JP2013001876A - Chitosan-iodine complex film producing method, and bactericidal chitosan-iodine complex film or the like - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bactericide having high bactericidal properties with reduced iodine content, unlike conventional chitosan-iodine complexes that require a large amount of iodine to achieve high bactericidal properties.SOLUTION: As a means for solving the issue, a chitosan-iodine complex film producing method and a bactericidal chitosan-iodine complex film are proposed in which the chitosan-iodine complex film producing method includes a chitosan film preparing step of preparing a chitosan film, and a chitosan-iodine complex film producing step of reacting the prepared chitosan film with iodine to produce a chitosan-iodine complex film.

Description

  The present invention relates to a method for producing a chitosan-iodine complex film and a bactericidal chitosan-iodine complex film.

  Iodine has a strong bactericidal action and has been used as a bactericidal agent for a long time, but it is highly irritating and corrosive when used alone. For this reason, iodine is often supported on a polymer and a surfactant to form a composite, which is often used while suppressing irritation and corrosivity. Povidone iodine is widely used as a complex in which iodine is supported on a polymer.

  Povidone iodine is a complex of water-soluble polymer polyvinylpyrrolidone and iodine. It is a disinfectant that dissolves in water at a high concentration and suppresses irritation, corrosivity, and volatility of iodine. And generally used in the field of food hygiene and the like. The method for producing povidone iodine is described in Patent Document 1, for example.

  On the other hand, chitosan is a substance obtained by deacetylating chitin obtained by removing proteins and inorganic salts from shells such as crustaceans with concentrated alkali. Chitosan has a property of forming a complex with iodine, and is used as an iodophor as disclosed in Patent Document 2. In Patent Document 3, an alkylammonium chitosan-iodine complex is disclosed as a bactericidal composition comprising chitosan and iodine.

US Pat. No. 2,739,922 Japanese Patent Publication No. 60-19762 JP 2002-88101 A

  However, the bactericidal action of popidone iodine is due to active iodine, and iodine, which is an active ingredient, exhibits an immediate bactericidal property at a low concentration, but often lacks the sustainability of bactericidal power. In addition, when a large amount of organic matter is present, iodine is deactivated, so that sufficient bactericidal properties may not be ensured. Furthermore, polyvinyl pyrrolidone used as a carrier has no bactericidal action, and since it is a synthetic polymer, it does not have biodegradability and remains undegraded in the environment.

  In addition to polyvinyl pyrrolidone, polyether glycol, polyvinyl alcohol, polyacrylic acid, polyamide, polyoxyalkylene, and the like are known as substances carrying iodine, but none of them has bactericidal performance comparable to popidone iodine. The field of use is limited.

  In addition, the conventional chitosan-iodine complex as disclosed in Patent Documents 2 and 3, etc., requires a large amount of iodine in order to exhibit high antibacterial properties, and has a high economic cost. Moreover, in order to produce | generate a composite_body | complex, it was necessary to perform many processes and many time costs were also required. Therefore, there has been a demand for a simple method for producing an antibacterial agent that exhibits high antibacterial properties with a small amount of iodine.

  As means for solving the above-mentioned problems, a chitosan film preparation step for preparing a chitosan film, a chitosan-iodine composite film generation step for generating a chitosan-iodine composite film by reacting the prepared chitosan film with iodine, and A chitosan-iodine complex film production method and a chitosan-iodine complex film production method are proposed.

  The chitosan-iodine composite film produced by the production method of the present invention can obtain high antibacterial properties with a small amount of iodine, and can be used as a solid antibacterial material that is environmentally friendly and has good biocompatibility.

The figure which shows the flow of a process of a chitosan-iodine composite film production method The figure which shows an example of the flow of a process of a chitosan film preparation step The figure which shows UV / Vis spectra, such as a chitosan-iodine composite film

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In addition, this invention should not be limited to the said embodiment at all, and can be implemented with a various aspect in the range which does not deviate from the summary.

<Method for producing chitosan-iodine composite film>
As shown in FIG. 1, the chitosan-iodine complex film production method includes a chitosan film preparation step (S0101) and a chitosan-iodine complex film production step (S0102). Hereinafter, each step will be described.

(Chitosan film preparation step)
In the chitosan film preparation step, a chitosan film is prepared. For example, as shown in FIG. 2, the chitosan film is prepared by dissolving solid chitosan in an organic acid aqueous solution to generate a chitosan solution (chitosan solution generation step), and generating a chitosan film from the generated chitosan solution (chitosan film generation). Step). However, when a chitosan film in a pre-generated state exists, it is not necessary to perform these steps.

  The organic acid aqueous solution for dissolving the solid chitosan is mainly an acetic acid aqueous solution, but a lactic acid aqueous solution, an ascorbic acid aqueous solution, a citric acid aqueous solution, a glutamic acid aqueous solution, or the like can also be used, and is not particularly limited.

  In the chitosan film production step, for example, the produced chitosan solution is heated and dried to produce a chitosan film (heat drying step). Here, the heating temperature is preferably about 90 to 120 ° C., and the heating time is preferably about 12 to 36 hours.

(Chitosan-iodine complex film production step)
In the chitosan-iodine complex film production step, the prepared chitosan film is reacted with iodine to produce a chitosan-iodine complex film.

  In the chitosan-iodine complex film production step, for example, the dried chitosan film produced in the chitosan film production step is reacted with iodine (drying reaction step). Here, it is preferable that the iodine reacted with the chitosan film is in a vapor state from the viewpoint of efficiently adsorbing the chitosan film. In addition, it is preferable that the reaction temperature of a chitosan film and iodine shall be about 30-50 degreeC, and reaction time shall be about 12-36 hours. Moreover, it is preferable to carry out in sealed space so that an iodine may not leak outside during reaction.

  In the above composite production method, a chitosan fiber sheet or a chitin fiber sheet may be used instead of the chitosan film. In this case, a chitosan fiber-iodine composite sheet or a chitin fiber-iodine composite sheet is produced.

  That is, the chitosan fiber iodine composite sheet is a chitosan fiber preparation step in which chitosan fiber is prepared, and a chitosan fiber-iodine composite sheet is produced by reacting the prepared chitosan fiber with iodine to produce a chitosan fiber-iodine composite sheet. Steps.

  The chitin fiber-iodine composite sheet includes a chitin fiber preparation step for preparing a chitin fiber, and a chitin fiber-iodine composite sheet for generating a chitin fiber-iodine composite sheet by reacting the prepared chitin fiber with iodine. Generating step.

  The chitosan fiber and chitin fiber may be those manufactured by a conventional manufacturing method. In addition, the step of producing a composite sheet by reacting these substances with iodine is the same as the case of producing a composite film by reacting a chitosan film with iodine, and thus the description thereof is omitted.

<Chitosan-iodine composite film, etc.>
The chitosan-iodine composite film of this embodiment can be produced by a simple method as described above. While chitosan and iodine no reason clear to form a stable complex, chitosan backbone and the active iodine (I ₂ and I ₃ ^- · I ^-, etc.) interact strongly, since forming the complexes It is thought that.

  As described above, chitosan having antibacterial properties as an iodine carrier does not exhibit a strong bactericidal action like iodine, but has a continuous bactericidal action even in the presence of organic substances. That is, the growth of bacteria can be suppressed over a long period of time even in the presence of an organic substance that cannot be expected to be immediately sterilized by iodine.

  Thus, the chitosan-iodine complex film of this embodiment exhibits a synergistic bactericidal activity between chitosan and iodine. Moreover, since chitosan is a derivative derived from a natural product and biodegradable, the chitosan-iodine composite film is an environmentally friendly substance.

  Moreover, it becomes easy to utilize as a skin contact layer of a wound dressing material by making it into a film or a sheet form. For example, it becomes possible to exert a more lasting effect on the affected area than in liquid form. Further, since the thickness is small, the flexibility is excellent and the contact area with the affected part is increased.

  As shown in the following examples, the effective iodine amount of the chitosan-iodine complex film of the present embodiment increases as the temperature rises. This is thought to be due to the increase in the amount of active iodine immobilized on the chitosan skeleton depending on the temperature as the chitosan and iodine are combined.

  Moreover, the chitosan-iodine composite film, the chitosan fiber-iodine composite sheet, and the chitin fiber-iodine composite sheet exhibit high antibacterial properties even with a small amount of iodine, as shown in the following examples.

  Furthermore, since chitosan and chitin are derivatives derived from natural products and biodegradable, the chitosan-iodine composite film, chitosan fiber-iodine composite sheet, and chitin fiber-iodine composite sheet of this embodiment are environmentally friendly. Is also kind.

  The chitosan-iodine composite film, chitosan fiber-iodine composite sheet, and chitin fiber-iodine composite sheet can be used as substances intended for sterilization and antibacterial purposes. For example, it can be used as an antibacterial film / sheet for an object in addition to a sterilizing film / sheet for a living body.

<Effect>
The bactericidal chitosan-iodine complex film produced by the chitosan-iodine complex film production method produced by the production method of the present invention can obtain high antibacterial properties with a small amount of iodine, and is environmentally friendly It can be used as a solid antibacterial material with good affinity.

(Generation Example 1)
First, 0.5 g of chitosan (Koyo Chemical Chitosan DDA100) was added and dissolved in an acetic acid aqueous solution (acetic acid 1 ml, ion-exchanged water 297.5 ml). Next, 100 ml of the chitosan solution was transferred to a fluororesin container and dried at 105 ° C. for 24 hours to produce a chitosan film. Further, the produced chitosan film was reacted with vapor iodine in a saturated vapor atmosphere for 24 hours at 40 ° C. to produce a chitosan-iodine composite film.

(Analysis example 1)
The chitosan-iodine composite film obtained above was measured for UV / Vis spectrum (ultraviolet / visible spectrum) and effective iodine amount. Regarding the UV / Vis spectrum, a chitosan film was also measured as a control. FIG. 3 is a diagram showing UV / Vis spectra of a chitosan-iodine composite film and a chitosan film.

  From the result of FIG. 3, the absorption (290 nm, 360 nm vicinity) resulting from an iodine was confirmed in the chitosan-iodine composite film. Moreover, the purple coloration in the film was also confirmed by observation. Since such absorption and coloration are indicators of complex formation between chitosan and iodine, it was confirmed that a chitosan-iodine complex was produced.

Effective iodine content was quantified using UV-Vis. Specifically, UV-Vis is measured for each dilution of a hexane-iodine solution having a known concentration to obtain a maximum absorption value of iodine (I ₂ ) that appears in the vicinity of 521 nm. Further, the chitosan-iodine complex film is crushed and dissolved with a hydrochloric acid solution, and then iodine is extracted with hexane to measure UV-Vis to obtain a maximum absorption value of 521 nm. Both values are plotted, and a calibration curve for the effective iodine amount and a conversion formula for the effective iodine amount are obtained. The effective iodine amount was calculated by applying the UV-Vis absorbance at 521 nm of the chitosan-iodine complex film to the conversion formula for the effective iodine amount obtained from the calibration curve. The results are shown in Table 1.

As Table 1 shows, it was confirmed that the effective iodine amount in a chitosan-iodine composite film increases as the reaction temperature increases. This is considered to be due to a temperature-dependent increase in I ₂ and I ₃ ⁻ · I ⁻ fixed to the chitosan skeleton with the combination of chitosan and iodine.

  (Storage stability test) The chitosan-iodine composite film was allowed to stand at room temperature, and the amount of effective iodine was quantified over time by the method shown in Analysis Example 1. The effective iodine amount of the chitosan-iodine composite film was stabilized 5 days after standing. Further, the chitosan-iodine composite film was visually discolored due to volatilization of iodine, but was stable in a color different from that of the chitosan film.

Table 2 shows the amount of iodine adsorbed per unit weight with respect to the chitosan film, chitosan fiber sheet, and chitin fiber sheet. From this result, the iodine adsorption amount per unit weight of the chitosan film was less than that of the chitosan fiber sheet and the chitin fiber sheet. This is thought to be the difference in the number of iodine adsorption sites due to the difference in surface area.

(Evaluation of bactericidal properties) A 20 mg chitosan-iodine complex film was immersed in a PBS solution containing about 1 × 10 ⁷ cells / ml of E. coli, and the bactericidal rate of E. coli after 4 days was calculated by the plate dilution agar method. .

  Table 3 shows the results of the bactericidal rate for the chitosan-iodine composite, chitosan film, chitosan fiber iodine composite sheet, chitosan fiber sheet, chitin fiber-iodine composite sheet, and chitin fiber sheet. In addition, since the surface area of the chitosan fiber iodine composite sheet and the chitosan fiber sheet is larger than that of other materials, it is set to 2 mg.

  From this result, it was found that the chitosan-iodine complex has a high bactericidal rate. In other words, chitosan-iodine composite film can obtain high antibacterial properties with a small amount of iodine compared to conventional solid antibacterial agents, and is superior as a solid antibacterial material that is environmentally friendly and has good biocompatibility Was found.

Moreover, it was shown that chitosan fiber-iodine composite sheet and chitin fiber-iodine composite sheet also have high antibacterial properties. These substances can also have high antibacterial properties with a small amount of iodine compared to conventional solid antibacterial agents, and, like chitosan-iodine complex films, are solid antibacterials that are environmentally friendly and have good biocompatibility. It can be used as an agent.

Claims (11)

A chitosan film preparation step for preparing a chitosan film;
A chitosan-iodine complex film forming step of reacting the prepared chitosan film with iodine to form a chitosan-iodine complex film;
A method for producing a chitosan-iodine composite film comprising: Chitosan film preparation steps
A chitosan solution generation step of dissolving solid chitosan in an organic acid aqueous solution to generate a chitosan solution;
A chitosan film producing step for producing a chitosan film from the produced chitosan solution;
The method for producing a chitosan-iodine complex film according to claim 1, comprising:   The method for producing a chitosan-iodine complex film according to claim 2, wherein the chitosan film production step includes a heat drying step for producing a chitosan film by heating and drying the produced chitosan solution.   The chitosan-iodine complex film production step has a drying reaction step in which a dried product of the chitosan film produced in the chitosan film production step is reacted with iodine. Composite film production method.   The chitosan-iodine composite film production step includes a dry steam reaction step in which a dried product of the chitosan film produced in the chitosan film production step is reacted with vapor iodine. -Iodine composite film production method.   The method for producing a chitosan-iodine complex film according to any one of claims 1 to 5, wherein the organic acid aqueous solution is an acetic acid aqueous solution.   A bactericidal chitosan-iodine composite film produced by the method for producing a chitosan-iodine composite film according to any one of claims 1 to 6.   A chitosan fiber iodine composite comprising: a chitosan fiber preparation step for preparing chitosan fiber; and a chitosan fiber-iodine composite sheet generation step for reacting the prepared chitosan fiber with iodine to produce a chitosan fiber-iodine composite sheet. Sheet generation method.   A bactericidal chitosan fiber-iodine composite sheet produced by the method for producing a chitosan fiber-iodine composite sheet according to claim 8.   A chitin fiber-iodine composite comprising: a chitin fiber preparation step for preparing a chitin fiber; and a chitin fiber-iodine composite sheet generation step for generating a chitin fiber-iodine composite sheet by reacting the prepared chitin fiber with iodine. Body sheet generation method.   The bactericidal chitin fiber-iodine composite sheet produced | generated by the chitin fiber-iodine composite sheet production | generation method of Claim 10.

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