JP7111306B2 - Antifungal packaging for the space inside a storage container - Google Patents

Description

TECHNICAL FIELD The present invention relates to an anti-mold packaging body for use in a storage container forming a closed space.

As an anti-mold package for a closed space, there is a package containing allyl isothiocyanate as an active ingredient in a container during transportation of leather products. Allyl isothiocyanate has a strong antifungal effect, but it is extremely irritating and difficult to use.

A patent application has been filed for an antifungal agent using fragrance, but this is only based on test data in containers such as petri dishes and glass tubes (see Patent Documents 1 and 2). A patent application has been filed for an antibacterial composition using 2-hydroxybenzaldehyde (sometimes referred to as salicylaldehyde), but it does not refer to antifungal properties for space (see Patent Document 3). Salicylaldehyde is exemplified as an active ingredient of a volatile antibacterial and antifungal agent product (see Patent Document 4), but experimental data regarding salicylaldehyde is not shown in the Examples. Further, the experiment in Patent Document 4 is nothing more than an antifungal property in a vacuum cleaner paper pack, and the antifungal effect for small gaps is only verified.

JP-A-4-21606 JP 2016-199478 A Japanese Patent Application Laid-Open No. 2003-192581 JP-A-10-194905

In prior art documents, it was confirmed that compounds derived from hypoallergenic fragrances, which are said to have an antifungal effect, actually exhibit an antifungal effect in a closed space with an area of about several tens of liters. There was no description, and there was a problem that it was not possible to actually provide an anti-mold product for space that truly exhibits such an anti-mold effect.

Here, the antifungal effect on closed spaces refers to the effect of completely suppressing the germination of fungal spores.

Therefore, as a means for solving the above problems, the antifungal package for the inner space of a storage container according to the present invention contains 2-hydroxybenzaldehyde as an active ingredient in the bag of the package made of a gas barrier resin film. It is characterized in that a small hole penetrating to the inside of the bag is formed on the surface of the package.

Moreover, it is preferable that the gas-barrier resin film is made of polyethylene terephthalate.

Furthermore, it is preferable that the resin is an ethylene-vinyl acetate copolymer resin, or that the resin is a polypropylene resin or a polyethylene resin.

Furthermore, it is also preferable that the small hole is formed to have a diameter of 0.3 mmφ to 0.8 mmφ.

Furthermore, it is also preferable that the small holes are formed in an amount of 0.2 to 1.0/cm ² .

The storage container includes, for example, a shoebox, a trash can, a small container for transportation, and the like, and refers to a container having a capacity of about several tens of liters. Specifically, it is a container with a capacity of 1 L or more and 100 L or less, more preferably a container with a capacity of 30 L or more and 70 L or less. If it is less than the lower limit, the volume of the storage container is insufficient, and if it is greater than the upper limit, a sufficient antifungal effect cannot be expected.

According to the present invention, it is possible to provide an anti-mold packaging body for a storage container interior space that exhibits a particularly excellent anti-mold effect in a storage container having a closed space of several tens of liters.

Further, according to the present invention, 2-hydroxybenzaldehyde is contained in a granular resin, and the granular resin is filled in a gas barrier resin film having small pores, thereby exhibiting an antifungal effect for a long period of 20 weeks or more. can be made

Furthermore, since the 2-hydroxybenzaldehyde used in the present invention is less irritating, it is possible to suppress the generation of irritation to the mucous membranes of people's eyes, nose, etc., and it is not necessary for people to bring their faces close to the container during work. It is also useful as an antifungal agent for use in certain spaces.

4 is a perspective view showing an outline of the overall shape of the container 4. FIG. Packages 16(a) to 16(h) and potato dextrose placed on the inner surface 13 of the overturned container 4 in the verification of the effectiveness of the anti-mold package for the inner space of the storage container contained in the granular resin. FIG. 4 is a vertical cross-sectional view of the container 4 showing the positional relationship with the agar media 7a to 7f as viewed from above. 4 is a graph showing volatilization amounts of chemicals from packages 16(a) to 16(d) in Examples 1 to 4 with respect to the verification period. FIG. 10 is a graph showing the volatilization rate of drugs from packages 16(a)-16(d) in Examples 1-4 against the verification period; FIG. FIG. 10 is a graph showing volatilization amounts of drugs from packages 16(e) to 16(h) in Examples 5 to 8 with respect to the verification period; FIG. FIG. 10 is a graph showing the volatilization rate of the drug from packages 16(e)-16(h) in Examples 5-8 against the verification period; FIG.

(Anti-mildew package for inner space of storage container)
In the antifungal package for the interior space of a storage container according to the present embodiment, the inside of the bag of the package made of a gas-barrier resin film is filled with a granular resin containing 2-hydroxybenzaldehyde as an active ingredient. By forming small holes penetrating to the inside of the bag on the surface of the package, it is possible to exert an antifungal effect on the closed space.

(package)
The package must be made of a gas-barrier resin film. In addition, it is necessary that the surface of the package is formed with a small hole penetrating to the inside of the bag. With such a configuration, it is possible to control the amount of volatilization of the active ingredient of the antifungal agent into the space, and to adjust the duration of the antifungal effect.
The size of the small holes is preferably 0.3 mmφ to 0.8 mmφ in diameter from the viewpoint of controlling volatilization amount and maintaining the strength of the film itself.
Moreover, the number of the small holes is preferably 0.2 to 1.0/cm ² per unit area from the viewpoint of volatilization amount control. The volatilization rate can be controlled by the number of pores.

(Gas barrier resin film)
From the viewpoint of sufficient gas barrier properties and strength, the gas barrier resin film is preferably a film using a resin containing at least one of polyethylene terephthalate and polypropylene. The film can be perforated with a needle at regular intervals to form a film having small holes. Generally, the diameter of the small hole is 60% of the diameter of the needle, and a needle that matches the diameter of the target small hole can be selected.

(Active ingredient of antifungal agent)
In the antifungal package of the present invention, it is necessary to use 2-hydroxybenzaldehyde as an active ingredient of the antifungal agent from the viewpoint of antifungal effect and low irritation.

(granular resin)
The resin with which the active ingredient of the antifungal agent is mixed is preferably an ethylene-vinyl acetate copolymer resin, a polypropylene resin, or a polyethylene resin. In particular, an ethylene-vinyl acetate copolymer resin is preferable because it can swell and exhaust 2-hydroxybenzaldehyde at room temperature, so that there is little volatilization loss during processing. When 2-hydroxybenzaldehyde is used in combination with a relatively low-boiling perfume, it is preferable to use an ethylene-vinyl acetate copolymer resin if the perfume in question is easily swelled and exhausted by the ethylene-vinyl acetate copolymer resin. On the other hand, when 2-hydroxybenzaldehyde is used in combination with a material that is difficult to be swollen and exhausted by an ethylene-vinyl acetate copolymer resin, for example, using a technique such as Japanese Patent No. 3963941 or Japanese Patent No. 4576479, a polypropylene resin or polyethylene is used. Melt-kneading into the resin is preferred.

(Preparation of antifungal package for inner space of storage container)
When packaging granular resin in a film having small holes, a three-way sealing method can be suitably used, in which the film is folded in two, the bottom and side surfaces are heat-sealed, and the top is heat-sealed after the granular resin is filled. Alternatively, a 4-side sealing method can be used in which two films are stacked, the bottom and two sides are heat-sealed, and the top is sealed after being filled with granular resin.

Next, the present invention will be described in more detail with test examples and the like, but the present invention is not limited to these. It should be noted that the numerical value indicating the content of each component in the table in this example is expressed in weight %.

The effect of the anti-mold package for the inner space of the storage container containing the granular resin containing the anti-mold agent will be verified below.

[Specific examples of gas barrier film]
A polyethylene terephthalate (PET) film with holes 114 (0.6 mm diameter holes, 0.25 holes/cm ² ) and film holes 112A (0.4 mm diameter holes, 0.4 holes/cm ² ) were formed. Using. The perforated PET film 114 and the perforated film 112A consist of a three-layer structure of 20 μm thick CPP (Cast Polypropylene), 20 μm thick PET, and PET spunbond in order from the inside.

[Preparation of polypropylene (PP) resin granules containing antifungal agent]
According to Japanese Patent No. 3963941, PP resin (manufactured by Nippon Polypro, J-107G), Septon 2014 (manufactured by Kuraray) and 2-hydroxybenzaldehyde are mixed with 60 parts by weight, 20 parts by weight, and 20 parts by weight, respectively. Melt kneading was carried out at 180° C. using kneading equipment to obtain PP resin granules containing 20% of 2-hydroxybenzaldehyde.
[Preparation of polyethylene (PE) resin containing perfume]
According to Patent No. 3963941, PE resin (UJ-790, manufactured by Japan Polyethylene), Septon 2014 (manufactured by Kuraray) and fragrance (PEACH JDIO-1271, manufactured by Taiyo Perfume) are added at 60 parts by weight and 20 parts by weight, respectively. , and 20 parts by weight were melt-kneaded at 160° C. using a twin-screw kneading equipment to obtain PE resin granules containing 20% of perfume.

[Preparation of package]
A 3-side sealing method was used using film perforations 114 (diameter 0.6 mmφ holes, 0.25 holes/cm ² ) and film perforations 112A (diameter 0.4 mmφ holes, 0.4 holes/cm ² ). Each of the antifungal agent-containing PP resin granules and perfume-containing PE resin granules was filled with a predetermined amount to prepare a rectangular package having a seal width of 5 mm, which was designated as Examples 1 to 4. Table 1 shows the contents of the packages of Examples 1-4.

As shown in FIG. 2, the prepared packages according to Examples 1 to 4, 16(a) to 16(d), are placed sideways in the accommodation space of the container 4, and the inner surface 13 is attached to each container 4. Placed one on top. Then, around each of the packages 16(a) to 16(d), containers 8a to 8c containing potato dextrose agar media 7a to 7c seeded with previously prepared fungal spore liquid, It was installed so as to surround the package, and the lid 5 was closed. As the fungi to be evaluated, Aspergillus niger was seeded in the container 8a, Penicillium citrinum was seeded in the container 8b, and Cladosporium cladosporioides was seeded in the container 8c. After installation, the lid 5 of the container 4 was opened and closed once a day to replace the internal air. Four days after installation, the number of colonies on potato dextrose agar medium 7a to 7c seeded with the spore liquid of each mold was counted to verify the durability of the antifungal effect, and new spore liquid was seeded every 14 days. It was replaced with containers 8a to 8c containing potato dextrose agar media 7a to 7c. In addition, blanks were prepared as comparative samples and evaluated in the same manner as the packages 16(a) to 16(d). The blanks were prepared under the same conditions except that the packages 16(a) to 16(d) were not installed, and contained three containers containing potato dextrose agar media 7a to 7c inoculated with three types of fungal spore liquids. The container 4 was set on the side surface 13 .

In addition to the operation of counting the number of colonies, the weights of the packages 16(a) to 16(d) of Examples 1 to 4 were measured, and the volatilization amount of the drug contained in the resin grains was recorded. The results regarding changes in weight of packages 16(a)-16(d) are shown in FIGS. 3 and 4. FIG. In FIG. 3, the horizontal axis represents the number of days elapsed, and the vertical axis represents the amount of volatilized 2-hydroxybenzaldehyde and fragrance volatilized to the outside. FIG. 4 is a graph showing the volatilization rate of 2-hydroxybenzaldehyde volatilized to the outside and the perfume, with the horizontal axis representing the verification period. The volatilization rates of 2-hydroxybenzaldehyde and perfume are 2-hydroxybenzaldehyde and perfume contained in packages 16 (a) to 16 (d) of Examples 1 to 4 on the verification start date (day 0). When the weight of 100%, the amount of weight reduction of packages 16 (a) to 16 (d) measured at each specific period during the verification period is expressed in 100%.

As can be seen from FIG. 3, the volatilization amounts from the packages 16(b) and 16(c) according to Example 2 and Example 3 exhibited almost the same tendency during the verification period. This is because while the packages 16(b) and 16(c) are the same size, the number of perforations is different, but each package 16(b) and 16(c) has a Taking the ratio of the total area of the small holes, Example 2: Example 3 was 1.1:1.0, which was almost the same. On the other hand, the amount of volatilization in Example 1, which has fewer pores than in Example 2, is the lowest, and the amount of volatilization in Example 4, which has more pores than in Example 3, tends to be the largest. Therefore, it can be said that the volatilization amount of the drug has a correlation with the area of the small pores. On the other hand, as shown in FIG. 4, there was no significant difference in the volatilization rates of Examples 1-4.

The results regarding the persistence of the antifungal effect are shown in Table 2 for container 8a (test fungus: Aspergillus niger), shown in Table 3 for container 8b (test fungus: Penicillium citrinum), and container 8c (test fungus: Cladosporium cladosporioides). is shown in Table 4. In Tables 7 to 9, ">300" indicates that more than 300 colonies were confirmed.

From the results in Tables 2 to 4, among Examples 1 to 4, Example 1 confirmed the earliest formation of colonies for any of the test bacteria. On the other hand, in Examples 2 and 4, colony formation was confirmed for the first time at the 31st week. As for the blank, the generation of a large number of colonies was confirmed in all weeks. It should be noted that the anti-fungal effect varied to some extent between Examples 1 to 4, and the correlation was not shown only with the total area of the small holes provided in the packages 16(a) to 16(d).

[Ethylene-vinyl acetate copolymer resin (EVA) grains containing antifungal agent and fragrance]
Resin particles are prepared by adding 20 parts by weight of a 2/1 mixture of 2-hydroxybenzaldehyde and perfume (PEACH JDIO-1271) to 70 parts by weight of EVA particles and stirring at room temperature. The objective resin granules were obtained by uniformly swelling and exhausting 2-hydroxybenzaldehyde and perfume in the EVA granules.

[Preparation of package]
A 3-side sealing system was used using film perforations 114 (diameter 0.6 mmφ holes, 0.25 holes/cm ² ) and film perforations 112A (diameter 0.4 mmφ holes, 0.4 holes/cm ² ). A rectangular package having a seal width of 5 mm was prepared by filling predetermined amounts of EVA resin grains containing an antifungal agent and a perfume, respectively, as Examples 5 to 8. Table 5 shows the contents of the packages of Examples 5-8.

Packages 16 (e) to 16 (h) produced according to Examples 5 to 8 were placed sideways in the accommodation space of the container 4 in the same manner as in FIG. 4 were installed on the inner surface 13 one by one. Then, around each of the packages 16(e) to 16(h), containers 8d to 8f containing potato dextrose agar media 7d to 7f seeded with mold spore liquid prepared in advance, It was installed so as to surround the packages 16(e) to 16(h), and the lid 5 was closed. As the fungi to be evaluated, Aspergillus niger was seeded in the container 8d, Penicillium citrinum was seeded in the container 8e, and Cladosporium cladosporioides was seeded in the container 8f. After installation, the lid 5 of the container 4 was opened and closed once a day to replace the internal air. Four days after installation, the number of colonies on potato dextrose agar medium 7d to 7f was sown with the spore liquid of each mold to verify the durability of the antifungal effect, and new spore liquid was sown every 14 days. It was replaced with containers 8d to 8f containing potato dextrose agar media 7d to 7f. In addition, blanks were prepared as comparative samples and evaluated in the same manner as the packages 16(e) to 16(h). The blanks were prepared under the same conditions except that the packages 16(e) to 16(h) were not installed, and contained three containers containing potato dextrose agar media 7d to 7f inoculated with three types of fungal spore liquids. The container 4 was set on the side surface 13 .

In addition to the operation of counting the number of colonies, the weights of the packages 16(e) to 16(h) of Examples 5 to 8 were measured, and the volatilization amount of the drug contained in the resin grains was recorded. The results regarding changes in weight of packages 16(e) to 16(h) are shown in FIGS. 5 and 6. FIG. In FIG. 5, the horizontal axis represents the elapsed days, and the vertical axis represents the volatilization amount of 2-hydroxybenzaldehyde volatilized from the EVA grains to the outside of the packages 16(e) to 16(h) and the perfume. In FIG. 6, the horizontal axis represents the verification period, and the vertical axis represents the volatilization rate of 2-hydroxybenzaldehyde volatilized from the EVA grains to the outside of the packages 16(e) to 16(h) and the perfume. In addition, the volatilization rate of 2-hydroxybenzaldehyde and fragrance was based on the weight of 2-hydroxybenzaldehyde and fragrance contained in packages 16 (e) to 16 (h) on the verification start date (day 0) as 100%. In this case, the amount of decrease in the weight of the packages 16(e) to 16(h) measured at specific intervals during the verification period is expressed as a percentage of 100.

As can be seen from FIG. 5, the volatilization amounts from the packages 16(f) and 16(g) according to Examples 6 and 7 showed almost the same tendency during the verification period. This is because the packages 16(f) and 16(g) have the same size, but the numbers of small holes formed in the packages 16(f) and 16(g) are different. Taking the ratio of the total area of the small holes formed in the broadcasting bodies 16(f) and 16(g), Example 11: Example 12 = 1.1:1.0, which was almost the same. On the other hand, the package 16(e), which has a smaller number of small holes H than the package 16(f), has the smallest amount of volatilization, and the package 16(g), which has a larger number of small holes. It can be said that the fact that the volatilization amount of 16(h) tended to be the largest indicates that the volatilization amount of the drug has a correlation with the area of the small pores. On the other hand, as shown in FIG. 6, there was no significant difference in the volatilization rates of Examples 5-8.

The results regarding the persistence of the antifungal effect are shown in Table 6 for container 8d (test fungus: Aspergillus niger), shown in Table 7 for container 8e (test fungus: Penicillium citrinum), and shown in Table 7 for container 8f (test fungus: Cladosporium cladosporioides). is shown in Table 8. In Tables 10 to 12, ">300" indicates that more than 300 colonies were confirmed.

From the results in Table 6, among Examples 5 to 8, the earliest colony formation was confirmed for any of the test bacteria in Example 5, which was the 23rd week. On the other hand, in Examples 6 and 7, colony formation was confirmed for the first time at 37 weeks, and in Example 8, colony formation was confirmed for the first time at 35 weeks. As for the blank, the generation of a large number of colonies was confirmed in all weeks. It should be noted that the antifungal effect varied to some extent between Examples 5 to 8, and there was no correlation only with the total area of the small holes provided in the packages 16(e) to 16(h).

Furthermore, by incorporating 2-hydroxybenzaldehyde into the EVA grains, the antifungal effect could be sustained over a longer period of time than in the case of using the PP grains.

The anti-mold package for the inner space of a storage container according to the present invention prevents the growth of mold in a closed space such as a container during transportation or storage, and contamination of goods due to the growth and proliferation of mold. It is used to prevent

4: Container 5: Lid 7a, d: Potato dextrose agar medium 7b seeded with Aspergillus niger spore liquid, e: Potato dextrose agar medium 7c seeded with Penicillium citrinum spore liquid, f: Cladosporium cladosporioides seeded with spore liquid Potato dextrose agar medium 8a, d: Container 8b containing potato dextrose agar medium seeded with spore liquid of Aspergillus niger, e: Container 8c containing potato dextrose agar medium seeded with spore liquid of Penicillium citrinum, f: Cladosporium cladosporioides Container 13 containing potato dextrose agar medium inoculated with spore liquid: inner surface 16 (a) of container 4: package 16 (b) of Example 1: package 16 (c) of Example 2: Example Package 16 (d) of Example 4: Package 16 (e) of Example 4: Package 16 (f) of Example 5: Package 16 (g) of Example 6: Package 16 of Example 7 ( h): Package of Example 8

Claims (5)

The inside of the bag of the package formed by the gas barrier resin film is filled with a granular resin containing 2-hydroxybenzaldehyde as an active ingredient, and the surface of the package has a diameter penetrating to the inside of the bag. An anti-mold package for a space inside a storage container, characterized in that a small hole of 0.3 mmφ to 0.8 mmφ is formed. 2. An anti-mold package for a storage container interior space according to claim 1, wherein said gas-barrier resin film is made of a resin containing at least one of polyethylene terephthalate and polypropylene. 2. An anti-mold package for a container interior space according to claim 1 , wherein said resin is an ethylene-vinyl acetate copolymer resin. 2. An anti-mold package for a container interior space according to claim 1 , wherein said resin is polypropylene resin or polyethylene resin. 5. The anti-mold package for the internal space of a storage container according to any one of claims 1 to 4, wherein said small holes are formed at 0.2 to 1.0/cm ² .

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