製品にこの出願の発明の効果を付与することができるため好ましい。もちろん、これらは混合して用いられていてもよいし、あるいは併用されていてもよい。 Further, the type of the hydrophobic substance in the invention of this application is not particularly limited, but it is preferably a natural polymer or a synthetic polymer for realizing a suitable functional article. As the synthetic polymer in this case, for example, polyolefin such as polyethylene and polypropylene, polyacryl, polycarbonate, polyacetal and the like can be used. In particular, polyethylene and polypropylene are one of the constituents of nonwoven fabrics widely used in wipers and napkins such as hand towels, wet tissues, and sanitary products such as paper diapers. This is preferable because the effect of the invention of this application can be imparted to the product. Of course, these may be used as a mixture or may be used in combination.
この出願の発明においては、以上のような部分アシル化キトサンの溶液に疎水性物質を浸漬させ、乾燥処理を施すことで、ポリエチレンやポリプロピレン等の合成高分子等の疎水性物質にも、従来のキトサンよりも抗菌効果や親水性等が向上された部分アシル化キトサンを簡便に被覆固着させることができる。また、上記のとおりの各種の有益な効果が付与された付加価値の高い機能物品を提供することができる。 In the invention of this application, a hydrophobic substance such as a synthetic polymer such as polyethylene or polypropylene can be applied to a hydrophobic substance by immersing the hydrophobic substance in a solution of the partially acylated chitosan as described above and performing a drying treatment. A partially acylated chitosan having improved antibacterial effect and hydrophilicity than chitosan can be easily coated and fixed. Moreover, the functional article with high added value to which various beneficial effects as described above are given can be provided.
疎水性物質を浸漬する部分アシル化キトサンの濃度や浸漬時の溶液温度、浸漬時間、さらには乾燥のための条件等については、生産性、そして被覆層の厚みや被覆層による作用の発現程度等を考慮して定めることができる。 Concentration of partially acylated chitosan in which hydrophobic substance is immersed, solution temperature at the time of immersion, immersion time, conditions for drying, etc., productivity, degree of coating layer, degree of manifestation of action by coating layer, etc. Can be determined in consideration of
部分アシル化キトサンの溶液濃度としては、たとえば０．１〜５重量％の範囲の水溶液が考慮され、疎水性物質への被覆量としては、たとえば０．５〜１０ｗｔ／ｗｔ％程度とすることが、さらに乾燥は４０℃〜８０℃程度の温風により行うことなどが考慮される。もちろんこれらは限定的ではない。 As the solution concentration of the partially acylated chitosan, for example, an aqueous solution in the range of 0.1 to 5% by weight is considered, and the coating amount to the hydrophobic substance may be, for example, about 0.5 to 10 wt / wt%. Further, it is considered that the drying is performed with warm air of about 40 ° C. to 80 ° C. Of course, these are not limiting.
以下に実施例を説明し、さらに詳しくこの出願の発明について説明する。もちろん、以下の例によって発明が限定されることはない。 Examples will be described below, and the invention of this application will be described in more detail. Of course, the invention is not limited by the following examples.
＜実施例１＞ポリプロピレン（ＰＰ）からなる不織布への部分アシル化キトサンの被覆固着
１．部分アシル化キトサンの調製
１）キトサンにピロリドンカルボン酸（ＰＣＡ）または乳酸をキトサンのヘキソサミン塩１残基当たり１モル当量加えて溶解させ、１倍量のメタノールを加えて、均一溶液とした。
<Example 1> Covering and fixing a partially acylated chitosan to a nonwoven fabric made of polypropylene (PP) Preparation of partially acylated chitosan 1) Pyrrolidone carboxylic acid (PCA) or lactic acid was added to chitosan in an amount of 1 molar equivalent per hexosamine salt of chitosan and dissolved, and 1-fold amount of methanol was added to obtain a homogeneous solution.
２）この溶液にメタノールで溶解した無水ミリスチン酸をキトサンのヘキソサミン塩１残基当たり０．１モル当量を添加し、室温で一晩攪拌した。 2) 0.1 molar equivalent of myristic anhydride dissolved in methanol per residue of the hexosamine salt of chitosan was added to this solution and stirred overnight at room temperature.
３）ついで、公知の方法である限外濾過、濃縮、凍結ろ過およびアセトン洗浄により部分アシル化キトサンを得た。 3) Next, partially acylated chitosan was obtained by known methods such as ultrafiltration, concentration, freeze filtration and acetone washing.
なお、アシル基の導入率は、ＮＭＲ（５００ＭＨｚ）測定により置換基の状態を調べることにより算出した。本実施例においては、キトサンのアミノ基は１０％がアシル化された（Ｐ−Ｃ12（１０％）−キトサン）。
２．部分アシル化キトサンの被覆固着
このＰ−Ｃ12（１０％）−キトサンの水溶液（０．５％）にＰＰからなる不織布を浸した後、６０℃の温風による乾燥処理を施して、不織布に４．８３ｗｔ／ｗｔ％のキトサン（Ｐ−Ｃ12（１０％）−キトサン）を被覆固着させた。
３．蛍光プローブ法による被覆固着の状態検討
Ｐ−Ｃ１２（１０％）−キトサンが被覆固着された不織布（以下、ＰＰＣＰとする）およびキトサン被覆固着未処理のＰＰ不織布（以下、ＰＰ不織布とする）それぞれを、酸性の蛍光プローブであるフルオレスセイン水溶液（２５０ｐｐｍ，Ｈ2Ｏ：Ethanol ＝１：１）に２４時間浸した後、水で数回洗浄した。この蛍光プローブ処理したＰＰＣＰおよびＰＰ不織布を高精細クイックマイクロスコープ（ＶＨ−５０００、ＫＥＹＥＮＣＥ社製）を用いて観察を行った。
The introduction rate of the acyl group was calculated by examining the state of the substituent by NMR (500 MHz) measurement. In this example, 10% of the amino group of chitosan was acylated (P—C 12 (10%)-chitosan).
2. Covering and fixing the partially acylated chitosan After immersing a non-woven fabric made of PP in this aqueous solution of P-C 12 (10%)-chitosan (0.5%), drying treatment with hot air at 60 ° C. 4.83wt / wt% of chitosan (P-C 12 (10% ) - chitosan) was coated fixation.
3. Examination of the state of coating fixation by the fluorescent probe method Each of P-C12 (10%)-nonwoven fabric coated with chitosan (hereinafter referred to as PPCP) and untreated PP nonwoven fabric (hereinafter referred to as PP nonwoven fabric) treated with chitosan coating The sample was immersed in a fluorescein aqueous solution (250 ppm, H 2 O: Ethanol = 1: 1) as an acidic fluorescent probe for 24 hours, and then washed several times with water. The PPCP and PP nonwoven fabric treated with the fluorescent probe were observed using a high-definition quick microscope (VH-5000, manufactured by KEYENCE).
その結果、ＰＰＣＰの表面は、強く蛍光を発していることが確認された。これは、フルオレスセインが多量に吸着していることを意味する。そして、フルオレスセインは、カルボキシル基を有しており、キトサンのアミノ基と静電的な相互作用で結合することから、ＰＣＰＰの繊維の表面上には均一にキトサンがコーティングされていることを確認することができた。 As a result, it was confirmed that the PPCP surface was strongly fluorescent. This means that a large amount of fluorescein is adsorbed. Fluorescein has a carboxyl group and binds to the amino group of chitosan by electrostatic interaction, so that the surface of the PCPP fiber is uniformly coated with chitosan. I was able to confirm.
一方、ＰＰ不織布の表面を観察した結果は、当然にも蛍光を発していなかった。
＜実施例２＞ＰＣＰＰの親水性（濡れ性）
ＰＣＰＰの親水性を検討するため、着色された蒸留水にＰＣＰＰまたはＰＰ不織布を浸し、水に接したサンプル裏面から水が浸透し、サンプル表面にまで達して、表面が着色されるまでの時間を計測した。
On the other hand, as a result of observing the surface of the PP nonwoven fabric, it was naturally not emitting fluorescence.
<Example 2> Hydrophilicity (wetting property) of PCPP
In order to study the hydrophilicity of PCPP, PCPP or PP nonwoven fabric is immersed in colored distilled water, water penetrates from the back of the sample in contact with water, reaches the sample surface, and the time until the surface is colored is determined. Measured.
具体的には、５ｃｍ×５ｃｍの大きさにカットした実施例１のＰＣＰＰおよびＰＰ不織布をそれぞれ３枚用意し、染色剤のビクトリアピュアブルー（１００ｐｐｍを添加）で着色した蒸留水２０ｍｌが入れられたシャーレ（直径９ｃｍ）に浸した。 Specifically, three PCPP and PP nonwoven fabrics of Example 1 each cut to a size of 5 cm × 5 cm were prepared, and 20 ml of distilled water colored with a dyeing agent Victoria Pure Blue (added with 100 ppm) was added. It was immersed in a petri dish (diameter 9 cm).
その結果、ＰＣＰＰは、平均して約２３秒でＰＣＰＰ表面が青色に着色された。一方、ＰＰ不織布においては、約１時間経過してもその表面は着色されなかった。 As a result, the PCPP surface was colored blue in about 23 seconds on average. On the other hand, the surface of the PP nonwoven fabric was not colored even after about 1 hour.
この結果から、明らかなように、ＰＣＰＰは、ＰＰ不織布と比較して、親水性（濡れ性）が向上し、疎水性物質であるＰＰからなる不織布においても親水性を保有させることができる。
＜実施例３＞Ｐ−Ｃ12（１０％）−キトサンの抗菌性
実施例１において調製した部分アシル化キトサン（Ｐ−Ｃ12（１０％）−キトサン）の抗菌効果を検討するため、まず以下の手順で、ＰＣＡを除去した。
As is clear from this result, PCPP has improved hydrophilicity (wetting property) compared to PP nonwoven fabric, and can retain hydrophilicity even in a nonwoven fabric made of PP which is a hydrophobic substance.
<Example 3> P-C 12 (10 %) - partially acylated chitosan prepared in antimicrobial Example 1 Chitosan (P-C 12 (10% ) - chitosan) To study the antimicrobial efficacy of, first, the following In this procedure, PCA was removed.
１）調整直後のＰ−Ｃ12（１０％）−キトサン溶液に０．５Ｎ ＮａＯＨを徐々に添加し、Ｐ−Ｃ12（１０％）−キトサン溶液のｐＨを１０−１３（アルカリ性）に調整し、Ｐ−Ｃ12（１０％）−キトサンを沈殿させた。 1) Gradually add 0.5N NaOH to the P-C 12 (10%)-chitosan solution immediately after adjustment to adjust the pH of the P-C 12 (10%)-chitosan solution to 10-13 (alkaline). , P-C 12 (10% ) - precipitated chitosan.
２）沈殿したＰ−Ｃ12（１０％）−キトサンを水洗することにより、ＰＣＡを除去した。 2) PCA was removed by washing the precipitated P—C 12 (10%)-chitosan with water.
次いで、Ｐ−Ｃ12（１０％）−キトサンの抗菌性の試験は、ＪＩＳ Ｚ ２８０１法を改変した以下の方法で行った。 Next, the antibacterial property test of P-C 12 (10%)-chitosan was carried out by the following method obtained by modifying the JIS Z 2801 method.
１）ＬＢ寒天培地上で前培養を行った黄色ブドウ球菌(Staphylococcus aureus(NBRC 12732)）を白金耳で採取し、２０ｍｌのＬＢ液体培地に植菌し、３７℃で２０−２４時間培養した。 1) Staphylococcus aureus (NBRC 12732) pre-cultured on LB agar medium was collected with a platinum loop, inoculated into 20 ml of LB liquid medium, and cultured at 37 ° C. for 20-24 hours.
２）Ｐ−Ｃ12（１０％）−キトサンおよびこのＰ−Ｃ１２（１０％）−キトサンの調整に用いた原料のキトサン粉末（ＰＳＨ−８０（分子量８０００００）、焼津水産化学工業社製）を用意し、抗菌試験用の試料として用いた。なお、この試験試料は、全量が０．１ｇとなるよう以下の４種類の系を調整した。
（Ｉ）キトサン粉末（ＰＳＨ）のみ、０．１ｇ
（II）Ｐ−Ｃ12（１０％）−キトサンのみ、０．１ｇ
(III)Ｐ−Ｃ12（１０％）−キトサン：ＰＳＨ＝１：１，０．０５ｇ：０．０５ｇ
（IV）Ｐ−Ｃ12（１０％）−キトサン：ＰＳＨ＝２：１，０．０６７ｇ：０．０３３ｇ
３）上記各系の試料をそれぞれ２０ｍｌのＬＢ液体培地に添加した。次に、上記３．１）にて培養した培養液０．４ｍｌを植菌し、３７℃で８時間の培養を行った。
2) Prepare P-C 12 (10%)-chitosan and chitosan powder (PSH-80 (molecular weight 800,000), manufactured by Yaizu Suisan Kagaku Kogyo Co., Ltd.) as a raw material used to prepare this P-C12 (10%)-chitosan And used as a sample for antibacterial tests. In this test sample, the following four types of systems were prepared so that the total amount was 0.1 g.
(I) Chitosan powder (PSH) only, 0.1 g
(II) P-C 12 ( 10%) - chitosan alone, 0.1 g
(III) P-C 12 ( 10%) - Chitosan: PSH = 1: 1,0.05g: 0.05g
(IV) P-C 12 ( 10%) - Chitosan: PSH = 2: 1,0.067g: 0.033g
3) Each system sample was added to 20 ml of LB liquid medium. Next, 0.4 ml of the culture solution cultured in 3.1) above was inoculated and cultured at 37 ° C. for 8 hours.
４）そして、培養前および培養後の菌数測定をＪＩＳ Ｚ ２８０１法にしたがい、希釈平板法にて行い、得られた菌数から（Ｉ）から（IV）の各系における黄色ブドウ球菌に対する静菌活性値を算出した。結果は、図１のとおりであった。すなわち、ＰＳＨ単独の系でも静菌活性値が２．２を示し、ＪＩＳで認める抗菌値＞２．０をクリアーした。以降、Ｐ−Ｃ12（１０％）−キトサンの含有量が増加するにつれ、静菌活性値も増加する傾向にあり、このことは、部分アシル化キトサン（この実施例では、Ｐ−Ｃ12（１０％）−キトサン）は、通常のキトサンよりも高い抗菌性を有することが確認された。 4) The number of bacteria before and after culturing was measured by the dilution plate method according to JIS Z 2801 method. From the obtained number of bacteria, static against Staphylococcus aureus in each system (I) to (IV) was obtained. The fungal activity value was calculated. The result was as shown in FIG. That is, even in the system of PSH alone, the bacteriostatic activity value was 2.2, and the antibacterial value> 2.0 recognized by JIS was cleared. Thereafter, as the content of P-C 12 (10%)-chitosan increases, the bacteriostatic activity value also tends to increase. This indicates that partially acylated chitosan (in this example, P-C 12 ( 10%)-chitosan) was confirmed to have higher antibacterial properties than normal chitosan.
そして以上のような優れた抗菌性は、実施例１のように被覆固着した状態においても確認された。 The excellent antibacterial properties as described above were confirmed even in the state where the coating was fixed as in Example 1.
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