JP2005350358A - Antibacterial sheet-formed material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means having a high safety and capable of sterilizing microorganisms contained in a polluted material in a good efficiency. <P>SOLUTION: The subject antibacterial sheet-formed material contains an iodine-cyclodextrin inclusion compound obtained by including iodine within a water soluble cyclodextrin by 0.01-20 mass% effective iodine based on the total mass of the sheet-formed material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an antibacterial sheet. Specifically, the present invention relates to an antibacterial sheet-like material containing iodine.

  There are various microorganisms such as bacteria and mold in our living space. These microorganisms can cause us to feel uncomfortable, causing food rot and odors. In addition, the human body causes various diseases such as food poisoning. In order to lead a sanitary life, it is important to suppress the growth of these microorganisms or to remove these microorganisms.

  From this viewpoint, conventionally, various proposals have been made for the purpose of providing a clean living space.

  For example, a technique for imparting antibacterial properties to a substrate by holding a component having antibacterial properties on the substrate such as paper or sheet is known.

  One of them is known to use iodine. This is based on the fact that iodine has a broad antibacterial spectrum, but is also highly safe for humans and has excellent antibacterial properties.

  For example, Patent Document 1 discloses a sterilized and antiseptic wrapping paper provided with a β-cyclodextrin inclusion product of iodine. According to the literature 1, a wrapping paper having sustained and slow-acting bactericidal and antiseptic effects can be obtained by providing an inclusion product formed by inclusion of iodine in β-cyclodextrin on a packaging substrate. It is said.

  Patent Document 2 discloses a functional sheet obtained by adhering β-cyclodextrin containing iodine having a bactericidal and antiseptic effect to the resin film surface. According to Document 2, when a food product such as a fish paste product is packaged using a packaging sheet to which a β-cyclodextrin clathrate powder of iodine is adhered, β-cyclohexane is formed from the surface of the sheet by the moisture in the fish paste product. It is said that dextrin partially dissolves, and as a result, iodine is liberated to achieve sterilization or preserving in the package. In addition, since the clathrate is hardly soluble in water and cannot be dissolved at one time, the release of iodine is also maintained over a long period of time, and excellent sustainability is exhibited.

  On the other hand, in toiletry-related, pet-related, kitchen-related, and research facility-related spaces, pollutants containing many microorganisms adhere to the environment, causing odor and rot. .

  However, as described in Reference 2, iodine-β-cyclodextrin inclusion compound (also referred to as “BCDI” in the present specification) in which iodine is included in β-cyclodextrin is not dissolved in water. Slightly soluble (solubility in water at 25 ° C .: 1.1 mg / mL). For this reason, when the wrapping paper or the wrapping sheet described in the above-mentioned documents 1 and 2 is used as they are to sterilize microorganisms in the sheet deposit, only a small part of BCDI can be dissolved and diffused in the deposit. Therefore, it is difficult to effectively sterilize microorganisms.

Further, as a method of sterilizing microorganisms at contaminated sites using iodine, a method of spraying a solution containing iodine by spraying or the like can be considered. However, this method has a problem that the iodine color adheres to the portion sprayed with the solution and the appearance is impaired.
JP-A-51-100892 JP 51-140964 A

  Therefore, an object of the present invention is to provide means that is highly safe and that can efficiently sterilize microorganisms contained in contaminants.

  The present invention contains an iodine-cyclodextrin clathrate compound in which iodine is clathrated in a water-soluble cyclodextrin, and effective iodine is 0.01 to 20% by mass with respect to the total mass of the sheet. Sheet.

  Moreover, this invention is a mat for toilets etc. characterized by using the said antibacterial sheet-like material.

  The antibacterial sheet-like material of the present invention is an iodine-cyclodextrin inclusion compound (hereinafter referred to as “SCDI”) in which iodine is included in a water-soluble cyclodextrin (hereinafter also referred to as “SCD (Soluable CD)”). Contain). For this reason, when contaminants containing microorganisms adhere to the antibacterial sheet-like material of the present invention, the water-soluble SCDI can be dissolved in the adhered material and diffused into the adhered material. Thereby, the contained microorganisms can be efficiently sterilized by SCDI.

  Therefore, the antibacterial sheet-like material of the present invention can be suitably used for various applications in a space to which contaminants containing microorganisms can adhere.

  Embodiments of the present invention will be described below.

  The first of the present invention contains an iodine-cyclodextrin inclusion compound (SCDI) in which iodine is included in a water-soluble cyclodextrin (SCD), and the effective iodine is 0.000 based on the total mass of the sheet. It is an antibacterial sheet-like material which is 01 to 20% by mass.

  The inventors of the present invention have found that SCDI is effective as a result of intensive studies on means capable of efficiently sterilizing microorganisms in contaminated deposits generated in various daily living spaces. That is, because it has been found that by containing an appropriate amount of SCDI with respect to the substrate constituting the sheet-like material, microorganisms contained in the contaminants attached to the sheet-like material can be effectively sterilized. is there.

  In addition, it is conventionally difficult to produce an antibacterial sheet containing SCDI by immersing a substrate in an aqueous solution of SCDI that is water-soluble, because iodine is expected to be volatilized when moisture is dried. It was thought to be. Nevertheless, the present inventors have found that once SCDI is held in a substrate, it can be stably held in the substrate for a long time, and the present invention has been completed.

  In conventional antibacterial paper or sheet using iodine, iodine was used as a form of BCDI encapsulated in β-cyclodextrin. As mentioned above, the solubility of BCDI in water is very low. For this reason, when trying to sterilize microorganisms contained in contaminants scattered on the floor by laying the conventional antibacterial paper or sheet on the floor, for example, it adheres to the antibacterial paper or sheet. The amount of BCDI that can be dissolved and diffused in the contaminated material was negligible, and it was difficult to effectively sterilize the microorganisms in the contaminant.

  On the other hand, in the antibacterial sheet material of the present invention, iodine showing a bactericidal effect is contained in the form of SCDI encapsulated in water-soluble cyclodextrin (SCD). SCDI in which iodine is included in a water-soluble SCD is also excellent in water solubility. For this reason, it is possible to effectively sterilize microorganisms contained in the contaminants by laying the antibacterial sheet material of the present invention on a place where the contaminants containing the microorganisms can adhere, such as a toilet floor. It becomes. As a result, malodor generated by the growth of microorganisms can be effectively prevented. The technique described in the above-mentioned document 1 is expected to be preserved by iodine sublimated during packaging by wrapping and sealing food or the like as a wrapping paper, and the antibacterial sheet material of the present application. Its action is different.

  Hereinafter, the preferable form of the antibacterial sheet material of the present invention will be described in detail.

  In the present invention, “antibacterial” is a concept that means that the growth of microorganisms is suppressed by iodine. This concept includes both a bactericidal action in which microorganisms are killed by iodine and a bacteriostatic action in which the survival state of microorganisms is maintained by iodine but growth is suppressed. Microorganisms whose growth is suppressed by the antibacterial sheet-like material of the present invention are not particularly limited, and include viruses and fungi in addition to bacteria.

  The antibacterial sheet material of the present invention contains, as an active ingredient, SCDI in which iodine is included in a water-soluble SCD.

  As described above, iodine is contained in the form of an inclusion compound, so that retention and release of iodine can be easily controlled. Moreover, it is possible to adjust the abundance ratio of iodine and cyclodextrin to a desired value according to the environment of the place where the antibacterial sheet material of the present invention is used. Furthermore, iodine, which is the main form of the antibacterial effect, is included in cyclodextrin, so it varies somewhat depending on the iodine content, but has almost no iodine-specific odor and is used in various places in the living space. However, it rarely generates iodine odor.

  In addition, when using the antibacterial sheet-like material of the present invention, iodine is volatilized little by little from the sheet-like material. Here, the amount of iodine that volatilizes within a certain period of time and the amount of iodine that can remain and exert the effect of the present invention also varies depending on the effective iodine initially contained in the sheet material, the environment in use, etc. Yes. However, according to the sheet-like material of the present invention, a secondary effect due to the volatilized iodine is also obtained in some cases. That is, the antibacterial sheet-like material of the present invention has a deodorizing property of removing bad odor in the space around the sheet-like material by volatilized iodine, and a sterilization of microorganisms existing in the space around the sheet-like material. It may also have space sterilization properties. However, the antibacterial sheet-like material of the present invention is not limited to the sheet-like material having such a secondary effect. If the antibacterial properties described above are obtained, the bactericidal property of the surrounding space is obtained. Of course, it does not have to have deodorizing properties.

  The production method of SCDI is not particularly limited. For example, by using iodine and SCD as raw materials and adopting a conventionally known method or a combination thereof for the production of an iodine-cyclodextrin inclusion compound, the SCDI used in the present invention can be produced. For example, methods described in JP-A-51-88625, JP-A-51-100892, JP-A-2002-322008, JP-A-2003-40717, etc .; iodine amount and iodine dissolution aid amount; A method in which iodine is dissolved in a predetermined range and SCD is added thereto; or a method in which SCD is further added to SCDI produced by these methods to bring effective iodine to a value in a desired range Etc.

  The iodine as a raw material is not particularly limited, and a commercially available product may be used as it is. Moreover, what was synthesize | combined according to the method of heat-distilling potassium iodide and potassium dichromate may be used.

  As another raw material, water-soluble cyclodextrin (SCD) is used. “Cyclodextrin” is a compound in which D-glucose is bound cyclically by α-1,4 bonds. Cyclodextrins are roughly classified into α-cyclodextrin (6), β-cyclodextrin (7), and γ-cyclodextrin (8) depending on the number of D-glucose constituting the cyclodextrin.

  In this specification, “water-soluble” means that the solubility in water at 25 ° C. is 20 mg / mL or more. The solubility in water is not particularly limited. For example, the solubility is measured by the method described in the Chemical Society of Japan, “Experimental Chemistry Course 1—Basic Operation I”, 4th edition, Maruzen Co., Ltd., pages 151-159. Can be done.

  The water-soluble cyclodextrin (SCD) used in the present invention is not particularly limited as long as it is water-soluble. That is, the solubility in water at 25 ° C. may be 20 mg / mL or more. The solubility is preferably 50 mg / mL or more, more preferably 100 mg / mL or more. By using cyclodextrin having high solubility in water, the solubility of SCDI contained in the antibacterial sheet of the present invention in water is also improved. As the water-soluble cyclodextrin (SCD), methyl-β-cyclodextrin is preferably used. Methyl-β-cyclodextrin is a compound that has significantly improved water solubility compared to β-cyclodextrin by methylation of the hydroxyl group of β-cyclodextrin. The solubility of methyl-β-cyclodextrin in water at 25 ° C. is 2000 mg / mL or more.

  Methyl-β-cyclodextrin is not particularly limited, and for example, one synthesized by a method of adding sodium hydroxide and methyl chloride to β-cyclodextrin and reacting them may be used, or a commercially available product may be used. . Examples of commercially available products of β-cyclodextrin, which is a raw material for synthesizing methyl-β-cyclodextrin, include β-cyclodextrin (manufactured by Cyclochem Co., Ltd.) commercially available as CAVAMAX (registered trademark) W7 series. It is done. Examples of commercially available methyl-β-cyclodextrin include CAVASOL (registered trademark) W7 M series (manufactured by Cyclochem).

  As water-soluble cyclodextrin (SCD), in addition to methyl-β-cyclodextrin, α-cyclodextrin and γ-cyclodextrin, and chemical modifications thereof may be used. Examples of commercially available products of α-cyclodextrin include CAVAMAX (registered trademark) W6 series and the like, and examples of commercially available products of γ-cyclodextrin include CAVAMAX (registered trademark) W8 series (all are , Manufactured by Cyclochem Co., Ltd.). Here, the solubility of α-cyclodextrin in water at 25 ° C. is 145 mg / mL, and the solubility of γ-cyclodextrin in water at 25 ° C. is 232 mg / mL. In addition, only 1 type may be used independently for a raw material cyclodextrin, and 2 or more types may be used together. When two or more kinds are used in combination, it is preferable that all cyclodextrins are water-soluble, but the present invention is not limited to such a form, and at least one cyclodextrin is a water-soluble cyclodextrin ( SCD).

In the present invention, when synthesizing itself from cyclodextrin, for example, those synthesized by a known method such as causing amylase derived from Bacillus macerans to act on starch may be used.

  The “dissolution aid” refers to a compound that assists in dissolving iodine in a solution. Examples of solubilizers include halogen acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, and hydrofluoric acid, sodium iodide, potassium iodide, magnesium iodide, calcium iodide, barium iodide, and chloride. Illustrative are alkali metal or alkaline earth metal halides such as sodium, potassium chloride, magnesium chloride, calcium chloride, barium chloride, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, barium bromide.

  The effective iodine in the antibacterial sheet-like material of the present invention may vary depending on the base material and use of the antibacterial sheet-like material, but is preferably 0.01 to 20% by mass relative to the total mass of the sheet-like material. More preferably, it is 0.1-20 mass%, Most preferably, it is 0.3-15 mass%. When the effective iodine is in such a range, the stability of iodine is improved, and the antibacterial effect of the antibacterial sheet can be maintained for a long period of time. Effective iodine in the antibacterial sheet can be controlled by adjusting the amount of iodine or SCD added to produce SCDI. The effective iodine can also be controlled by adjusting the amount of SCDI added to the substrate. By controlling the effective iodine in the antibacterial sheet, the release of iodine from the antibacterial sheet can be controlled.

  The base material which comprises the antimicrobial sheet-like material of this invention is not restrict | limited in particular. Examples of the substrate constituting the antibacterial sheet material of the present invention include paper, woven fabric, and non-woven fabric. For paper, Japanese paper, filter paper, drawing paper, fine paper, cardboard paper, cardboard, recycled paper, synthetic paper, white paperboard, yellow paperboard, chipboard, colored paperboard, building material base paper, backing paper, thin paper, thermal paper, synthetic fiber paper, etc. Is included. Either organic fiber or inorganic fiber may be used as a raw material for the woven fabric and the nonwoven fabric. Here, the organic fibers include plant fibers, animal fibers, regenerated fibers, semi-synthetic fibers, synthetic fibers, and the like. The inorganic fiber includes glass fiber, carbon fiber, ceramic fiber and the like. Furthermore, examples of plant fibers include woods such as wood pulp, straw pulp, bamboo pulp, and kenaf pulp, as well as herbs, cotton, and hemp. Examples of animal fibers include fibers such as silk and wool. . Examples of recycled fibers include rayon and cupra. Examples of semi-synthetic fibers include acetate, triacetate, and promix. Examples of synthetic fibers include nylon, acrylic, vinylon, vinylidene, polyvinyl chloride, polyester, polyethylene, and polypropylene. , Benzoate, polyclar, phenol and the like. In addition, as a base material, a commercially available thing may be used and what was synthesize | combined itself may be used.

  In addition, SCDI which is an active ingredient of the antibacterial sheet material of the present invention is composed of iodine and cyclodextrin and has biodegradability. When SCDI is decomposed, iodine is ionized to become potassium salt or sodium salt, and cyclodextrin is decomposed into water, carbon dioxide and the like by microorganisms in the soil. From such a viewpoint, the antibacterial sheet-like substrate of the present invention is also preferably biodegradable. Since the base material is also made of a biodegradable material, the safety of the antibacterial sheet-like material of the present invention can be further improved, and the burden on the environment can be further reduced.

  In the antibacterial sheet material of the present invention, the size and shape of the substrate used are not particularly limited, and can be appropriately determined according to the application of the antibacterial sheet material.

  The form in which SCDI is contained in the antibacterial sheet-like material of the present invention is not particularly limited. For example, it may be contained only on one or both surfaces of the substrate constituting the sheet-like material. It may be contained not only on the surface but also inside. The form in which the SCDI is contained can be adjusted by appropriately selecting a method for producing a sheet-like material, which will be described later, according to the desired value of effective iodine, the intended use, and the like.

  The antibacterial sheet material of the present invention may further contain an additive in addition to SCDI. As the additive that can be added to the antibacterial sheet-like material of the present invention, conventionally known additives can be used depending on the substrate and application. For example, when the base material is paper, an internal adhesive based on cationic starch or amphoteric starch, a paper strength agent such as polyacrylamide, various fillers such as talc, diatomaceous earth and titanium oxide, aniline, etc. And various sizing agents such as rosin, starch, glue, carboxymethyl cellulose and polyvinyl alcohol, brighteners such as glycerin, surfactants, fragrances, dyes, pigments and the like. Moreover, when the base material is a woven or non-woven fabric made of fibers, an antistatic agent, a stabilizer, an anti-yellowing agent, a lubricant and the like can be added. Moreover, you may contain a well-known antibiotic, a synthetic antibacterial agent, etc. if necessary. Known antibiotics include, for example, β-lactam antibiotics such as penicillin, cephem, carbapenem, and monobactam antibiotics; aminoglycoside antibiotics; macrolide antibiotics; tetracycline antibiotics; chloramphenic acid Cole; lincomycin; fosfomycin; peptide antibiotics; and antifungal antibiotics. Examples of the synthetic antibacterial agent include nalidixic acid, a new quinolone antibacterial agent, and an azole antifungal agent. In addition, it is not restricted only to these, The various compounds used as an external preparation and a disinfectant may be added as an additive. In some cases, an antiviral agent may be added. Moreover, as for the additive illustrated, only 1 type may be used independently and 2 or more types may be used together. When additives are added in the antibacterial sheet material of the present invention, the total amount of all additives is not particularly limited, but is preferably 0.1 to 30 with respect to the total mass of the antibacterial sheet material. % By mass, more preferably 0.3 to 20% by mass.

  The antibacterial sheet-like product of the present invention may be dried or wet. When the antibacterial sheet material of the present invention is wet, examples of the impregnating liquid impregnated in the sheet material include water, water-containing alcohol, and surfactant.

  Moreover, the sheet-like material of the present invention may be formed into a laminated sheet by providing a sheet-like material other than the sheet-like material of the present invention on one or both surfaces. Since the antibacterial sheet material of the present invention contains iodine, the sheet material may exhibit an iodine color. In such a case, the antibacterial sheet-like material of the present invention exhibiting iodine color can be coated and improved in appearance by forming a laminated sheet using another sheet-like material. Even in such a laminated sheet, contaminants including microorganisms attached to the surface of the laminated sheet can diffuse to the layer of the sheet-like material of the present invention. Or conversely, SCDI may diffuse into deposits on the sheet surface. Thus, the SCDI contained in the sheet-like material of the present invention can be effectively dissolved and diffused in the contaminant, and the microorganisms in the contaminant can be sterilized. In addition, when the antibacterial sheet material of the present invention is a laminated sheet, the sheet material other than the sheet material of the present invention provided on the surface is not particularly limited, but can be used in the present invention, for example. Substrates can be used as well.

  There is no restriction | limiting in particular about the manufacturing method of the antimicrobial sheet-like material of this invention. For example, SCDI is added to a suitable solvent such as water to prepare a solution containing SCDI (also referred to herein as “SCDI solution”), and the substrate is immersed in the solution, or the solution is added to the substrate. The method of apply | coating or spraying is mentioned. According to such a production method, SCDI dissolved in a solvent such as water can sufficiently penetrate into the inside of the substrate. For this reason, a desired amount of SCDI can be held on and inside the substrate in a very simple manner.

  Moreover, the method of making paper using a SCDI solution, and the method of attaching a SCDI solution on a base material with a roll may be used. At this time, specific procedures and devices for immersing the base material in the SCDI solution, applying or spraying the SCDI solution to the base material, making paper using the SCDI solution, or attaching by a roll, etc. A form in particular is not restrict | limited, A conventionally well-known form may be employ | adopted suitably.

  The solvent of the SCDI solution is preferably water from the viewpoint of workability, but an alcohol solvent or the like can be used in addition to water. Moreover, these mixed solvents may be used.

  Various additives described above can be added to the SCDI solution at the same time. However, based on known knowledge, other additives such as stabilizers can be used for the purpose of changing the properties of the solution. Other additives may be added.

  The effective iodine in the SCDI solution can be appropriately determined according to the type of substrate, production method, and the like, but is usually about 1 to 8% by mass with respect to the total amount of the solution. However, the present invention is not limited to this value, and SCDI solutions having different concentrations may be used.

  The antibacterial sheet-like material of the present invention can be applied to various uses by appropriately adjusting the SCDI content, the form of the substrate and the like. For example, by using the antibacterial sheet-like material of the present invention in a compartment to which contaminants including microorganisms can adhere, the contaminant adheres to the antibacterial sheet-like material of the present invention, and the SCDI dissolves in the adhered contaminant. And by diffusing, contained microorganisms can be effectively sterilized by iodine. However, the use of the present invention is not limited to such a form, and can be similarly applied as long as the SCDI contained in the sheet-like material of the present invention can exhibit antibacterial properties.

  Therefore, the specific use of the antibacterial sheet-like material of the present invention is, for example, laid on the toilet floor as a toilet mat; laid on a laboratory bench or floor in a research facility that handles microorganisms as a laboratory bench sheet; Lay it on a workbench or floor in a medical institution as a plastic sheet; lay it in a pet toilet or birdcage as a pet sheet; lay it on a kitchen workbench or floor as kitchen paper; Examples of the filter include, but are not limited to, the form of being attached to an air conditioner, an air cleaner, and a vacuum cleaner. Of course, it may be used as a wiping sheet for wiping off contaminants in various places as described above.

  Hereinafter, the present invention will be described in more detail with reference to examples.

<Example>
<Preparation of antibacterial sheet>
A stock solution of MCDI aqueous solution (effective iodine: 6% by mass) and a 10-fold diluted solution with water (effective iodine: 0.6% by mass), both commercially available as “MCDI-6” from Niho Chemical Co., Ltd., were prepared.

Commercially available ink-jet paper, Japanese paper, and filter paper were cut into 10 cm squares and immersed in the stock solution and dilution solution prepared above (wool fiber woven fabric was the stock solution only) for 30 seconds. Then, it was made to dry at room temperature for 24 hours, and the antimicrobial sheet-like material of this invention was produced. The prepared antibacterial sheet was cut into 2 cm squares, immersed in 20 mL of distilled water, and prepared by an iodine titration method using a 0.01 mol / L sodium thiosulfate aqueous solution. Effective iodine contained in the sheet was measured (unit: mass% and g / cm ² ). The results are shown in Table 1 below.

  As can be seen from Table 1, the effective iodine contained in the sheet-like material also changed according to the effective iodine in the immersion solution. That is, when an immersion solution containing a high concentration of iodine is used, the effective iodine contained in the sheet is also increased. When the MCDI-6 stock solution is used, about 8% by mass of effective iodine is obtained in the paper base material, and when the wool fiber woven fabric is used as the base material, the effective iodine is 3% by mass. there were. On the other hand, when the 10-fold diluted solution was used, the effective iodine in the paper substrate was around 1% by mass.

  The effective iodine contained per unit area of the sheet-like material was relatively large when the base material was Japanese paper and filter paper, while it was relatively small when the base material was ink-jet paper and wool fiber woven fabric. This difference is thought to be due to the thickness and bulk density of the base material, but if you want to produce an antibacterial sheet with a large amount of effective iodine per unit area, Japanese paper or filter paper can be used effectively as the base material. I understand.

<Antimicrobial activity test>
Antibacterial against Escherichia coli F1 which is a Gram-negative bacilli and Staphylococcus aureus IFM2014 by a halo test method (filter paper disk method) using the antibacterial sheet material prepared above. An activity test was performed.

First, 100 μL of each of the above E. coli and S. aureus cell suspensions prepared using physiological saline to a cell concentration of 10 ⁶ CFU / mL was applied onto a standard agar medium. Next, each of the antibacterial sheet-like materials produced above was cut into 2 cm squares to form test pieces, which were placed in the center of the medium on which the bacterial cell suspension was applied.

  Thereafter, the test bacteria are cultured at 37 ° C. for 24 hours, and the antibacterial activity of each antibacterial sheet is determined according to the size of the growth inhibition zone (halo) formed around the test piece placed in the center of the medium. Was judged.

  As a result, formation of a growth inhibition zone showing antibacterial activity was confirmed in all the prepared samples. In addition, even when any base material is used, a large growth inhibition zone is confirmed using the immersion solution containing high concentration of effective iodine, and effective iodine contained per unit area of the base material is confirmed. The result depends on. The growth inhibition zone for S. aureus was slightly larger than the growth inhibition zone for E. coli.

  From the above, it can be seen that the antibacterial sheet of the present invention exhibits excellent antibacterial properties against microorganisms such as Escherichia coli and Staphylococcus aureus.

<Sustained release test of iodine from antibacterial sheet>
Using the antibacterial sheet-like material prepared above (base materials: ink painting paper, Japanese paper, and filter paper), a sustained release test of iodine (100 ° C.—drying conditions—1 hour, and 25 ° C.—relative humidity 75% -1 week).

  First, each of the sheet-like materials produced above was cut into 2 cm squares to form test pieces, and each was suspended in a dryer whose temperature was adjusted to 100 ° C. for 1 hour to test the sustained release property.

  Each of the sheet-like materials produced above was cut into 2 cm squares to form test pieces, and each was suspended in a thermostatic chamber adjusted to a temperature of 25 ° C. and a relative humidity of 75% for 7 days to provide sustained release. Was tested.

  Thereafter, the effective iodine remaining in the test piece was measured for each test piece using the same iodine titration method as described above. The results are shown in Table 2.

  From Table 2, it can be seen that the antibacterial sheet-like material of the present invention has an excellent sustained release property and can be used continuously over a long period of time. Moreover, even if it was a case where any base material was used, the case where the immersion solution containing a high concentration of effective iodine was used showed the especially high effective iodine residual rate.

<Reference example>
An antibacterial sheet-like material containing BCDI was prepared according to the method described in Example (2) of JP-A-51-100892 (Patent Document 1). A specific method for producing the antibacterial sheet is as follows.

<Preparation of antibacterial sheet>
BCDI powder (effective iodine: 10% by mass) commercially available as “BCDI-10” from Niho Chemical Co., Ltd. was prepared.

  Next, 0.16 g of the BCDI powder, 0.04 g of β-cyclodextrin, and 20 g of ethyl cellulose were added to 100 g of acetone to prepare a BCDI solution.

  After thoroughly stirring the BCDI solution using a mortar, the BCDI solution is applied on a cellophane film so as to have a thickness of 4 μm, and dried at room temperature for 24 hours to obtain an antibacterial sheet. Produced.

<Antimicrobial activity test>
In place of the antibacterial sheet material of the present invention, an antibacterial activity test was performed in the same manner as in the examples of the present application except that the antibacterial sheet material prepared in this reference example was used.

  As a result, in the antibacterial activity test of this reference example, only a growth inhibition zone smaller than that in the above examples was formed against S. aureus, and no growth inhibition zone was formed against E. coli. .

  Therefore, it can be seen that the antibacterial sheet-like material produced by the method described in the examples of JP-A-51-100892 is inferior in antibacterial properties as compared with the antibacterial sheet-like material of the present invention. As a cause of this, first, the antibacterial sheet-like material of the present reference example does not contain sufficient amount of effective iodine to show antibacterial properties. In addition, the fact that BCDI is sparingly soluble in water and that ethylcellulose contained as a binder for holding BCDI on a base material is difficult to adapt to water are also considered as causes of insufficient antibacterial properties. .

  From the above results, even if the sheet described in the above publication is used as it is, it is expected that it is difficult to efficiently sterilize microorganisms contained in the contaminants.

Claims (6)

  An antibacterial sheet material comprising an iodine-cyclodextrin clathrate compound in which iodine is clathrated in a water-soluble cyclodextrin and having an effective iodine content of 0.01 to 20% by mass relative to the total mass of the sheet material .   The antibacterial sheet-like product according to claim 1, wherein the water-soluble cyclodextrin is methyl-β-cyclodextrin.   The antibacterial sheet-like material according to claim 1 or 2, wherein the substrate is paper, woven fabric, or non-woven fabric.   The antibacterial sheet-like material according to claim 3, wherein the substrate is Japanese paper or filter paper.   The antibacterial sheet-like material according to any one of claims 1 to 4, further having a deodorizing property.   It is used for any one of a toilet mat, an experimental table sheet, a medical sheet, a pet sheet, kitchen paper, an immersion sterilization sheet, a filter, or a wiping sheet. The antibacterial sheet-like material according to item.