TWI425126B - Chitosan fiber matrix and preparing method and use thereof - Google Patents

Chitosan fiber matrix and preparing method and use thereof Download PDF

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TWI425126B
TWI425126B TW099140402A TW99140402A TWI425126B TW I425126 B TWI425126 B TW I425126B TW 099140402 A TW099140402 A TW 099140402A TW 99140402 A TW99140402 A TW 99140402A TW I425126 B TWI425126 B TW I425126B
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chitosan
chitosan fiber
solution
fiber
substrate
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TW201221712A (en
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Wenchung Chang
Chuli Peng
Yiting Shu
Juisheng Lee
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Taiwan Textile Res Inst
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幾丁聚醣纖維基材及其製備方法與用途Chitosan fiber substrate, preparation method and use thereof

本發明是有關於一種纖維基材的製備方法,且特別是有關於一種幾丁聚醣纖維基材的製備方法。The invention relates to a method for preparing a fibrous substrate, and in particular to a method for preparing a chitosan fiber substrate.

幾丁聚醣纖維的製備方法通常有兩種,一種為濕式紡絲,另一種為電氣紡絲。但是這兩種紡絲方法不是要用到高濃度的強酸強鹼,就是要用到有機溶劑才能進行紡絲的工作,使得環保問題較難處理。濕式紡絲方法所得的幾丁聚醣纖維為微米尺寸,一般須要進行不織布製程,才能形成纖維基材,且製程中強鹼之中和或有機溶劑清洗,也使得纖維基材的製程較為複雜。電氣紡絲雖然可得到奈米尺寸的纖維,然而製程中使用較毒的有機溶劑或高濃度的有機酸,以及昂貴的製程設備和量化成熟度,使得需進一步考量奈米幾丁聚醣纖維需求之必要性。There are usually two methods for preparing chitosan fibers, one is wet spinning and the other is electric spinning. However, the two spinning methods do not require the use of a high concentration of strong acid and alkali, that is, the use of an organic solvent to perform the spinning work, making the environmental protection problem more difficult to handle. The chitosan fiber obtained by the wet spinning method has a micron size, generally requires a non-woven process to form a fibrous substrate, and the neutral alkali or organic solvent is cleaned in the process, which also makes the process of the fiber substrate more complicated. . Although electrospinning can obtain nanometer-sized fibers, the use of more toxic organic solvents or high concentrations of organic acids in the process, as well as expensive process equipment and quantitative maturity, requires further consideration of nano-butanose fiber requirements. The necessity.

單一纖維型態的幾丁聚醣,雖然較其它型態具有較佳的機械性質,但其膨潤性也受限。而海綿、凝膠等型態具有較佳膨潤性,但需要利用化學修飾劑或化學交聯劑來維持其結構穩定性。上述化學交聯劑及化學修飾劑不是常使合成步驟變得較為複雜難以控制,就是常具有毒性。此外單一的纖維或海綿型態結構,其物化性質及功能性會受限。The chitosan of a single fiber type has a better mechanical property than other types, but its swelling property is also limited. While sponges, gels, and the like have better swelling properties, chemical modifiers or chemical crosslinking agents are required to maintain their structural stability. The above chemical crosslinking agents and chemical modifiers are not often complicated and difficult to control, and are often toxic. In addition, a single fiber or sponge structure has limited physical and chemical properties and functionality.

因此,本發明之一態樣是在提供一種幾丁聚醣纖維基材的製備方法。製備方法包含下面各步驟。Accordingly, one aspect of the present invention is to provide a method of preparing a chitosan fiber substrate. The preparation method comprises the following steps.

依據一實施方式,先分別製備紡絲液及成型液。上述紡絲液包含幾丁聚醣之乳酸水溶液,其中幾丁聚醣與乳酸的濃度分別約為0.1-2.5 w/v%。上述成型液包含弱鹼之水溶液,弱鹼的濃度為0.1-2.5 w/v%。上述之弱鹼例如可為三(羥甲基)氨基甲烷(tris(hydroxymethyl) aminomethane;簡稱Tris base)。接著,讓紡絲液滴入成型液中,進行快速攪拌,讓紡絲液凝固成纖維,並讓纖維均勻地分佈在成型液中,形成幾丁聚醣纖維溶液。然後,讓幾丁聚醣纖維溶液進行成型乾燥的步驟,以形成纖維基材。According to one embodiment, the spinning solution and the molding liquid are separately prepared. The spinning solution comprises an aqueous solution of lactic acid of chitosan, wherein the concentration of chitosan and lactic acid is about 0.1-2.5 w/v%, respectively. The above molding liquid contains an aqueous solution of a weak base, and the concentration of the weak base is 0.1 to 2.5 w/v%. The above weak base may be, for example, tris(hydroxymethyl)aminomethane (referred to as Tris base). Next, the spinning is dropped into the molding liquid, and rapid stirring is carried out to solidify the spinning solution into fibers, and the fibers are uniformly distributed in the molding liquid to form a chitosan fiber solution. Then, the chitosan fiber solution is subjected to a step of molding drying to form a fibrous substrate.

依據另一實施方式,上述快速攪拌步驟需讓成型液之雷諾數為1.47×104 -1.176×105 ,讓幾丁聚醣可以形成直徑為10 μm以下的纖維。According to another embodiment, the rapid stirring step requires the Reynolds number of the molding liquid to be 1.47 × 10 4 - 1.176 × 10 5 to allow the chitosan to form fibers having a diameter of 10 μm or less.

因此,依據上述之實施方式,由於使用低濃度的弱酸與弱鹼,因此可解決習知濕紡/電紡的環保問題。又,讓含有幾丁聚醣纖維之成型液直接進行成型乾燥步驟,因此可簡化纖維基材的製程。Therefore, according to the above embodiment, since the low concentration of weak acid and weak base is used, the environmental problem of the conventional wet spinning/electrospinning can be solved. Further, since the molding liquid containing the chitosan fiber is directly subjected to the molding and drying step, the process of the fiber base material can be simplified.

上述發明內容旨在提供本揭示內容的簡化摘要,以使閱讀者對本揭示內容具備基本的理解。此發明內容並非本揭示內容的完整概述,且其用意並非在指出本發明實施例的重要/關鍵元件或界定本發明的範圍。在參閱下文實施方式後,本發明所屬技術領域中具有通常知識者當可輕易瞭解本發明之基本精神及其他發明目的,以及本發明所採用之技術手段與實施態樣。The Summary of the Invention is intended to provide a simplified summary of the present disclosure in order to provide a basic understanding of the disclosure. This Summary is not an extensive overview of the disclosure, and is not intended to be an The basic spirit and other objects of the present invention, as well as the technical means and implementations of the present invention, will be readily apparent to those skilled in the art of the invention.

依據上述,提供一種幾丁聚醣纖維基材的製備方法。此幾丁聚醣纖維基材的製備方法使用濃度的弱酸及弱鹼來得到直徑約1-10 μm的幾丁聚醣纖維。在下面的敘述中,將會介紹上述之幾丁聚醣纖維基材的例示製造方法。為了容易瞭解所述實施例之故,下面將會提供不少技術細節。當然,並不是所有的實施例皆需要這些技術細節。同時,一些廣為人知之結構或元件,僅會以示意的方式在圖式中繪出,以適當地簡化圖式內容。According to the above, a method for preparing a chitosan fiber substrate is provided. The method for preparing the chitosan fiber substrate uses a weak acid and a weak base to obtain chitosan fibers having a diameter of about 1-10 μm. In the following description, an exemplary manufacturing method of the chitosan fiber substrate described above will be described. In order to facilitate an understanding of the described embodiments, a number of technical details are provided below. Of course, not all embodiments require these technical details. At the same time, some well-known structures or elements are only shown in the drawings in a schematic manner to appropriately simplify the contents of the drawings.

幾丁聚醣纖維基材的製備方法Method for preparing chitosan fiber substrate

第1圖為依照本發明一實施方式之幾丁聚醣纖維基材的製備流程圖。在步驟110中,先製備紡絲液,紡絲液包含幾丁聚醣之乳酸水溶液。依照一實施方式,上述幾丁聚醣之乳酸水溶液的pH值需小於幾丁聚醣的等電點(pKa為6.0-6.5),以完全溶解幾丁聚醣。此外,幾丁聚醣的濃度需小於2.5 w/v%,以避免形成幾丁聚醣的凝膠,而無法進行後續形成纖維的步驟。因此,上述幾丁聚醣的濃度與乳酸的濃度分別約為0.1-2.5 w/v%。Fig. 1 is a flow chart showing the preparation of a chitosan fiber substrate according to an embodiment of the present invention. In step 110, a spinning solution is prepared, and the spinning solution contains an aqueous solution of lactic acid of chitosan. According to one embodiment, the pH of the lactic acid aqueous solution of the chitosan is less than the isoelectric point of chitosan (pKa is 6.0-6.5) to completely dissolve the chitosan. In addition, the concentration of chitosan needs to be less than 2.5 w/v% to avoid the formation of a gel of chitosan, and the subsequent step of forming fibers is not possible. Therefore, the concentration of the above chitosan and the concentration of lactic acid are respectively about 0.1 to 2.5 w/v%.

依照另一實施方式,上述紡絲液還可以包含至少一種功能成分,以增加最後所得纖維基材之功效。上述功能成分的添加量例如可為幾丁聚醣重量的25 wt%以下,以免影響幾丁聚醣纖維基材的穩定性及吸濕/保濕性。According to another embodiment, the above spinning solution may further comprise at least one functional ingredient to increase the efficacy of the resulting fibrous substrate. The amount of the above functional component added may be, for example, 25 wt% or less of the weight of chitosan, so as not to affect the stability and moisture absorption/moisture retention of the chitosan fiber substrate.

例如,若想增加最後所得纖維基材的結構穩定度,可以添加帶有酸根官能基的聚合物,與幾丁聚醣形成多電荷複合物(polyelectrolyte complex),以增加纖維基材結構的穩定度。上述帶有酸根官能基的聚合物例如可為羧甲基纖維素(carboxymethyl cellulose;CMC)、透明質酸(Hyaluronic Acid)或海藻酸鹽(alginate)。例如,若想增加最後所得纖維基材的韌性,可添加聚乙二醇。若想增加最後所得纖維基材的生理功效,例如可添加膠原蛋白(collagen)、明膠(gelatin)、凝血因子或生長因子。For example, if it is desired to increase the structural stability of the finally obtained fibrous substrate, a polymer having an acid functional group may be added to form a polyelectrolyte complex with chitosan to increase the stability of the fibrous substrate structure. . The above polymer having an acid functional group may be, for example, carboxymethyl cellulose (CMC), hyaluronic acid or alginate. For example, if it is desired to increase the toughness of the finally obtained fibrous substrate, polyethylene glycol may be added. If it is desired to increase the physiological efficacy of the finally obtained fibrous substrate, for example, collagen, gelatin, coagulation factor or growth factor may be added.

在步驟120中,製備成型液,成型液包含弱鹼之水溶液,其pH值約為9-12。為了幾丁聚醣在成型液中凝固所得外形是以直徑小於等於10 μm之纖維為主,弱鹼的濃度可為3.0 w/v%以下,例如可為0.1-2.5 w/v%。上述之弱鹼例如可為三(羥甲基)氨基甲烷或丙氨酸、氨、甲胺、吡啶、氨水、氫氧化鋁、氫氧化銅、氫氧化亞鐵、氫氧化鐵、氫氧化鋅等。In step 120, a molding fluid is prepared which comprises an aqueous solution of a weak base having a pH of about 9-12. The shape obtained by solidifying chitosan in the molding liquid is mainly composed of fibers having a diameter of 10 μm or less, and the concentration of the weak base may be 3.0 w/v% or less, for example, 0.1 to 2.5 w/v%. The weak base may be, for example, tris(hydroxymethyl)aminomethane or alanine, ammonia, methylamine, pyridine, aqueous ammonia, aluminum hydroxide, copper hydroxide, ferrous hydroxide, iron hydroxide, zinc hydroxide, or the like. .

在步驟130中,讓上述紡絲液滴入成型液中,並同時進行快速攪拌,紡絲液凝固成幾丁聚醣纖維,形成幾丁聚醣纖維溶液。在此步驟中,為了可以形成直徑在10 μm以下之幾丁聚醣纖維,必須要控制紡絲液之液滴大小以及成型液在攪拌時讓成型液所產生的剪應力(shear stress)來控制。In step 130, the spinning solution is dropped into a molding liquid and simultaneously stirred rapidly, and the spinning solution is solidified into chitosan fibers to form a chitosan fiber solution. In this step, in order to form a chitosan fiber having a diameter of 10 μm or less, it is necessary to control the droplet size of the spinning solution and the shear stress generated by the molding liquid when the molding liquid is stirred to control. .

上述紡絲液之液滴大小及流量速度可藉由讓紡絲液透過紡口大小及齒輪幫浦來提供穩定的液滴大小及流量,再滴入成型液中。上述紡口的孔徑可為1-100 μm,例如為約10 μm,齒輪幫浦的流量可為5-100 ml/min,例如為約20 ml/min。The droplet size and flow rate of the above-mentioned spinning solution can be supplied to the molding liquid by allowing the spinning solution to pass through the spun size and the gear pump to provide a stable droplet size and flow rate. The above-mentioned spun orifice may have a pore diameter of 1-100 μm, for example, about 10 μm, and the gear pump may have a flow rate of 5 to 100 ml/min, for example, about 20 ml/min.

控制攪拌時成型液所產生的剪應力是藉由攪拌裝置中之攪拌翼與攪拌槽的設計來達成,讓紡絲液的液滴在成型液中因為高剪應力的作用而被分散成微米等級之液滴並被拖曵成纖維狀。而攪拌過程中成型液所產生之剪應力與下式(1)中之雷諾數(NRe ;Reynolds number)相關:The shear stress generated by the molding liquid during the mixing is controlled by the design of the stirring blade and the stirring tank in the stirring device, so that the droplets of the spinning solution are dispersed into the micron level in the molding liquid due to the high shear stress. The droplets are dragged into a fibrous shape. The shear stress generated by the molding liquid during the stirring process is related to the Reynolds number (N Re ; Reynolds number) in the following formula (1):

雷諾數=慣性力/黏滯力=ρuD/μ (1)Reynolds number = inertial force / viscous force = ρuD / μ (1)

其中雷諾數定義中之ρ為流體的密度(單位kg/m3 ),流體的速度u常以攪拌翼之翼端速度nD代表,n攪拌翼的轉速(單位rps),D為攪拌翼的翼徑(單位m),μ為流體的黏度(單位kg/ms),雷諾數(符號NRe )將如下式(2)所示:Where ρ in the Reynolds number definition is the density of the fluid (in kg/m 3 ), the velocity u of the fluid is often represented by the wing end speed nD of the agitating wing, the rotational speed of the n agitating wing (in rps), and D is the wing of the agitating wing The diameter (in m), μ is the viscosity of the fluid (in kg/ms), and the Reynolds number (symbol N Re ) is as shown in the following equation (2):

NRe =ρnD2 /μ (2)N Re =ρnD 2 /μ (2)

由上式可知,成型液在攪拌槽中之雷諾數會隨著攪拌翼的幾何設計而變。在此需讓成型液產生高剪應力以將液滴分散成微米等級後並被拖曵成纖維型態,但是過高之剪應力將使由液滴分散所得之纖維在成型後破碎,因而導致結構分散。因此以成型液為水溶液的情況下,用水來估算流體的密度(1000 kg/m3 )與黏度(1.02×106 kg/ms)來計算較佳的雷諾數範圍。此外,依據式(2)也可依據攪拌翼的直徑來估算攪拌翼的轉速範圍應為多少。例如,若攪拌翼的直徑為0.03 m時,攪拌翼的轉速可為16.6-133.3 rps,亦即約1,000-8,000 rpm。It can be seen from the above formula that the Reynolds number of the molding liquid in the stirring tank varies with the geometric design of the stirring blade. Here, it is necessary to cause the molding liquid to generate high shear stress to disperse the droplets into micron grades and to be dragged into a fiber type, but too high shear stress will cause the fibers dispersed by the droplets to be broken after molding, thus resulting in The structure is scattered. Therefore, in the case where the molding liquid is an aqueous solution, the density (1000 kg/m 3 ) and viscosity (1.02 × 10 6 kg/ms) of the fluid are estimated by water to calculate a preferred Reynolds number range. In addition, according to the formula (2), the range of the rotational speed of the stirring wing should be estimated according to the diameter of the stirring wing. For example, if the diameter of the agitating wing is 0.03 m, the speed of the agitating blade may be 16.6-13.33 rps, that is, about 1,000-8,000 rpm.

此外,若考慮攪拌翼的消耗功率,希望能達成節省能源的目的,可以考慮使用高剪應攪拌翼。常見的高剪應攪拌翼例如有鋸齒邊緣修飾渦輪(sawtooth-edge modified turbine)、修飾渦輪(modified turbine)、直片葉輪(strait bald)、螺絲葉輪(screw impeller或auger impeller)、雙螺帶葉輪(double helical ribbon impeller)。In addition, considering the power consumption of the stirring wing, it is desirable to achieve energy saving, and it is conceivable to use a high shearing agitating wing. Common high shear agitating wings such as sawtooth-edge modified turbines, modified turbines, strait balds, screw impellers or auger impellers, double ribbon impellers (double spiral ribbon impeller).

步驟130的執行時間終點是以幾丁聚醣纖維溶液的酸鹼值來判斷的,也就是當紡絲液加入至成型液中的量讓最後幾丁聚醣纖維溶液的酸鹼值約為pH 7左右時,亦即pH 6.5-7.5時,則停止執行步驟130。此時若再加入幾丁聚醣紡絲液,由於幾丁聚醣纖維溶液的酸鹼值太低,小於其等電點而不足以讓紡絲液凝固成型,形成幾丁聚醣纖維。The end time of the execution time of step 130 is judged by the pH value of the chitosan fiber solution, that is, when the spinning solution is added to the molding liquid, the pH value of the last chitosan fiber solution is about pH. At about 7 or so, that is, at pH 6.5-7.5, step 130 is stopped. At this time, if the chitosan spinning solution is further added, the chitosan fiber is formed because the pH value of the chitosan fiber solution is too low, less than its isoelectric point, and is not enough for the spinning solution to solidify.

接著,進行步驟140,讓幾丁聚醣纖維溶液進行各種不同的成型乾燥步驟,以形成各種不同的纖維基材。舉例來說,當纖維基材的形式為海綿(sponge)、薄膜(thin film)、膠體(hydrocolloid)或水膠(hydrogel)時,可先讓幾丁聚醣纖維溶液注入至適當的模具中,接著以不同方式來乾燥模具中的幾丁聚醣纖維溶液。海綿的乾燥方式為冷凍乾燥,薄膜的乾燥方式為真空加熱乾燥,膠體的方式為熱風乾燥,水膠的方式為室溫乾燥。Next, step 140 is performed to allow the chitosan fiber solution to undergo various different molding drying steps to form a variety of different fibrous substrates. For example, when the fiber substrate is in the form of a sponge, a thin film, a hydrocolloid or a hydrogel, the chitosan fiber solution can be first injected into a suitable mold. The chitosan fiber solution in the mold is then dried in different ways. The drying method of the sponge is freeze-drying, the drying method of the film is vacuum heating and drying, the way of colloid is hot air drying, and the way of water gel is drying at room temperature.

由步驟140可知,由於在成型乾燥時,幾丁聚醣纖維已經分佈在幾丁聚醣纖維溶液中。所以在乾燥成型後,這些幾丁聚醣纖維都已經互相交錯纏雜在一起,也就不需要不織布的製程或化學交聯劑來穩定纖維基材的結構,同時具有可吸液/保濕功能之間隙空間。As can be seen from step 140, the chitosan fibers have been distributed in the chitosan fiber solution during molding drying. Therefore, after drying and forming, these chitosan fibers have been intertwined with each other, so that no non-woven process or chemical crosslinking agent is needed to stabilize the structure of the fiber substrate, and at the same time, it has a liquid absorbing/moisturizing function. Clearance space.

下文將提出一些幾丁聚醣纖維基材的實驗例,探討幾丁聚醣濃度、弱鹼濃度、攪拌速率以及各種功能成分濃度對幾丁聚醣纖維型態的影響。Experimental examples of chitosan fiber substrates will be presented below to investigate the effects of chitosan concentration, weak base concentration, stirring rate and concentration of various functional components on chitosan fiber type.

實驗例一:紡絲液中幾丁聚醣濃度對幾丁聚醣纖維型態的影響Experimental Example 1: Effect of Chitosan Concentration in Spinning Solution on Chitosan Fiber Type

幾丁聚醣分子量約為930,000,去乙醯度大於75%。紡絲液中幾丁聚醣及乳酸的濃度分別皆為0.1-2.5 w/v%,成型液為1 w/v%之三(羥甲基)氨基甲烷水溶液。攪拌翼直徑為3 cm,攪拌速率為4,000 rpm,形成幾丁聚醣纖維溶液。然後再取含2 w/v%之幾丁聚醣纖維溶液倒入模具中,進行冷凍乾燥,以得到海綿型態之纖維基材。The chitosan has a molecular weight of about 930,000 and a deacetylation degree of greater than 75%. The concentration of chitosan and lactic acid in the spinning solution were respectively 0.1-2.5 w/v%, and the molding liquid was a 1 w/v% aqueous solution of tris(hydroxymethyl)aminomethane. The agitating wing has a diameter of 3 cm and a stirring rate of 4,000 rpm to form a chitosan fiber solution. Then, a solution containing 2 w/v% of chitosan fiber was poured into a mold and freeze-dried to obtain a sponge-type fibrous substrate.

由結果可知,當幾丁聚醣濃度為0.1-2.5 w/v%時,濃度越大,幾丁聚醣纖維的直徑越粗,約為1-10 μm。而且在產物中,摻雜有少量片狀型態的結構,但是也隨著幾丁聚醣濃度的增加而增加。這些片狀型態的結構可以連接各纖維結構,增加纖維基材結構的強度與穩定度。From the results, it is understood that when the concentration of chitosan is 0.1-2.5 w/v%, the larger the concentration, the thicker the chitosan fiber is, about 1-10 μm. Moreover, in the product, a small amount of a sheet-like structure is doped, but it also increases as the concentration of chitosan increases. These sheet-like structures can join the fiber structures to increase the strength and stability of the fibrous substrate structure.

但是,當幾丁聚醣濃度大於3 w/v%時,產物結構則主要為片狀型態,只有少數為纖維型態可以互相交錯連接來穩定基材結構,而導致結構較不穩定,且易有片狀型態潰散出來。當幾丁聚醣濃度小於0.1 w/v%時,產物的結構主要為纖維型態。但是纖維微細使其強度受限,導致結構較不穩定而容易有細纖維絲分散出,同時也難在吸液後將液體保持在其結構中。However, when the concentration of chitosan is more than 3 w/v%, the structure of the product is mainly in the form of flakes, and only a few of the fiber types can be intertwined to stabilize the structure of the substrate, resulting in a relatively unstable structure, and It is easy to have a flaky pattern that collapses. When the chitosan concentration is less than 0.1 w/v%, the structure of the product is mainly a fiber type. However, the fineness of the fibers makes the strength limited, resulting in a structure which is relatively unstable and easily disperses the fine fiber filaments, and it is also difficult to maintain the liquid in its structure after the liquid absorption.

此外,結構中因微纖維與片狀型態互相交錯所形成的孔洞,可以提供基材吸液及保濕之能力,能使原先單一纖維型態的膨潤度由原來的1倍提升至10-15倍,可解決現有單一纖維型態其吸液及保濕性受限之問題。同樣,當幾丁聚醣濃度越大而使其結構中片狀型態越多時,將導致結構間的間隙減少,使其膨潤度也相對減低。In addition, the pores formed by the interdigitation of the microfibers and the sheet-like pattern in the structure can provide the ability of the substrate to absorb and moisturize the substrate, and the swelling degree of the original single fiber type can be increased from 1 to 10-15. It can solve the problem of limited absorption and moisture retention of the existing single fiber type. Similarly, when the concentration of chitosan is larger and the flaky form in the structure is increased, the gap between the structures is reduced, and the degree of swelling is also relatively reduced.

表一:紡絲液中幾丁聚醣濃度對幾丁聚醣纖維型態的影響。Table 1: Effect of chitosan concentration in spinning solution on chitosan fiber type.

*膨潤度的測量方法為浸在pH 7-7.4之生理實驗水中,計算方法為(纖維成型基材吸水後重-纖維成型基材原重)/纖維成型基材原重。* The method of measuring the degree of swelling is immersed in physiological test water of pH 7-7.4, and the calculation method is (the weight of the heavy-fiber-formed substrate after the fiber-formed substrate is absorbed) / the original weight of the fiber-formed substrate.

**結構穩定度的測量方法為浸在生理食鹽水中攪拌過夜。** Structural stability was measured by immersing in physiological saline overnight.

實驗例二:成型液中弱鹼濃度對幾丁聚醣纖維型態的影響Experimental Example 2: Effect of weak alkali concentration in molding solution on chitosan fiber type

幾丁聚醣波峰分子量(Mp)約為930,000,去乙醯度大於75%。紡絲液由1 w/v%幾丁聚醣溶解在1 w/v%之乳酸水溶液中所形成,成型液為濃度不等之Tris base水溶液。攪拌翼直徑為3 cm,攪拌速率為4000 rpm,形成幾丁聚醣纖維溶液。然後再取含2 w/v%之幾丁聚醣纖維溶液倒入模具中,再進行冷凍乾燥,以得到海綿型態之纖維基材。The chitosan peak molecular weight (Mp) is about 930,000 and the deacetylation degree is greater than 75%. The spinning solution was formed by dissolving 1 w/v% chitosan in a 1 w/v% aqueous lactic acid solution, and the molding liquid was an aqueous solution of Tris base having a unequal concentration. The agitating wing has a diameter of 3 cm and a stirring rate of 4000 rpm to form a chitosan fiber solution. Then, a solution containing 2 w/v% of chitosan fiber was poured into a mold, and then freeze-dried to obtain a sponge-type fibrous substrate.

由結果可知,Tris base濃度越大時,幾丁聚醣纖維的直徑越粗,約為1-10 μm。而且在產物中,摻雜有少量片狀型態的結構,但是也隨著Tris base濃度的增加而增加。From the results, it is understood that the larger the concentration of the Tris base, the thicker the chitosan fiber is, about 1-10 μm. Moreover, in the product, a small amount of a sheet-like structure is doped, but it also increases as the concentration of the Tris base increases.

當Tris base濃度大於3 w/v%時,產物結構主要為片狀型態,只有少數為纖維型態可以互相交錯連接來穩定基材結構,而導致結構較不穩定,且易有片狀型態潰散出來。由於Tris base的濃度越高,使溶液的pH值越高,使幾丁聚醣原帶正電荷的胺基(NH3 + )狀態轉變成未帶電荷之胺基(NH2 ),因此導致幾丁聚醣之液滴在尚未拉長前就直接析出形成片狀型態。When the concentration of Tris base is more than 3 w/v%, the structure of the product is mainly in the form of flakes, and only a few of the fiber types can be interlaced to stabilize the structure of the substrate, resulting in a structure that is unstable and easy to have a sheet shape. The state collapsed. The higher the concentration of the Tris base, the higher the pH of the solution, which converts the positively charged amine (NH 3 + ) state of chitosan into an uncharged amine group (NH 2 ), thus causing several The droplets of the chitosan are directly precipitated to form a sheet form before they have been elongated.

相反地,當Tris base濃度小於0.1 w/v%時,幾丁聚醣之原帶正電荷的胺基(NH3 + )被中和的速率較慢,而使得幾丁聚醣的析出速率較慢,因此液滴有充足的時間被拉長而形成纖維型態。但也如此,使得未能有足夠之片狀結構來穩定纖維基材的結構,而導致纖維基材的結構較不穩定,容易有細纖維絲分散出,也難保持液體在結構的間隙中。Conversely, when the Tris base concentration is less than 0.1 w/v%, the positively charged amine group (NH 3 + ) of chitosan is neutralized at a slower rate, resulting in a higher rate of chitosan precipitation. Slow, so the droplets have sufficient time to be elongated to form a fiber form. However, the same is true, so that there is not enough sheet structure to stabilize the structure of the fiber substrate, and the structure of the fiber substrate is unstable, the fine fiber filaments are easily dispersed, and it is difficult to keep the liquid in the gap of the structure.

此外,如前所述,由於微纖維與片狀型態互相交錯所形成的孔洞,因此能提供基材吸液及保濕之功能,使其具有10-16倍的膨潤度。然而當Tris base濃度越大時,片狀型態同樣導致結構間隙空間減少,膨潤度也相對降低。Further, as described above, since the microfibers and the sheet-like patterns are interlaced to form pores, it is possible to provide a function of absorbing and moisturizing the substrate to have a swelling degree of 10 to 16 times. However, when the concentration of the Tris base is larger, the sheet form also causes a decrease in the structure gap space and a relative decrease in the degree of swelling.

表二:成型液中弱鹼Tris base濃度對幾丁聚醣纖維型態的影響。Table 2: Effect of the concentration of weak base Tris base in the molding solution on the chitosan fiber type.

*膨潤度與結構穩定度的測量方法與表一相同。* The method of measuring the degree of swelling and structural stability is the same as in Table 1.

實驗例三:攪拌速率對幾丁聚醣纖維型態的影響Experimental Example 3: Effect of stirring rate on chitosan fiber type

幾丁聚醣波峰分子量(Mp)約為930,000,去乙醯度大於75%。紡絲液由1 w/v%幾丁聚醣溶解在1 w/v%之乳酸水溶液中所形成,成型液為1 w/v%之三(羥甲基)氨基甲烷(Tris base)水溶液。攪拌翼的直徑為3 cm,攪拌速率不等,形成幾丁聚醣纖維溶液。然後再取含2 w/v%之幾丁聚醣纖維溶液倒入模具中,再進行冷凍乾燥,以得到海綿型態之纖維基材。The chitosan peak molecular weight (Mp) is about 930,000 and the deacetylation degree is greater than 75%. The spinning solution was formed by dissolving 1 w/v% chitosan in a 1 w/v% aqueous solution of lactic acid, and the molding solution was a 1 w/v% aqueous solution of tris(hydroxymethyl)aminomethane (Tris base). The agitating wings have a diameter of 3 cm and the stirring rates are not equal, forming a chitosan fiber solution. Then, a solution containing 2 w/v% of chitosan fiber was poured into a mold, and then freeze-dried to obtain a sponge-type fibrous substrate.

表三:攪拌速率對幾丁聚醣纖維型態的影響。Table 3: Effect of stirring rate on chitosan fiber type.

*膨潤度與結構穩定度的測量方法與表一相同。* The method of measuring the degree of swelling and structural stability is the same as in Table 1.

由結果可知,在攪拌速率1,000-8,000 rpm下可得直徑範圍約為1-10 μm之纖維與片狀型態互相交錯之纖維基材,且其具有吸液及保濕能力10-15倍。然而,當攪拌速率越大時,液滴所受之剪應力越大,使得幾丁聚醣纖維的直徑越細且片狀型態的結構也隨之減少。From the results, it was found that a fiber substrate having a fiber-to-sheet shape interlaced with a diameter ranging from about 1 to 10 μm was obtained at a stirring rate of 1,000 to 8,000 rpm, and it had a liquid absorbing and moisturizing ability of 10 to 15 times. However, as the agitation rate is larger, the shear stress to which the droplets are subjected is increased, so that the diameter of the chitosan fibers is finer and the structure of the sheet form is also reduced.

當攪拌速率大於8,000 rpm時,產物為小纖維及小片狀型態。其因為攪拌所產生之拖曳剪應力過大,使所析出之微纖維及片狀型態因承受高剪應力之剪切作用而成。因此,進而影響基材的架構及穩定性,且使其吸液及保濕之功能受限。When the agitation rate is greater than 8,000 rpm, the product is in the form of small fibers and flakes. The drag shear stress generated by the agitation is too large, so that the precipitated microfibers and the sheet form are sheared by high shear stress. Therefore, the structure and stability of the substrate are further affected, and the functions of aspirating and moisturizing are limited.

當攪拌速率小於1,000 rpm時,產物結構主要為片狀型態。其因為攪拌所產生之拖曳剪應力較小,在幾丁聚醣微滴尚未變形拉長前,就已經析出成片狀型態。因此,其較佳之攪拌速率範圍為1,000-8,000 rpm,以水計算之其較佳雷諾數範圍為1.47×104 -1.176×105When the agitation rate is less than 1,000 rpm, the product structure is mainly in the form of a sheet. The drag shear stress generated by the agitation is small, and the chitosan droplets have been precipitated into a sheet form before they have been deformed and elongated. Therefore, its preferred agitation rate ranges from 1,000 to 8,000 rpm, and its preferred Reynolds number in water ranges from 1.47 x 10 4 to 1.176 x 10 5 .

實驗例四:幾丁聚醣/聚乙二醇複合纖維Experimental Example 4: Chitosan/polyethylene glycol composite fiber

幾丁聚醣波峰分子量(Mp)約為930,000,去乙醯度大於75%,而聚乙二醇之重量平均分子量(weight average molecular weight;Mw)約為4,000。在紡絲液中,幾丁聚醣與聚乙二醇之總濃度為1 w/v%,溶劑為1 w/v%之乳酸水溶液。成型液為1 w/v%之Tris base水溶液。攪拌翼之直徑為3 cm,攪拌速率為4,000 rpm,形成幾丁聚醣/聚乙二醇複合纖維溶液。然後再取含2 w/v%之幾丁聚醣/聚乙二醇複合纖維溶液倒入模具中,再進行冷凍乾燥,以得到海綿型態之複合纖維基材。The chitosan peak molecular weight (Mp) is about 930,000, the deacetylation degree is greater than 75%, and the weight average molecular weight (Mw) of the polyethylene glycol is about 4,000. In the spinning solution, the total concentration of chitosan and polyethylene glycol was 1 w/v%, and the solvent was 1 w/v% of an aqueous lactic acid solution. The molding solution was a 1 w/v% aqueous solution of Tris base. The agitating wing has a diameter of 3 cm and a stirring rate of 4,000 rpm to form a chitosan/polyethylene glycol composite fiber solution. Then, a chitosan/polyethylene glycol composite fiber solution containing 2 w/v% was poured into a mold, and then freeze-dried to obtain a sponge-type composite fiber substrate.

表四:幾丁聚醣/聚乙二醇複合纖維Table 4: Chitosan/polyethylene glycol composite fiber

*膨潤度與結構穩定度的測量方法與表一相同。* The method of measuring the degree of swelling and structural stability is the same as in Table 1.

由結果可知,當聚乙二醇/幾丁聚醣的比例為0.05-0.25時,聚乙二醇的比例越大,片狀型態的結構越多。雖然聚乙二醇可隨幾丁聚醣一起承受拖曳剪應力而一起變形拉長,但聚乙二醇無法在成型液中產生相變化而析出,仍以黏液形式複合於已產生相變化析出的幾丁聚醣中。因此在凍乾之後,才可產生聚乙二醇和幾丁聚醣之複合纖維基材。From the results, it is understood that when the ratio of polyethylene glycol/chitosan is 0.05-0.25, the larger the proportion of polyethylene glycol, the more the structure of the sheet form. Although polyethylene glycol can be deformed and elongated together with the chitosan along with the drag shear stress, polyethylene glycol cannot precipitate in the molding liquid to form a phase change, and is still compounded in the form of mucus to the phase change precipitated. In chitosan. Therefore, after lyophilization, a composite fiber substrate of polyethylene glycol and chitosan can be produced.

加入聚乙二醇能使幾丁聚醣纖維基材的膨潤度提升,由原來之約15倍提升至約24倍,其因為聚乙二醇比幾丁聚醣具有更好之親水性及吸液性。但是,當聚乙二醇所添加的比例越大時,其片狀型態結構也隨之增多,可提供吸收液體之纖維結構間的間隙減少,因此使其膨潤度也跟著減少。此外,當結構主要為片狀型態時,因其無法利用纖維間交錯的構型來穩定基材結構,使其結構較不穩定而容易潰散。The addition of polyethylene glycol can increase the swelling degree of the chitosan fiber substrate, from about 15 times to about 24 times, because polyethylene glycol has better hydrophilicity and absorption than chitosan. Liquid. However, when the proportion of polyethylene glycol added is increased, the sheet-like structure is also increased, and the gap between the fiber structures absorbing liquid can be reduced, so that the degree of swelling is also reduced. In addition, when the structure is mainly in the form of a sheet, it is impossible to stabilize the structure of the substrate by the staggered configuration between the fibers, so that the structure is unstable and easily collapsed.

實驗例五:幾丁聚醣/膠原蛋白複合纖維Experimental Example 5: Chitosan/collagen composite fiber

幾丁聚醣波峰分子量(Mp)約為930,000,去乙醯度大於75%,而來自魚鱗的膠原蛋白之重量平均分子量(Mw)大於180,000。在紡絲液中,幾丁聚醣與膠原蛋白之總濃度為1 w/v%,溶劑為1 w/v%之乳酸水溶液。成型液為1 w/v%之Tris base水溶液。攪拌速率為4,000 rpm,形成幾丁聚醣/膠原蛋白複合纖維溶液。然後再取含2 w/v%幾丁聚醣/膠原蛋白的複合纖維溶液倒入模具中,再進行冷凍乾燥,以得到海綿型態之複合纖維基材。The chitosan peak molecular weight (Mp) is about 930,000, the deacetylation degree is greater than 75%, and the weight average molecular weight (Mw) of the collagen from the fish scale is greater than 180,000. In the spinning solution, the total concentration of chitosan and collagen was 1 w/v%, and the solvent was 1 w/v% of an aqueous lactic acid solution. The molding solution was a 1 w/v% aqueous solution of Tris base. The stirring rate was 4,000 rpm to form a chitosan/collagen composite fiber solution. Then, a composite fiber solution containing 2 w/v% chitosan/collagen was poured into a mold, and then freeze-dried to obtain a sponge-type composite fiber substrate.

由結果可知,在酸性複合液環境下,魚鱗膠原蛋白雖為電中性,但其分子鏈上帶負電荷的自由羧基(-COO- )可與幾丁聚醣上帶正電荷的自由胺基(-NH3+ )靜電相吸,使魚鱗膠原蛋白可隨幾丁聚醣一起承受拖曳剪應力而一起變形拉長析出。再依乾燥脫水的程度,形成醯胺鍵(可在紅外線(IR)振動光譜中偵測到),增加基材結構的穩定性,使其所含片狀型態的結構僅微幅漸增。It can be seen from the results that although the fish scale collagen is electrically neutral in the acidic composite liquid environment, the negatively charged free carboxyl group (-COO - ) on the molecular chain and the positively charged free amine group on chitosan. (-NH 3+ ) electrostatically attracts, so that the fish scale collagen can undergo deformation and elongation with the chitosan together with the drag shear stress. Further, according to the degree of dry dehydration, a guanamine bond (which can be detected in the infrared (IR) vibrational spectrum) is formed, and the stability of the substrate structure is increased, so that the structure of the flaky form is only slightly increased.

當膠原蛋白/幾丁聚醣比例為0.05-0.25時,加入魚鱗膠原蛋白可使幾丁聚醣纖維基材的膨潤度提升至約30倍。然而,當魚鱗膠原蛋白與幾丁聚醣的比例為0.25時,其膨潤度卻略微下降。其因可能是魚鱗膠原蛋白與幾丁聚醣進行靜電複合的官能基數目有限,且魚鱗膠原蛋白為水溶性,部分的魚鱗膠原蛋白會被成型液溶解而流失,使其膨潤度略微下降。When the collagen/chitosan ratio is 0.05-0.25, the addition of fish scale collagen can increase the degree of swelling of the chitosan fiber substrate to about 30 times. However, when the ratio of fish scale collagen to chitosan was 0.25, the degree of swelling decreased slightly. The number of functional groups which may be electrostatically complexed with fish scale collagen and chitosan is limited, and the fish scale collagen is water-soluble, and some of the fish scale collagen is dissolved and lost by the molding liquid, so that the degree of swelling is slightly decreased.

表五:幾丁聚醣/膠原蛋白複合纖維Table 5: Chitosan/collagen composite fiber

*醯胺鍵可由IR振動光譜測定,醯胺鍵的振動約在1550,1660 cm-1 左右。* The guanamine bond can be determined by IR vibration spectroscopy, and the vibration of the guanamine bond is about 1550, 1660 cm -1 .

**膨潤度與結構穩定度的測量方法與表一相同。** The method of measuring the degree of swelling and structural stability is the same as in Table 1.

實驗例六:幾丁聚醣/透明質酸複合纖維Experimental Example 6: Chitosan/hyaluronic acid composite fiber

幾丁聚醣波峰分子量(Mp)約為930,000,去乙醯度大於75%,而透明質酸(Hyaluronic Acid)之重量平均分子量(Mw)大於300,000。在紡絲液中,幾丁聚醣與透明質酸之總濃度為1 w/v%,溶劑為1 w/v%之乳酸水溶液。成型液為1 w/v%之Tris base水溶液。攪拌翼直徑為3 cm,攪拌速率為4,000 rpm,形成幾丁聚醣/透明質酸複合纖維溶液。然後再取含2 w/v%幾丁聚醣/透明質酸的複合纖維溶液倒入模具中,再進行冷凍乾燥,以得到海綿型態之複合纖維基材。The chitosan peak molecular weight (Mp) is about 930,000, the deacetylation degree is greater than 75%, and the weight average molecular weight (Mw) of hyaluronic acid is greater than 300,000. In the spinning solution, the total concentration of chitosan and hyaluronic acid was 1 w/v%, and the solvent was 1 w/v% of an aqueous lactic acid solution. The molding solution was a 1 w/v% aqueous solution of Tris base. The agitating wing has a diameter of 3 cm and a stirring rate of 4,000 rpm to form a chitosan/hyaluronic acid composite fiber solution. Then, a composite fiber solution containing 2 w/v% chitosan/hyaluronic acid was poured into a mold, followed by freeze-drying to obtain a sponge-type composite fiber substrate.

由結果可知,由於幾丁聚醣上具有的自由胺基(-NH2 )可與透明質酸之自由羧酸基(-COOH)進行離子複合,透明質酸與幾丁聚醣可一起承受拖曳剪應力而一起變形拉長析出。再依乾燥脫水的程度,形成醯胺鍵(可在紅外線(IR)振動光譜中偵測到),而增加基材結構的穩定性,也使其片狀型態結構僅微幅漸增。From the results, it can be seen that since the free amine group (-NH 2 ) on the chitosan can be ion-complexed with the free carboxylic acid group (-COOH) of hyaluronic acid, hyaluronic acid and chitosan can be towed together. The shear stress is deformed together and elongated. Further, according to the degree of dry dehydration, a guanamine bond (which can be detected in the infrared (IR) vibrational spectrum) is formed, and the stability of the substrate structure is increased, and the sheet-like structure is only slightly increased.

在透明質酸與幾丁聚醣比例為0.05-0.25範圍下,基材的膨潤度隨透明質酸的增加而遞增至約33倍。然而當透明質酸/幾丁聚醣的比例增加至0.5時,透明質酸和幾丁聚醣會快速進行離子複合,而形成凝膠而沉澱析出,導致複合液無法具有流動性而無法製造出纖維基材。In the range of hyaluronic acid to chitosan ranging from 0.05 to 0.25, the degree of swelling of the substrate increases to about 33 times as the hyaluronic acid increases. However, when the proportion of hyaluronic acid/chitosan is increased to 0.5, hyaluronic acid and chitosan rapidly undergo ion-complexation, forming a gel and precipitating, resulting in the fluid not being able to be produced and being unable to be produced. Fiber substrate.

表六:幾丁聚醣/透明質酸複合纖維Table 6: Chitosan/hyaluronic acid composite fiber

*醯胺鍵可由IR振動光譜測定,醯胺鍵的振動約在1640 cm-1 左右。* The guanamine bond can be determined by IR vibration spectroscopy, and the vibration of the guanamine bond is about 1640 cm -1 .

**膨潤度與結構穩定度的測量方法與表一相同。** The method of measuring the degree of swelling and structural stability is the same as in Table 1.

實驗例七:幾丁聚醣/羧甲基纖維素複合纖維Experimental Example 7: Chitosan/Carboxymethyl Cellulose Composite Fiber

幾丁聚醣波峰分子量(Mp)約為930,000,去乙醯度大於75%,而羧甲基纖維素(carboxymethyl cellulose;CMC)之羧甲基取代度大於0.8。在紡絲液中,幾丁聚醣與羧甲基纖維素之總濃度為1 w/v%,溶劑為1 w/v%之乳酸水溶液。成型液為1 w/v%之Tris base水溶液,攪拌速率為4,000 rpm,形成幾丁聚醣/羧甲基纖維素複合纖維溶液。然後再取含2 w/v%幾丁聚醣/羧甲基纖維素的複合纖維溶液倒入模具中,再進行冷凍乾燥,以得到海綿型態之複合纖維基材。The chitosan peak molecular weight (Mp) is about 930,000, the deacetylation degree is more than 75%, and the carboxymethyl cellulose (CMC) has a carboxymethyl substitution degree of more than 0.8. In the spinning solution, the total concentration of chitosan and carboxymethylcellulose was 1 w/v%, and the solvent was 1 w/v% of an aqueous lactic acid solution. The molding solution was a 1 w/v% Tris base aqueous solution at a stirring rate of 4,000 rpm to form a chitosan/carboxymethylcellulose composite fiber solution. Then, a composite fiber solution containing 2 w/v% chitosan/carboxymethylcellulose was poured into a mold, followed by freeze-drying to obtain a sponge-type composite fiber substrate.

由結果可知,相似於透明質酸材料,幾丁聚醣具有自由胺基(-NH2 )會與羧甲基纖維素上的自由羧酸基(-COOH)會進行離子複合,而可隨幾丁聚醣一起承受拖曳剪應力而一起變形拉長析出。再依乾燥脫水的程度,有些進一步形成醯胺鍵(可在紅外線振動光譜中偵測到),使其片狀型態結構僅微幅漸增。As can be seen from the results, similar to hyaluronic acid materials, chitosan has a free amine group (-NH 2 ) which will be ion-complexed with a free carboxylic acid group (-COOH) on carboxymethyl cellulose. The chitosan is subjected to the towing shear stress together and deformed together to form an elongated precipitate. According to the degree of dry dehydration, some further form a guanamine bond (which can be detected in the infrared vibration spectrum), and the sheet-like structure is only slightly increased.

同樣,羧甲基纖維素可使幾丁聚醣的膨潤度增加至約25倍,然而當其比例在範圍0.05-0.25時,其膨潤度變化不大。其可能因羧甲基纖維素與幾丁聚醣可進行靜電複合的官能基數目有限。也可能因為羧甲基纖維素為水溶性且其分子量低,使其溶解度較高,導致部分未與幾丁聚醣離子複合的成分較易溶解在成型液中而流失。因此,羧甲基纖維素的濃度對膨潤度的影響不大。Similarly, carboxymethyl cellulose increases the degree of swelling of chitosan to about 25 times, whereas when the ratio is in the range of 0.05-0.25, the degree of swelling does not change much. It may have a limited number of functional groups that can be electrostatically complexed with carboxymethyl cellulose and chitosan. It is also possible that carboxymethylcellulose is water-soluble and has a low molecular weight, so that its solubility is high, and some components which are not combined with chitosan ions are more easily dissolved in the molding liquid and are lost. Therefore, the concentration of carboxymethylcellulose has little effect on the degree of swelling.

表七:幾丁聚醣/羧甲基纖維素複合纖維Table 7: Chitosan/carboxymethyl cellulose composite fiber

*醯胺鍵可由IR振動光譜測定,醯胺鍵的振動約在1550,1660 cm-1 左右。* The guanamine bond can be determined by IR vibration spectroscopy, and the vibration of the guanamine bond is about 1550, 1660 cm -1 .

**膨潤度與結構穩定度的測量方法與表一相同。** The method of measuring the degree of swelling and structural stability is the same as in Table 1.

由上述本發明實施方式可知,不僅利用低濃度的弱酸弱鹼來形成幾丁聚醣的纖維,且利用攪拌所產生的剪應力讓幾丁聚醣的紡絲液在成型液中直接凝固成纖維。並且在纖維結構中摻有少量的片狀結構,這些片狀結構可以連接各纖維結構,增加纖維基材結構的強度與穩定度。接著,讓幾丁聚醣纖維直接進行各種成型乾燥的步驟,形成各種不同型式的纖維基材。因此,應用上述本發明之實施方式,不僅可解決習知方法的環保問題,且可以省略不織布製程,而大幅簡化習知纖維基材的製備方法。It can be seen from the above embodiments of the present invention that not only the low-concentration weak acid weak base is used to form the chitosan fiber, but also the shearing stress generated by the stirring causes the spinning solution of the chitosan to directly solidify into the fiber in the molding liquid. . And the fiber structure is doped with a small amount of sheet-like structure, which can connect the fiber structures to increase the strength and stability of the fiber substrate structure. Next, the chitosan fibers are directly subjected to various steps of molding drying to form various types of fiber substrates. Therefore, the application of the above-described embodiments of the present invention not only solves the environmental problems of the conventional method, but also omits the non-woven process, and greatly simplifies the preparation method of the conventional fiber substrate.

此外,所得之纖維基材之膨潤度高達10-35倍,又可添加各種功能成分。因此,可以廣泛地應用在醫藥領域之止血材、創傷敷材、組織工程基材或活性物質之控制釋放基材上。Further, the obtained fibrous base material has a degree of swelling of 10 to 35 times, and various functional ingredients can be added. Therefore, it can be widely applied to a hemostatic material, a wound dressing, a tissue engineering substrate or a controlled release substrate of an active material in the medical field.

雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

110、120、130、140...步驟110, 120, 130, 140. . . step

為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂,所附圖式之說明如下:The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.

第1圖為依照本發明一實施方式之幾丁聚醣纖維基材的製備流程圖。Fig. 1 is a flow chart showing the preparation of a chitosan fiber substrate according to an embodiment of the present invention.

110、120、130、140...步驟110, 120, 130, 140. . . step

Claims (10)

一種幾丁聚醣纖維基材的製備方法,該製備方法包含:製備一紡絲液,該紡絲液包含幾丁聚醣乳酸水溶液,該幾丁聚醣與該乳酸的濃度分別為0.1-2.5w/v%;製備一成型液,該成型液包含一弱鹼之水溶液,該弱鹼的濃度為0.1-2.5w/v%;讓該紡絲液滴入該成型液中,進行快速攪拌以讓該紡絲液凝固成纖維,並讓該些纖維均勻地分佈在該成型液中,形成幾丁聚醣纖維溶液;以及讓該幾丁聚醣纖維溶液進行成型乾燥的步驟,以形成一纖維基材。 A preparation method of a chitosan fiber substrate, the preparation method comprising: preparing a spinning solution, the spinning solution comprising an aqueous solution of chitosan lactic acid, the concentration of the chitosan and the lactic acid being 0.1-2.5 respectively w/v%; preparing a molding liquid, the molding liquid comprises an aqueous solution of a weak base having a concentration of 0.1-2.5 w/v%; allowing the spinning to be dropped into the molding liquid, and rapidly stirring Allowing the spinning solution to solidify into fibers, and uniformly distributing the fibers in the molding liquid to form a chitosan fiber solution; and subjecting the chitosan fiber solution to a shape drying step to form a fiber Substrate. 如請求項1所述之幾丁聚醣纖維基材的製備方法,其中該紡絲液更包含一功能性成分,該功能性成分為透明質酸、羧甲基纖維素、海藻酸鹽、聚乙二醇、膠原蛋白或明膠。 The method for preparing a chitosan fiber substrate according to claim 1, wherein the spinning solution further comprises a functional component, which is hyaluronic acid, carboxymethyl cellulose, alginate, poly Ethylene glycol, collagen or gelatin. 如請求項1所述之幾丁聚醣纖維基材的製備方法,其中該快速攪拌讓該成型液之雷諾數為1.47×104 -1.176×105The method for producing a chitosan fiber substrate according to claim 1, wherein the rapid stirring causes the Reynolds number of the molding liquid to be 1.47 × 10 4 - 1.176 × 10 5 . 如請求項1所述之幾丁聚醣纖維基材的製備方法,其中該弱鹼包含三(羥甲基)氨基甲烷。 The method for producing a chitosan fiber substrate according to claim 1, wherein the weak base comprises tris(hydroxymethyl)aminomethane. 一種幾丁聚醣纖維基材,其係使用如請求項1-4任一項方法所製備。 A chitosan fiber substrate prepared by the method of any one of claims 1-4. 如請求項5所述之幾丁聚醣纖維基材,其中該些纖維之直徑10μm以下。 The chitosan fiber substrate according to claim 5, wherein the fibers have a diameter of 10 μm or less. 如請求項5所述之幾丁聚醣纖維基材,其中該幾丁聚醣纖維基材的型式為海綿、膠體、水膠或上述之任意結合。 The chitosan fiber substrate according to claim 5, wherein the chitosan fiber substrate is in the form of a sponge, a gel, a water gel or any combination thereof. 如請求項7所述之幾丁聚醣纖維基材,其中該海綿基材的膨潤度為10-35倍。 The chitosan fiber substrate according to claim 7, wherein the sponge substrate has a degree of swelling of 10-35 times. 一種醫藥基材,其使用包含如請求項5-8中任一項所述之該幾丁聚醣纖維基材所製成。 A pharmaceutical substrate made using the chitosan fiber substrate of any one of claims 5-8. 如請求項9所述之醫藥基材,其係為止血材、創傷敷材、組織工程基材或活性物質之控制釋放基材。 The medical substrate according to claim 9, which is a controlled release substrate of a blood material, a wound dressing, a tissue engineering substrate or an active material.
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