JP6859801B2 - Antifungal resin film, antifungal laminated film and antifungal packaging - Google Patents

Description

The present invention relates to an antifungal resin film, an antifungal laminated film and an antifungal package.

Various preservative packages are used to contain and store the object. For example, when the object to be preserved is one that is orally ingested such as food, the package is required to be able to preserve the object while maintaining good quality. For example, when foods such as fruits and vegetables that have not been heat-treated are stored and stored, the packaging is required to be able to maintain the freshness of the foods without deteriorating the freshness of the foods.

When the fruits and vegetables are stored in the package, there is a problem that the concentration of oxygen and carbon dioxide in the package changes due to the fact that the fruits and vegetables continue to breathe during storage. .. It is known that fruits and vegetables are consumed by breathing actively when the oxygen concentration is high in the package. Therefore, in order to suppress the consumption of fruits and vegetables and maintain the freshness, it is advantageous to lower the oxygen concentration in the package.

Further, when the fruits and vegetables are stored in the package, it is important to reduce the amount of water in the package. This is because if the amount of water in the package becomes excessive, mold will be generated and the fruits and vegetables will be damaged. However, the amount of water in the package is easily affected by the oxygen permeability of the package and the like.

On the other hand, as a package for plant materials such as vegetables, it has a specific range of water vapor transmittance peculiar to the material of the film constituting the package, and further, the pores of this film provide a specific range. A package having an oxygen permeability is disclosed (see Patent Document 1).

Special Fair 7-94263 Gazette

However, even with the package described in Patent Document 1, there is a problem that it is difficult to suppress the growth of mold depending on the storage state of vegetables.

The present invention has been made in view of the above circumstances, and is used to constitute an antifungal packaging that can maintain the freshness of non-heat-treated foods such as fruits and vegetables and has an excellent antifungal effect, and the antifungal packaging. An object of the present invention is to provide a suitable antifungal resin film and an antifungal laminated film.

In order to solve the above problems, the present invention adopts the following configuration.
[1]. An antifungal laminated film comprising an antifungal resin film, a first resin layer, and a second resin layer, wherein the antifungal resin film includes the first resin layer, the second resin layer, and the like. The antifungal resin film is arranged between the two, and contains a antifungal agent containing a compound represented by the following general formula (1) or a salt thereof as an active ingredient, and a resin. have an average diameter 8000μm or less of the through hole, and 40 ° C., is the water vapor permeation amount under an atmosphere of RH 90% is 5g ^/ m 2 · day or more, antifungal laminated film.

（式中、Ｘは炭素数１〜３の直鎖状又は分岐鎖状のアルキレン基であり；Ｒは炭素数１〜３の直鎖状又は分岐鎖状のアルキル基であり；ｍは１〜３の整数であり、ｍが２以上である場合、複数個のＸは互いに同一でも異なっていてもよく；ｎは０〜５の整数であり、ただしｍ＋ｎは６以下であり、ｎが２以上である場合、複数個のＲは互いに同一でも異なっていてもよい。）

(In the formula, X is a linear or branched alkylene group having 1 to 3 carbon atoms; R is a linear or branched alkyl group having 1 to 3 carbon atoms; m is 1 to 1. If it is an integer of 3 and m is 2 or more, the plurality of Xs may be the same or different from each other; n is an integer of 0 to 5, where m + n is 6 or less and n is 2 or more. If, the plurality of Rs may be the same or different from each other.)

[2]. The anti-mold laminated film, 20 ° C., the oxygen permeation amount in an atmosphere of RH 80% is not more than ^{2.0 × 10 8 cc / m 2} · day, antifungal laminate film according to [1].
[3]. The antifungal laminated film according to [1] or [2], wherein the number of through holes of the antifungal laminated film is 40 to 400 / m ^2.
[4]. The antifungal laminated film according to any one of [1] to [3], wherein the content of the antifungal agent in the antifungal resin film is 0.02 to ^{2 g / m 2.}
[5]. The antifungal resin film is selected from the group consisting of urethane-based adhesives, acrylic-based adhesives, titanate-based adhesives, imine-based adhesives, butadiene-based adhesives, polyester-based adhesives, and olefin-based adhesives as the resin. The antifungal laminated film according to any one of [1] to [4], which comprises one or more of the following, and the antifungal resin film has adhesiveness.
[6]. The antifungal laminated film according to any one of [1] to [5], wherein the first resin layer contains linear low-density polyethylene.
[7]. The antifungal laminated film according to any one of [1] to [6], wherein the second resin layer contains one or more selected from the group consisting of polyester, nylon and polypropylene.

[8]. An antifungal package obtained by using the antifungal laminated film according to any one of [1] to [7], and a part of the first resin layers is adhered to each other to form the antifungal package. An antifungal package having an accommodating space and the antifungal resin film being arranged closer to the accommodating space than the second resin layer.
[9]. The antifungal packaging according to [8], which is used for packaging fruits and vegetables.
[10]. The antifungal packaging according to [8] or [9], which is used for packaging citrus fruits.
[11]. An antifungal resin film containing an antifungal agent containing a compound represented by the following general formula (1) or a salt thereof as an active ingredient and a resin, wherein the antifungal resin film has an average diameter of 8000 μm or less. An antifungal resin film having 40 to 400 through holes / m ^2.

（式中、Ｘは炭素数１〜３の直鎖状又は分岐鎖状のアルキレン基であり；Ｒは炭素数１〜３の直鎖状又は分岐鎖状のアルキル基であり；ｍは１〜３の整数であり、ｍが２以上である場合、複数個のＸは互いに同一でも異なっていてもよく；ｎは０〜５の整数であり、ただしｍ＋ｎは６以下であり、ｎが２以上である場合、複数個のＲは互いに同一でも異なっていてもよい。）

(In the formula, X is a linear or branched alkylene group having 1 to 3 carbon atoms; R is a linear or branched alkyl group having 1 to 3 carbon atoms; m is 1 to 1. If it is an integer of 3 and m is 2 or more, the plurality of Xs may be the same or different from each other; n is an integer of 0 to 5, where m + n is 6 or less and n is 2 or more. If, the plurality of Rs may be the same or different from each other.)

According to the present invention, an antifungal packaging material capable of maintaining the freshness of non-heat-treated foods such as fruits and vegetables and having an excellent effect of suppressing the generation of mold, and an antifungal resin film and an antifungal resin film suitable for forming the antifungal packaging body. A mold laminate film is provided.

It is sectional drawing which shows typically one Embodiment of the antifungal laminated film of this invention. It is sectional drawing which shows typically one Embodiment of the antifungal package of this invention.

<< Mold-proof laminated film >>
The antifungal laminated film of the present invention is an antifungal laminated film including an antifungal resin film, a first resin layer, and a second resin layer, and the antifungal resin film is the first resin layer. And the second resin layer, and the antifungal resin film is a compound represented by the following general formula (1) (in the present specification, it may be referred to as "compound (1)". The antifungal laminated film contains a antifungal agent containing or a salt thereof as an active ingredient and a resin, and the antifungal laminated film has through holes having an average diameter of 8000 μm or less and is in an atmosphere of 40 ° C. and 90% RH. The amount of water vapor permeation in the above is 5 g / m ² · day or more.

（式中、Ｘは炭素数１〜３の直鎖状又は分岐鎖状のアルキレン基であり；Ｒは炭素数１〜３の直鎖状又は分岐鎖状のアルキル基であり；ｍは１〜３の整数であり、ｍが２以上である場合、複数個のＸは互いに同一でも異なっていてもよく；ｎは０〜５の整数であり、ただしｍ＋ｎは６以下であり、ｎが２以上である場合、複数個のＲは互いに同一でも異なっていてもよい。）

(In the formula, X is a linear or branched alkylene group having 1 to 3 carbon atoms; R is a linear or branched alkyl group having 1 to 3 carbon atoms; m is 1 to 1. If it is an integer of 3 and m is 2 or more, the plurality of Xs may be the same or different from each other; n is an integer of 0 to 5, where m + n is 6 or less and n is 2 or more. If, the plurality of Rs may be the same or different from each other.)

By using the antifungal resin film, the antifungal laminated film of the present invention has excellent antifungal properties, and is used for producing an antifungal package described later for accommodating and storing an object. Suitable. Since such an antifungal package has the through holes, the oxygen concentration in the accommodation space can be adjusted within an appropriate range, so that the freshness of non-heat-treated foods such as fruits and vegetables can be maintained. Further, such an antifungal package has the through hole, so that the amount of water in the accommodating space can be further adjusted, and further, the antifungal resin film is provided, so that the package can be combined with the contained object. , It is excellent in the effect of suppressing the growth of mold in the accommodation space for accommodating this.
In addition, in this specification, "mold generation" means that mold grows in an object from a state in which it cannot be visually confirmed to a extent to which it can be visually confirmed.

First, the overall configuration of the antifungal laminated film of the present invention will be described.
FIG. 1 is a cross-sectional view schematically showing an embodiment of the antifungal laminated film of the present invention. In addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged and shown, and the dimensional ratio of each component is the same as the actual one. Is not always the case.

The antifungal laminated film 1 shown here includes an antifungal resin film 12, a first resin layer 11, and a second resin layer 13, and the antifungal resin film 12 includes a first resin layer 11 and a second resin layer 13. It is generally configured by being arranged between the resin layer 13 and the resin layer 13. That is, in the antifungal laminated film 1, the first resin layer 11, the antifungal resin film 12, and the second resin layer 13 are laminated in this order in this order, and the exposed surface of the first resin layer 11 is formed. It is configured so that it becomes one surface and the exposed surface of the second resin layer 13 becomes the other surface.

The first resin layer 11 is a layer that is arranged closer to the object to be stored than the antifungal resin film 12 when the target object is stored using the antifungal laminated film 1. For example, in a bag-shaped package manufactured by using the antifungal laminated film 1, the first resin layer 11 is arranged closer to the accommodation space side of the package than the antifungal resin film 12.
Therefore, for example, when the first resin layer 11 is the outermost layer of one of the antifungal laminated films 1, the first resin layer 11 is a layer that comes into contact with the storage object.
In this way, the first resin layer 11 prevents the antifungal resin film 12 from coming into contact with the storage object, thereby suppressing excessive transfer of the antifungal agent to the storage object.

The second resin layer 13 is a layer that is arranged on the side opposite to the storage target side of the antifungal resin film 12 when the target object is stored using the antifungal laminated film 1. For example, in a bag-shaped package manufactured by using the antifungal laminated film 1, the antifungal resin film 12 is arranged closer to the accommodation space side of the second resin layer 13.
The second resin layer 13 has a function of protecting the antifungal resin film 12.

The antifungal laminated film 1 is referred to from one surface (sometimes abbreviated as "first surface" in the present specification) 1a to the other surface (in the present specification, "second surface"). It has a through hole 14 that penetrates up to 1b (which may be abbreviated). In other words, the first surface 1a of the antifungal laminated film 1 is the surface of the second resin layer 13 opposite to the side provided with the antifungal resin film 12 (in this specification, the "first surface"). It may be abbreviated) 13a. In other words, the second surface 1b of the antifungal laminated film 1 is the surface of the first resin layer 11 opposite to the side provided with the antifungal resin film 12 (in this specification, the "second surface"). It may be abbreviated) 11b.
In the antifungal laminated film 1, the through hole 14 is formed by continuously penetrating the second resin layer 13, the antifungal resin film 12, and the first resin layer 11.
Next, the antifungal laminated film of the present invention and its constituent elements will be described in detail.

<First resin layer>
The constituent material of the first resin layer is not particularly limited, but preferred ones are, for example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and metallocene-catalyzed linear low density polyethylene (metallocene LLDPE). ) Etc. can be mentioned.
Further, as a constituent material of the first resin layer, synthetic resins other than these can also be mentioned.

The constituent material of the first resin layer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected according to the purpose.

The first resin layer preferably contains linear low-density polyethylene (LLDPE), and the content of the linear low-density polyethylene in the first resin layer is preferably 60% by mass or more, preferably 80% by mass. The above is more preferable, and 90% by mass or more is particularly preferable, and for example, it may be 99% by mass or more, or 100% by mass.

The oxygen gas permeation amount of the first resin layer in an atmosphere of 25 ° C. and 65% RH (relative humidity) ^{is preferably 3000 cm 3} / m ² · atm · day or more, preferably ^{3000 to 10000 cm 3} / m ² ·. more preferably atm · day, more preferably from ^{3000~8000cm 3 / m 2 · atm ·} day, and particularly preferably ^{3000~6000cm 3 / m 2 · atm ·} day. When the oxygen gas permeation amount of the first resin layer is equal to or higher than the lower limit value, the antifungal agent that has migrated from the inside of the antifungal resin film to the side of the first resin layer is removed from the outside (through the first resin layer). It easily migrates to the outside of the first resin layer side of the antifungal laminated film). As a result, the antifungal laminated film exhibits an excellent antifungal effect.
The fungicide will be described in detail later.

The oxygen gas permeation amount of the first resin layer can be adjusted, for example, by adjusting the type or thickness of the constituent material of the first resin layer.

The first resin layer may be composed of one layer (single layer) or may be composed of two or more layers. When the first resin layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

In the present specification, not only in the case of the first resin layer, but also in the case of "a plurality of layers may be the same or different from each other", "all layers may be the same or all layers". May be different, and only some of the layers may be the same. ”Furthermore,“ a plurality of layers are different from each other ”means that“ at least one of the constituent materials and the thickness of each layer is different from each other. It means that.

The thickness of the first resin layer is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 150 μm, and particularly preferably 15 to 100 μm. When the thickness of the first resin layer is at least the above lower limit value, the strength of the first resin layer is further improved, and the excessive transfer of the fungicide to the storage object is further suppressed. Further, when the thickness of the first resin layer is not more than the upper limit value, the antifungal effect of the antifungal laminated film is further improved.
When the first resin layer is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the above-mentioned preferable thickness of the first resin layer.

<Second resin layer>
The constituent material of the second resin layer may be appropriately selected depending on the intended purpose, and is not particularly limited, but is not particularly limited, but is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate ( PEN), polyesters such as polybutylene terephthalate (PBN); nylon; polypropylene (PP) and the like.
Further, as a constituent material of the second resin layer, synthetic resins other than these can also be mentioned.

The constituent material of the second resin layer may be only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected according to the purpose.

The second resin layer preferably contains one or more selected from the group consisting of polyester, nylon and polypropylene, and the total content of polyester, nylon and polypropylene in the second resin layer is 80% by mass or more. It is preferably 90% by mass or more, more preferably 95% by mass or more, and for example, 99% by mass or more, or 100% by mass.

The oxygen gas permeation amount of the second resin layer in an atmosphere of 25 ° C. and 65% RH (relative humidity) ^{is preferably 3000 cm 3} / m ² · atm · day or less, and is preferably 2500 cm ³ / m ² · atm ·. It is more preferably less than or equal to day, and particularly preferably less than or equal to ^{2000 cm 3} / m ^{2 · atm · day.}
The smaller the upper limit of the oxygen gas permeation amount of the second resin layer, the more the antifungal agent is transferred from the inside of the antifungal resin film to the second resin layer and the outside (antifungal) via the second resin layer. The migration of the laminated film to the outside of the second resin layer side) is effectively suppressed. Therefore, since the amount of the antifungal agent transferred from the inside of the antifungal resin film to the storage object side can be maintained at an appropriate level for a long period of time, the antifungal laminated film exhibits a more excellent antifungal effect. Further, for example, when the target product is contained in a bag-shaped package manufactured by using the antifungal laminated film and sealed, the transfer of the antifungal agent to the outside of the package is suppressed. It is functionally preferable because it hardly reminds us of the use of an antifungal agent during storage of the target product.
Further, the smaller the upper limit value of the oxygen gas permeation amount of the second resin layer is, the more oxygen gas is introduced from the outside (outside of the second resin layer side of the antifungal laminated film) to the inside via the second resin layer. The transition is effectively suppressed. Therefore, the effect of preserving the target product without deteriorating the quality becomes higher.

On the other hand, the lower limit of the oxygen gas permeation amount of the second resin layer in an atmosphere of 25 ° C. and 65% RH (relative humidity) is not particularly limited, and is, for example, 50 cm ³ / m ² · atm · day, 500 cm ³ It can be either / m ² · atm · day and 1000 cm ³ / m ² · atm · day, but these are examples.

The oxygen gas permeation amount of the second resin layer can be adjusted, for example, by adjusting the type or thickness of the constituent material of the second resin layer.

The oxygen gas permeation amount of the first resin layer and the second resin layer are both values measured in accordance with JIS K7126B.

The second resin layer may be composed of one layer (single layer) or may be composed of two or more layers. When the second resin layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the second resin layer is not particularly limited, but is preferably 2 to 100 μm, more preferably 5 to 70 μm, and particularly preferably 8 to 40 μm. When the thickness of the second resin layer is equal to or greater than the lower limit, the strength of the second resin layer is further improved, and the same effect as when the oxygen gas permeation amount of the second resin layer is reduced is more remarkable. Obtained in. Further, when the thickness of the second resin layer is not more than the upper limit value, it is possible to prevent the thickness from becoming excessive.
When the second resin layer is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the above-mentioned preferable thickness of the second resin layer.

<Antifungal resin film>
The antifungal resin film contains an antifungal agent containing the compound (1) or a salt thereof as an active ingredient, and a resin. Compound (1) and a salt thereof will be described in detail later.
The antifungal resin film has excellent antifungal properties because it contains the antifungal agent.

In the antifungal resin film, the contained compound (1) or a salt thereof gradually migrates from the inside to the outside of the antifungal resin film to exhibit antifungal properties.
For example, when a volatile compound (1) or a salt thereof is used, this component can be transferred to the outside of the antifungal resin film in a gaseous state.

The antifungal resin film can be produced by using a resin composition containing components for forming the antifungal resin film, such as the antifungal agent and the resin. More specifically, the antifungal resin film can be obtained by applying the resin composition to the surface to be formed of the antifungal resin film and drying it if necessary.
An antifungal resin film composed of a plurality of layers as described later can be produced, for example, by producing a plurality of one-layer (single-layer) antifungal resin films and laminating them.

The resin composition uses, for example, various coaters such as a spin coater, an air knife coater, a curtain coater, a die coater, a blade coater, a roll coater, a gate roll coater, a bar coater, a rod coater, a gravure coater, and a multi-coater. Can be painted.

[resin]
The resin is a component necessary for maintaining the shape of the antifungal resin film. The resin is not particularly limited as long as it has such a function, and may be either an adhesive resin (sometimes referred to as an "adhesive" in the present specification) or a non-adhesive resin. It is good, but it is preferably an adhesive resin. By using an adhesive resin (adhesive) as the resin, the antifungal resin film can be made to have adhesiveness (that is, an adhesive antifungal resin film). For example, a separate adhesive layer can be used. The antifungal laminated film described later can be formed without providing the film.

Preferred adhesive resins include, for example, urethane-based adhesives such as polyurethane (adhesive resins having urethane bonds); acrylic adhesives such as acrylic copolymer resins (adhesive resins having (meth) acryloyl groups); Titanate-based adhesive (adhesive resin obtained using titanium acid ester); imine-based adhesive (adhesive resin obtained using ethyleneimine); butadiene-based adhesive such as styrene-butadiene copolymer (adhesive resin obtained using ethyleneimine) Adhesive resin obtained by using butadiene as a monomer component); Polyester-based adhesive such as polyvinyl acetate (adhesive resin having ester bond); Olefin-based adhesive such as isobutene / maleic anhydride copolymer resin (monomer) Adhesive resin obtained by using olefin as a component) and the like can be mentioned.

In the antifungal resin film, the resin may be only one type or two or more types, and when two or more types are used, the combination and ratio thereof can be arbitrarily selected according to the purpose.
For example, as the resin, only one or more non-adhesive resins having no adhesiveness may be used, one or two or more adhesive resins may be used, or the non-adhesive resin. And the adhesive resin may be used alone or in combination of two or more.

The antifungal resin film is selected from the group consisting of urethane-based adhesives, acrylic-based adhesives, titanate-based adhesives, imine-based adhesives, butadiene-based adhesives, polyester-based adhesives, and olefin-based adhesives as the resin. It is preferable that the resin contains one or more of the following substances and has adhesiveness.

[Other ingredients]
The antifungal resin film and the resin composition may contain other components in addition to the antifungal agent and the resin.
The other components in the antifungal resin film and the resin composition are not particularly limited as long as the effects of the present invention are not impaired, and can be arbitrarily selected.
In the antifungal resin film and the resin composition, the other components may be only one kind or two or more kinds, and when they are two or more kinds, the combination and the ratio thereof can be arbitrarily selected according to the purpose.

Examples of the other components in the antifungal resin film and the resin composition include a curing agent and a cross-linking agent. These act on the resin.

The resin composition may contain other components that do not correspond to any of the curing agent and the cross-linking agent, if necessary, and the preferable other components in this case include a solvent.

The solvent is for improving the handleability of the resin composition, and the type thereof is not particularly limited as long as the effect of the present invention is not impaired.
Preferred solvents include, for example, organic solvents and water.

Examples of the organic solvent include esters (carboxylic acid esters) such as ethyl acetate and butyl acetate; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and the like. Alcohols such as 2-methyl-2-propanol; ketones such as methyl ethyl ketone and acetone; ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; aromatic hydrocarbons such as toluene and xylene can be mentioned. ..

In the antifungal resin film and the resin composition, the solvent may be only one kind, two or more kinds, and when two or more kinds, the combination and the ratio thereof can be arbitrarily selected according to an object. For example, when two or more kinds of solvents are used in combination, only two or more kinds of organic solvents may be used in combination, and a mixed solvent of only organic solvents may be used, or one or more kinds of organic solvents and water may be used in combination. Then, an aqueous mixed solvent may be used.

The content of antifungal agent antifungal resin film is preferably 0.02~2g / ^{m 2,} more preferably from 0.02~1.75g / ^{m 2,} 0.03~1. It is particularly preferably 5 g / m ^2. When the content of the antifungal agent is at least the above lower limit value, the antifungal effect of the antifungal laminated film becomes higher. Further, when the content of the antifungal agent is not more than the above upper limit value, the excessive use of the antifungal agent is suppressed.

Total content of compound (1) and its salt in the antifungal resin film (in other words, the ratio of the total content of compound (1) and its salt to the total content of components other than the solvent in the resin composition) Is preferably 10 to 44% by mass, more preferably 14 to 40% by mass, and particularly preferably 18 to 36% by mass. When the total content of the compound (1) and its salt is at least the above lower limit value, the antifungal effect of the antifungal laminated film becomes higher. Further, when the total content of the compound (1) and its salt is not more than the above upper limit value, the compound (1) and its salt are more stably held in the antifungal resin film with high uniformity.

The content of the resin in the antifungal resin film (in other words, the ratio of the content of the resin to the total content of the components other than the solvent in the resin composition) is preferably 30 to 90% by mass. , 40 to 75% by mass, more preferably 50 to 65% by mass. When the content of the resin is at least the lower limit value, the strength of the antifungal resin film is further improved. Further, when the content of the resin is not more than the upper limit value, the antifungal effect of the antifungal resin film is further improved.

The content of the other component of the antifungal resin film (in other words, the ratio of the content of the other component to the total content of the component other than the solvent in the resin composition) is the content of the other component. It may be appropriately selected according to the type, and is not particularly limited.

For example, when the other component is the curing agent or the cross-linking agent, the ratio of the content of the other component to the content of the resin in the antifungal resin film and the resin composition is 10 to 40 mass. %, More preferably 20 to 30% by mass. When the ratio is equal to or higher than the lower limit, the effect of using the other components is more remarkable, and when the ratio is equal to or lower than the upper limit, excessive use of the other components is suppressed. ..

When the resin composition contains a solvent, the content of the solvent is preferably 10 to 80% by mass, more preferably 40 to 70% by mass. When the content of the solvent is at least the above lower limit value, the effect of using the solvent is more remarkable, and when the content of the solvent is at least the above upper limit value, the excessive use of the solvent is suppressed. ..

The content of the other component of the antifungal resin film, which does not correspond to any of the solvent, the curing agent and the cross-linking agent, can be, for example, 0 to 10% by mass.

The antifungal resin film may be composed of one layer (single layer) or may be composed of two or more layers. When the antifungal resin film is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the antifungal resin film may be appropriately selected depending on the intended use, and is not particularly limited.
When, for example, a bag-shaped package is produced using the antifungal resin film, the thickness of the antifungal resin film is preferably 0.1 to 15 μm, preferably 0.2 to 12 μm. More preferably, it is particularly preferably 0.3 to 10 μm, and for example, it may be 0.3 to 7.5 μm or the like.
When the antifungal resin film is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the above-mentioned preferable thickness of the antifungal resin film.

The antifungal laminated film of the present invention may further include other layers in addition to the first resin layer, the antifungal resin film and the second resin layer, as long as the effects of the present invention are not impaired.
The other layers are not particularly limited and may be appropriately selected depending on the intended purpose.

However, in the antifungal laminated film of the present invention, it is preferable that the first resin layer, the antifungal resin film and the second resin layer are laminated in direct contact with each other in this order. As described above, since none of the other layers is provided between the first resin layer and the antifungal resin film and between the antifungal resin film and the second resin layer, the antifungal lamination of the present invention is provided. The film has an even better antifungal effect.

Further, it is preferable that the antifungal laminated film of the present invention is not provided with the other layers on the side opposite to the side of the first resin layer provided with the antifungal resin film. As described above, since the first resin layer is the outermost layer of one of the antifungal laminated films, the antifungal laminated film of the present invention is further excellent in the antifungal effect.
When the antifungal laminated film of the present invention includes the other layer, it is preferable that the other layer is provided on the side opposite to the side of the second resin layer provided with the antifungal resin film.

In addition to having the above-mentioned laminated structure, the antifungal laminated film of the present invention has through holes having an average diameter (average diameter) of 8000 μm or less (for example, the through holes 14 in the antifungal laminated film 1 shown in FIG. 1). Has.

The shape of the opening of the through hole on the surface of the antifungal laminated film and the shape of the opening of the through hole in the cross section perpendicular to the longitudinal direction thereof are not particularly limited, and are, for example, circular; elliptical. A polygonal shape such as a triangular shape or a quadrangular shape; a shape in which two or more types of shapes selected from the group consisting of a circular shape, an elliptical shape, and a polygonal shape are combined may be used. However, the shape is preferably circular because it is easy to form through holes.
In the present specification, the "opening of the through hole" means the opening of the through hole on the surface of the above-mentioned antifungal laminated film and the through hole perpendicular to the longitudinal direction thereof, unless otherwise specified. It shall mean both an opening in a cross section.

When the shape of the opening of the through hole is other than a circular shape, the diameter of the through hole is the maximum length (maximum diameter) of the lengths of the line segments connecting two different points of the through holes. It shall mean.

The average diameter of the through holes is preferably 50 to 8000 μm, more preferably 60 to 7500 μm, and particularly preferably 70 to 7000 μm. When the average diameter of the through holes is in such a range, oxygen and carbon dioxide are stored when the contained material (non-heat-treated food) is stored in the storage space of the package made by using the antifungal laminated film. The concentration of carbon and water vapor can be adjusted in a more suitable range in a well-balanced manner. Further, when the average diameter of the through holes is at least the above lower limit value, the production of the antifungal laminated film becomes easier.

The number of the through holes with fungicide laminated film is not particularly limited, but is preferably 40 to 400 pieces / ^{m 2,} more preferably is 50 to 360 pieces / ^{m 2,} 60-320 pieces / more preferably m ^2, and particularly preferably 60 to 280 pieces / ^{m 2.} When the number of through holes is in such a range, oxygen and carbon dioxide are stored when the contained material (non-heat-treated food) is stored in the storage space of the package made by using the antifungal laminated film. And the concentration of water vapor can be adjusted in a more suitable range in a well-balanced manner.

The number of through holes of the antifungal laminated film, that ^{is, the number of through holes per unit area (1 m 2} ) of the antifungal laminated film is the area of the antifungal laminated film and the penetration per one antifungal laminated film. It can be adjusted by adjusting the number of holes and one or both of them.

The area of the antifungal laminated film may be appropriately adjusted according to the use of the antifungal laminated film, and is not particularly limited, but is preferably 0.01 to 1.5 ^{m 2, for example, 0.015 to 1.} It is more preferably 2 m ^{2 and particularly preferably 0.02 to 1} m 2, for example, 0.02 to 0.5 m ² , 0.02 to 0.3 m ² , and 0.02 to 0.1 m. ^It may be any of 2nd grade.

The number of through holes per antifungal laminated film may be one or more, may be one, or may be two or more, and may be appropriately adjusted according to the area and application of the antifungal laminated film. .. The number of through holes per antifungal laminated film is, for example, preferably 1 to 30, more preferably 1 to 25, and particularly preferably 1 to 20.

The position of the through hole in the antifungal laminated film is not particularly limited, but it is preferably a region other than the adhesive region at the time of manufacturing the antifungal package described later. By doing so, all the through holes in the antifungal laminated film can be effectively made to function even in the antifungal package.

Antifungal laminated film, 40 ° C., the water vapor permeation amount under an atmosphere of RH 90% is at 5g ^/ m 2 · day or more, preferably 7g ^/ m 2 · day or more, ^8g / m 2 · day The above is more preferable, and the amount of 10 g / m ² · day or more is particularly preferable. When the water vapor permeation amount of the antifungal laminated film is equal to or more than the lower limit value, the generation of mold in the contained material is remarkably suppressed in the accommodating space of the package manufactured by using the antifungal laminated film. ..

The upper limit of the amount of water vapor permeation of the antifungal laminated film in an atmosphere of 40 ° C. and 90% RH is not particularly limited. However, the antifungal laminated film has a higher effect of suppressing drying and wilting of the contained material (non-heat-treated foods, especially fruits and vegetables) in the accommodating space of the package made by using the antifungal laminated film. The amount of water vapor permeation ^{is preferably 50 g / m 2} · day or less. The amount of water vapor permeation of the antifungal laminated film is set by appropriately combining any of the above lower limit values and upper limit values. It is preferably within the range.

The amount of water vapor permeation of the antifungal laminated film can be adjusted by, for example, adjusting the size or number of the through holes, or the type or thickness of the constituent material of each layer constituting the antifungal laminated film.

The amount of water vapor permeation of the antifungal laminated film can be measured in accordance with JIS K 7129B.

The amount of oxygen permeated by the antifungal laminated film in an atmosphere of 20 ° C. and 80% RH is not particularly limited ^{, but is preferably 2.0 × 10 8} cc / m ² · day or less, and 1.5 × 10 more preferably ⁸ cc ^/ m 2 · day or less, particularly preferably not more than ^{1.0 × 10 8 cc / m 2} · day. When the oxygen permeation amount of the antifungal laminated film is equal to or less than the upper limit value, the contained material (non-heat-treated food) is of more preferable quality in the accommodating space of the package produced by using the antifungal laminated film. Can be saved with. In particular, when the non-heat-treated food is fruits and vegetables, the fruits and vegetables during storage breathe, but by suppressing the increase in oxygen concentration in the containment space, the breathing of fruits and vegetables is suppressed and the consumption of fruits and vegetables is suppressed. , Can store fruits and vegetables with higher freshness.

The lower limit of the oxygen permeation amount of the antifungal laminated film in an atmosphere of 20 ° C. and 80% RH is not particularly limited. However, the oxygen permeation amount of the antifungal laminated film is 30 g / m in that the contained material (non-heat-treated food, particularly fruits and vegetables) is prevented from becoming oxygen deficient in the contained space of the package. ^The oxygen permeation amount of the antifungal laminated film is preferably in the range set by appropriately combining any of the above lower limit values and upper limit values.

The oxygen permeation amount of the antifungal laminated film can be adjusted by, for example, adjusting the size or number of the through holes, or the type or thickness of the constituent material of each layer constituting the antifungal laminated film.

The oxygen permeation amount of the antifungal laminated film can be measured by, for example, the following method.
That is, in the atmosphere, a package is prepared using an antifungal laminated film, sealed, and then the atmosphere in the storage space of the package is replaced with nitrogen gas having a purity of 99.9% or more and V (cc). The elapsed time from the completion of replacement with nitrogen gas is t (hr), and the oxygen concentration inside the bag at this time is C _t (%), and t = 0 (that is, when replacement with nitrogen gas is completed). the _{C 0} in the case of measures, after measuring the _{C 0,} the package, 20 ° C., and stored under the conditions of RH 80%, to measure the _{C t} at the stage of t ≧ 3, the following formula (i ), The oxygen permeation amount F (cc / m ² · day) is calculated.
The atmosphere in the storage space of the package after sealing can be replaced with nitrogen gas having a purity of 99.9% or more by using, for example, an injection needle. Further, _Ct is obtained by preparing a calibration curve in advance and using this calibration curve.
F = 1.143 × (C _{t −} C ₀ ) × V / t ・ ・ ・ ・ (i)

<< Antifungal resin film with through holes >>
In the antifungal laminated film, each layer (the first resin layer, the antifungal resin film, the second resin layer, and the other layers provided as needed) constituting the same is between adjacent layers. It has through holes that are continuously formed. Of these, the antifungal resin film having through holes is a novel one, and can be useful by itself in applications other than the antifungal laminated film.
That is, a preferable antifungal resin film having such through holes is, for example, an antifungal resin film containing the antifungal agent and a resin, and the antifungal resin film has an average diameter. Examples thereof include those having through holes of 8000 μm or less in ^{a number of 40 to 400 pieces / m 2.}

<< Manufacturing method of antifungal laminated film >>
The antifungal laminated film of the present invention can be produced by using the above-mentioned resin composition for an antifungal resin film and applying a known production method of a multilayer laminated film.
For example, the resin composition is applied to the surface (one side) of either one of the first resin layer and the second resin layer and dried as necessary to form a mold-proof resin film. A first laminated body is formed by laminating a resin layer or a second resin layer and an antifungal resin film. The method for forming the antifungal resin film at this time is the same as the method for producing the antifungal resin film described above.

Next, the exposed surface of the antifungal resin film in the first laminated body (the surface on which the first resin layer or the second resin layer is not provided) and the other surface (one side) of the first resin layer and the second resin layer. And are bonded together to form a second laminated body. Here, "the other of the first resin layer and the second resin layer" refers to the second resin layer when the one laminated on the antifungal resin film in the first laminated body is the first resin layer. This means that when the second resin layer is laminated on the antifungal resin film in the first laminated body, it means the first resin layer.
The first laminated body and the second resin layer or the first resin layer can be bonded by applying various known laminating methods.

Next, the second laminated body is formed with the desired number of through holes at the desired location.
The through hole can be formed by a known method such as a method of piercing the second laminated body with a needle or a method of irradiating a laser.

As described above, the antifungal laminated film can be obtained. However, in the case of producing the antifungal laminated film provided with other layers in addition to the first resin layer, the antifungal resin film and the second resin layer, the above-mentioned In the manufacturing method of the above, an additional step of forming the other layer is performed at an appropriate timing so that the other layer is arranged at a desired laminated position, or the other layer of the preformed layer is formed. You can add the paste. In this case, the second laminated body may be formed with the other layers, and through holes may be formed in the second laminated body.

Up to this point, as a method for producing the antifungal laminated film, a method having a step of simultaneously forming the antifungal resin film and the first laminated body by using the resin composition has been described. However, other methods for producing the antifungal laminated film can be mentioned, and for example, a manufacturing method having a step of forming the first laminated body using a preformed antifungal resin film can also be mentioned.

In the case of using the preformed antifungal resin film as described above, for example, the antifungal laminated film may be produced as follows.
First, the antifungal resin film is formed on the peeled surface of the peeled film having the peeled surface by using the resin composition. The method for forming the antifungal resin film at this time is the same as the method for producing the antifungal resin film described above. The formed antifungal resin film may be provided with a release film on the surface on the side not provided with the release film.

Next, the release film is removed at an appropriate timing, the first resin layer is attached to one surface of the antifungal resin film, and the second resin layer is attached to the other surface of the antifungal resin film, whereby the second lamination is performed. Form the body. One of the antifungal resin film and the first resin layer and the antifungal resin film and the second resin layer may be bonded first, and the other may be performed later and sequentially. And may be done at the same time.

Next, the antifungal laminated film is obtained by forming the desired number of through holes in the target portion of the second laminated body by the same method as described above.
Also in this method, when the antifungal laminated film including the other layers is produced, in the above-mentioned production method, the other layers are arranged at a desired lamination position at an appropriate timing. The step of forming the other layer may be additionally performed, or the bonding of the other layer already formed may be added. In this case, the second laminated body may be formed with the other layers, and through holes may be formed in the second laminated body.

[Antifungal agent]
Next, the antifungal agent contained in the antifungal resin film will be described.
The fungicide is a novel one containing compound (1) or a salt thereof as an active ingredient.
By coexisting with the target object to be preserved, the fungicide suppresses the growth of mold in the object to be preserved.

(Compound (1))
Compound (1) has antifungal properties.
In the general formula (1), X is a linear or branched alkylene group having 1 to 3 carbon atoms, as such alkylene groups, and more specifically, a methylene group (-CH 2 _-), Examples thereof include an ethylene group (-CH ₂ CH _2- ), a propylene group (-CH (CH ₃ ) CH _2- , a methyl ethylene group), and a trimethylene group (-CH ₂ CH ₂ CH _2- ).

In the general formula (1), R is a linear or branched alkyl group having 1 to 3 carbon atoms, and as such an alkyl group, more specifically, a methyl group (-CH ₃ ) or ethyl. Examples include a group (-CH ₂ CH ₃ ), an n-propyl group (-CH ₂ CH ₂ CH ₃ ), and an isopropyl group (-CH (CH ₃ ) ₂ ).

In the general formula (1), m is an integer of 1 to 3, and is represented by the general formula "-O-X-OH (in the formula, X is the same as above)" in one molecule of the compound (1). Indicates the number of groups to be produced.
When m is 2 or more (that is, 2 or 3), a plurality of (that is, 2 or 3) Xs may be the same or different from each other. That is, when m is 2 or more, X may be all the same, all may be different, or only a part may be the same.

Regardless of the value of m, the bonding position of the group represented by the general formula "-OX-OH" to the benzene ring skeleton is not particularly limited.
However, when m is 2, the two carbon atoms constituting the benzene ring skeleton to which the group represented by the general formula "-OX-OH" is bonded are adjacent to each other. It is preferable that there is no such thing.
When m is 3, at least 2 of the 3 carbon atoms constituting the benzene ring skeleton to which the group represented by the general formula "-OX-OH" is bonded. It is preferable that the carbon atoms of the above are not adjacent to each other, and it is more preferable that all three carbon atoms are not adjacent to each other.

In the general formula (1), n is an integer of 0 to 5, and indicates the number of R in one molecule of compound (1). However, m + n is 6 or less.
When n is 2 or more (that is, 2, 3, 4 or 5), a plurality of (that is, 2, 3, 4, or 5) Rs may be the same or different from each other. That is, when n is 2 or more, R may be all the same, all may be different, or only a part may be the same.

Regardless of the value of n, the bond position of R to the benzene ring skeleton is not particularly limited.
However, when n is 2, it is preferable that the two carbon atoms constituting the benzene ring skeleton to which R is bonded are not adjacent to each other.
Further, when n is 3, it is preferable that at least two carbon atoms among the three carbon atoms constituting the benzene ring skeleton to which R is bonded are not adjacent to each other. More preferably, not all of the carbon atoms are adjacent to each other.
Further, when n is 4, one carbon atom among the four carbon atoms constituting the benzene ring skeleton to which R is bonded is any of the remaining three carbon atoms. It is preferable that they are not adjacent to each other.

The relationship between the relative bond positions of R and the group represented by the general formula "-OX-OH" in the benzene ring skeleton is not particularly limited.

Examples of the compound (1) when m is 1 include a compound represented by the following general formula (1) -1A (in the present specification, it may be referred to as "compound (1) -1A"). Be done.

（式中、Ｘ及びＲは上記と同じであり、ｎ１は０〜５の整数である。）

(In the formula, X and R are the same as above, and n1 is an integer from 0 to 5.)

In the general formula (1) -1A, X and R are the same as X and R in the general formula (1).
In the general formula (1) -1A, n1 is an integer of 0 to 5, which is the same as n in the general formula (1).

Examples of the compound (1) when m is 2, include the compound represented by the following general formula (1) -2A, the compound represented by the following general formula (1) -2B, and the following general formula (1)-. Compounds represented by 2C (in the present specification, "Compound (1) -2A", "Compound (1) -2B", "Compound (1) -2C", respectively, corresponding to the reference numerals. (Sometimes referred to as).

（式中、Ｘ及びＲは上記と同じであり、ｎ２は０〜４の整数である。）

(In the formula, X and R are the same as above, and n2 is an integer from 0 to 4.)

In the general formulas (1) -2A to (1) -2C, X and R are the same as X and R in the general formula (1).
In the general formulas (1) -2A to (1) -2C, n2 is an integer of 0 to 4, and is the same as n in the general formula (1) except that it does not become 5.

As the compound (1) when m is 3, the compound represented by the following general formula (1) -3A, the compound represented by the following general formula (1) -3B, and the following general formula (1)- Compounds represented by 3C (in this specification, "Compound (1) -3A", "Compound (1) -3B", "Compound (1) -3C", respectively, corresponding to the reference numerals. (Sometimes referred to as).

（式中、Ｘ及びＲは上記と同じであり、ｎ３は０〜３の整数である。）

(In the formula, X and R are the same as above, and n3 is an integer from 0 to 3.)

In the general formulas (1) -3A to (1) -3C, X and R are the same as X and R in the general formula (1).
In the general formulas (1) -3A to (1) -3C, n3 is an integer of 0 to 3, and is the same as n in the general formula (1) except that it does not become 4 and 5. is there.

In compound (1), m is preferably 1 or 2, and more preferably 1. Such compound (1) not only has an excellent antifungal effect, but can also be produced more easily and inexpensively.

Examples of the compound (1) when n is 0 include a compound represented by the following general formula (1) -0 (in the present specification, it may be referred to as “compound (1) -0”). Be done.

（式中、Ｘ及びＲは上記と同じであり、ｍ０は１〜３の整数である。）

(In the formula, X and R are the same as above, and m0 is an integer of 1-3.)

In the general formula (1) -0, X and R are the same as X and R in the general formula (1).
In the general formula (1) -0, m0 is an integer of 1 to 3, which is the same as m in the general formula (1).

Examples of the compound (1) when n is 1 include a compound represented by the following general formula (1) -1a (in the present specification, it may be referred to as "compound (1) -1a"). Be done.

（式中、Ｘ及びＲは上記と同じであり、ｍ１は１〜３の整数である。）

(In the formula, X and R are the same as above, and m1 is an integer of 1 to 3.)

In the general formula (1) -1a, X and R are the same as X and R in the general formula (1).
In the general formula (1) -1a, m1 is an integer of 1 to 3, which is the same as m in the general formula (1).

Examples of the compound (1) when n is 2 include a compound represented by the following general formula (1) -2a, a compound represented by the following general formula (1) -2b, and the following general formula (1)-. Compounds represented by 2c (in the present specification, "Compound (1) -2a", "Compound (1) -2b", "Compound (1) -2c", respectively, corresponding to the reference numerals. (Sometimes referred to as).

（式中、Ｘ及びＲは上記と同じであり、ｍ２は１〜３の整数である。）

(In the formula, X and R are the same as above, and m2 is an integer of 1 to 3.)

In the general formulas (1) -2a to (1) -2c, X and R are the same as X and R in the general formula (1).
In the general formulas (1) -2A to (1) -2C, m2 is an integer of 1 to 3, which is the same as m in the general formula (1).

Examples of the compound (1) when n is 3 include a compound represented by the following general formula (1) -3a, a compound represented by the following general formula (1) -3b, and the following general formula (1)-. Compounds represented by 3c (in the present specification, "Compound (1) -3a", "Compound (1) -3b", "Compound (1) -3c", respectively, corresponding to the reference numerals. (Sometimes referred to as).

（式中、Ｘ及びＲは上記と同じであり、ｍ３は１〜３の整数である。）

(In the formula, X and R are the same as above, and m3 is an integer of 1 to 3.)

In the general formulas (1) -3a to (1) -3c, X and R are the same as X and R in the general formula (1).
In the general formulas (1) -3A to (1) -3C, m3 is an integer of 1 to 3, which is the same as m in the general formula (1).

Examples of the compound (1) when n is 4, include the compound represented by the following general formula (1) -4a, the compound represented by the following general formula (1) -4b, and the following general formula (1)-. Compounds represented by 4c (in the present specification, "Compound (1) -4a", "Compound (1) -4b", "Compound (1) -4c", respectively, corresponding to the reference numerals. (Sometimes referred to as).

（式中、Ｘ及びＲは上記と同じであり、ｍ４は１又は２である。）

(In the formula, X and R are the same as above, and m4 is 1 or 2.)

In the general formulas (1) -4a to (1) -4c, X and R are the same as X and R in the general formula (1).
In the general formulas (1) -4a to (1) -4c, m4 is 1 or 2, and is the same as m in the general formula (1) except that it does not become 3.

Examples of the compound (1) when n is 5 include a compound represented by the following general formula (1) -5a (in the present specification, it may be referred to as "compound (1) -5a"). Be done.

（式中、Ｘ及びＲは上記と同じである。）

(In the formula, X and R are the same as above.)

In the general formula (1) -5a, X and R are the same as X and R in the general formula (1).
The compound represented by the general formula (1) -5a corresponds to the compound (1) when m in the general formula (1) is 1.

In compound (1), n is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, further preferably an integer of 0 to 2, and preferably 0 or 1. Especially preferable. Such compound (1) not only has an excellent antifungal effect, but can also be produced more easily and inexpensively.

In compound (1), both m and n are preferably any of the above-mentioned preferable numerical values.
For example, in compound (1), m is preferably 1 or 2 and n is preferably an integer of 0-4, more preferably m is 1 or 2 and n is an integer of 0-3. , M is 1 or 2 and n is an integer of 0 to 2, and m is 1 and n is 0 or 1.

A particularly preferable compound (1) is, for example, a compound represented by the following general formula (1) -1A-0 (in the present specification, it may be referred to as "Compound (1) -1A-0". ), And the compound represented by the following general formula (1) -1A-1, the compound (1) -1A-0 is most preferable.

（式中、Ｘ及びＲは上記と同じである。）

(In the formula, X and R are the same as above.)

<Salt of compound (1)>
The salt of compound (1) has antifungal properties.
Table In ^- The salt of compound (1), for example, groups anion represented by the formula in the compound (1) "-O-X-OH" (i.e., formula "-O-X-O" (In the formula, X is the same as above)) (in this specification, it may be referred to as "anion derived from compound (1)") and a cation. The salt that has been added can be mentioned.

The valence of the cation forming the salt of compound (1) is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more. When the cation is monovalent, the number of the cation forming the salt of the compound (1) and the number of anions derived from the compound (1) are both 1. When the cation has a p-valent value (p is an integer of 2 or more), the number of the cations forming the salt of the compound (1) is usually 1, and the anion derived from the compound (1) is formed. The number is p or less, preferably p.

As described above, the number of cations constituting the salt of one molecule of compound (1) may be only one, two or more, and when two or more, these cations may be all the same. It may be all different, or only partly the same.
However, the salt of compound (1) is electrically neutral as a whole molecule, that is, the total value of the valences of cations and the total value of the valences of anions in one molecule of compound (1) are the same. Is preferable.

The cation forming the salt of the compound (1) together with the anion derived from the compound (1) is not particularly limited, and may be either an inorganic cation or an organic cation.

Among the cations, examples of the inorganic cation include ^{alkali metal ions such as lithium ion (Li +} ), sodium ion (Na ⁺ ), and potassium ion (K ⁺ ); magnesium ion (Mg ²⁺ ), and calcium ion (Ca). Alkaline earth metal ions such as ²⁺ ) and barium ion (Ba ^{2+ ); typical metal ions such as aluminum ion (Al 3+} ), zinc ion (Zn ²⁺ ), tin ion (Sn ²⁺ , Sn ⁴⁺ ); copper ion (copper ion) Cu ^{+, Cu 2+),} iron ions ^(Fe 2+, Fe ^3+), manganese ion, transition metal ion nickel ion or the like; ammonium ion _(NH ^{4 +)} ions in the non-metal, and the like.

In the fungicide, only one type of active ingredient may be used, or two or more types may be used, and when two or more types of active ingredients are used, the combination and ratio thereof can be arbitrarily selected according to the purpose.
For example, the fungicide may contain only one or two or more compounds (1) as an active ingredient, or may contain only one or two or more salts of compound (1). Alternatively, the compound (1) and the salt of the compound (1) may be contained in one kind or two or more kinds, respectively.

The compound (1) and a salt thereof are preferably those that can be used as food additives. Here, "food additive" means an additive approved by the Ministry of Health, Labor and Welfare of Japan as of March 12, 2013.

The compound (1) and a salt thereof are preferably volatile. The volatile compound (1) and its salt are advantageous in the continuous action in the storage space of the package described later by changing from a liquid to a gas at room temperature, and are excellent in the package. The antifungal effect can be maintained for a longer period of time.
In addition, in this specification, "room temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

The molecular weight of compound (1) and its salt is preferably 300 or less in that it is easily volatilized, and may be, for example, 250 or less, 200 or less, 150 or less, etc., but these may be used. This is an example. The lower limit of the molecular weight of compound (1) and its salt is not particularly limited.

The compound (1) and a salt thereof are preferably odorless or have a weak odor. Such a compound (1) and a salt thereof, even if they adhere to the object to be preserved, are functionally preferable because their existence is not or hardly recollected at the time of use of the object to be preserved.
The odorous compound (1) and a salt thereof are preferably those that can be used as a fragrance. Examples of such a compound (1) and a salt thereof include those classified as natural flavors of food additives.

As described above, the compound (1) which can be used as a food additive, has volatile properties, is odorless or has a weak odor, or a salt thereof corresponds to, for example, compound (1) -1A-0. 2-Phenoxyethanol and the like represented by the following formula can be mentioned.

As the compound (1) and a salt thereof, a commercially available product may be used, or a product produced by a known method may be used.

<Production method of compound (1)>
The compound (1) is represented by, for example, a compound represented by the following general formula (101) (in the present specification, it may be referred to as “compound (101)”) and the following general formula (102). A step of reacting a compound (sometimes referred to as "compound (102)" in the present specification) with a compound (1) to obtain a compound (1) (referred to as "compound (1) manufacturing step" in the present specification). It can be manufactured by a manufacturing method having (may be).

（式中、Ｘ、Ｒ、ｍ及びｎは、上記と同じであり；Ｌｇは離脱基である。）

(In the formula, X, R, m and n are the same as above; Lg is a leaving group.)

The reaction in the compound (1) production step is known, and the reaction conditions may be appropriately selected according to the type of the raw material used.
Examples of Lg include halogen atoms such as chlorine atom, bromine atom and iodine atom; alkylsulfonyloxy group; fluoroalkylsulfonyloxy group and the like.
In the manufacturing process of compound (1), for example, a group such as a hydroxyl group (-OH) in compound (102), which may cause an unintended reaction in the raw material used, is protected with a protecting group in advance. After that, the reaction may be carried out, and the compound (1) may be obtained by carrying out deprotection after the reaction is completed.
Compound (101) can be produced by applying a conventional method for producing sodium alkoxide. For example, a corresponding phenolic compound as a raw material, that is, a compound in which the ^{group represented by the formula "-O-} Na ⁺ " is replaced with the group represented by the formula "-OH" in the compound (101) is used. Compound (101) can be obtained by allowing metallic sodium, sodium hydride, or the like to act.
In compound (102), the corresponding alcohol as a raw material, that is, the compound represented by the general formula “HO-X-OH (X is the same as above)” and the hydroxyl group of one of them are protected by a protecting group. It can be produced by a method of introducing Lg using the above compound. When a protecting group is used, the protecting group may be removed (deprotected) at an appropriate timing. However, the method for producing the compound (102) shown here is an example.

In the compound (1) production step, after the reaction of the compound (101) and the compound (102) is completed, a post-treatment is performed as necessary by a known method to take out the target compound (1). it can. That is, after the reaction is completed, post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, and concentration are performed individually or in combination of two or more as necessary, and concentration, crystallization, and reprecipitation are performed. , The compound (1) can be extracted by column chromatography or the like. Further, the extracted compound (1) is further subjected to operations such as crystallization, reprecipitation, column chromatography, extraction, and stirring and washing of crystals with a solvent, as necessary, either alone or in combination of two or more. It may be purified by performing it more than once.
After completion of the reaction, compound (1) may be subjected to post-treatment as necessary and then continued to be used for the intended purpose without being taken out.

The obtained compound (1) is known, for example, nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), ultraviolet / visible spectroscopy (UV-VIS absorption spectrum), and the like. The structure can be confirmed by the method of.

<Method for producing salt of compound (1)>
The salt of compound (1) can be produced by applying a usual method for producing a metal alkoxide. For example, in the case of the sodium salt (sodium alkoxide) of the compound (1), the isolated compound (1) or the compound (1) before withdrawal in the above-mentioned method for producing the compound (1). Therefore, the desired product can be obtained by applying the same method as in the case of producing the compound (101) described above. As the isolated compound (1), a commercially available product may be used.
As in the case of compound (1), the salt of compound (1) may be taken out and used, or may be used continuously for the intended purpose without being taken out.
The structure of the obtained salt of compound (1) can be confirmed by the same method as in the case of compound (1).

The fungicide may contain other components in addition to compound (1) or a salt thereof.
The other components in the fungicide are not particularly limited as long as the effects of the present invention are not impaired, and can be arbitrarily selected.
For example, the compound (1) or a salt thereof may be either solid or liquid at room temperature and under normal pressure, and a compound having suitable properties may be selected according to the type of antifungal resin film described later. Just do it. Then, compound (1) or a salt thereof may be used, for example, dissolved or dispersed in a solvent, or diluted with a solvent. That is, examples of the other components include solvents and the like.

The solvent may be appropriately selected depending on the type of compound (1) or a salt thereof, and the type is not particularly limited.
Preferred examples of the solvent include the same solvents that may be contained in the resin composition described above.

When the fungicide contains the solvent, the content of the solvent is not particularly limited and can be, for example, 10 to 90% by mass, but this is only an example.
The antifungal agent containing a solvent can be used as it is as the resin composition for forming an antifungal resin film.

When the fungicide contains other components other than the solvent, the content of the other components is not particularly limited as long as the effects of the present invention are not impaired, and may be appropriately selected depending on the type of the other components. Just do it.
However, usually, in the fungicide, the solvent other than the solvent is used with respect to the total content of the components other than the solvent (that is, the compound (1), the salt of the compound (1), and other components other than the solvent). The ratio of the content of other components is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, for example, 2% by mass or less, 1 It may be any of mass% or less.

The microorganisms (molds) whose growth-suppressing effect (antifungal effect) is observed by the use of the antifungal agent are not generally limited to those in a specific range, but those having a high antifungal effect are penicillium. (Penicularium), Aspergillus, Cladosporium, Fusarium, Alternaria, Rhizopus ) Microorganisms belonging to the genus, microorganisms belonging to the genus Botrytis, and the like can be mentioned.
Among these, examples of microorganisms belonging to the genus Penicillium include Penicillium and Mildew. Examples of microorganisms belonging to the genus Aspergillus include Aspergillus niger and the like. Examples of microorganisms belonging to the genus Cladosporium include black mold and the like. Examples of microorganisms belonging to the genus Fusarium include Fusarium solani and the like. Examples of microorganisms belonging to the genus Alternaria include Alternaria tenuis. Examples of microorganisms belonging to the genus Rhizopus include Rhizopus niglicans and the like. Examples of microorganisms belonging to the genus Botricis include Haiiro mold and the like.

Among the antifungal agents, those containing two or more kinds of components can be obtained by blending these components.

When blending each component, all the components may be added and then mixed, some components may be added sequentially and mixed, or all components may be added sequentially and mixed. Good.
The mixing method is not particularly limited, and from known methods such as a method of rotating and mixing a stirrer or a stirring blade; a method of mixing using a mixer, a kneader, a bead mill or the like; a method of adding ultrasonic waves to mix. It may be selected as appropriate.

The temperature at the time of blending and the blending time are not particularly limited as long as each component does not deteriorate. The temperature at the time of blending can be, for example, 5 to 50 ° C., and the blending time can be, for example, 5 to 60 minutes, but these are examples.

<< Mold-proof packaging >>
The antifungal packaging of the present invention is an antifungal packaging obtained by using the above-mentioned antifungal laminated film of the present invention, and is formed by partially adhering a part of the first resin layers to each other. It has a space, and the antifungal resin film is arranged on the accommodation space side of the second resin layer.
The antifungal package of the present invention has excellent antifungal properties by using the antifungal laminated film (antifungal resin film), and mold grows in the accommodation space during storage of the target product. Can be remarkably suppressed and the freshness of non-heat-treated foods such as fruits and vegetables can be maintained.

FIG. 2 is a cross-sectional view schematically showing an embodiment of the antifungal package of the present invention.
The antifungal package 10 shown here is formed by using the antifungal laminated film 1 shown in FIG. The antifungal packaging body 10 has a storage space S formed by partially adhering the first resin layers 11 and 11 of the pair of antifungal laminated films 1, 1 to each other, and the antifungal resin film 12 Is arranged closer to the accommodation space S than the second resin layer 13, and is roughly configured. That is, the pair of antifungal laminated films 1 and 1 are arranged so that the first resin layers 11 and 11 face each other.
The target storage object (not shown) is stored in the storage space S of the antifungal package 10.
In FIG. 2, the through hole is not shown.

In the antifungal package 10, the compound (1) or a salt thereof easily moves from the inside of the antifungal resin film 12 into the accommodation space S via the first resin layer 11. As a result, the antifungal package 10 can maintain the concentration of the compound (1) or a salt thereof in the storage space S at an appropriate level for a certain period of time, and exhibits an excellent antifungal effect.
Further, since the antifungal package 10 has the through hole, the amount of water in the accommodation space S can be adjusted, and thus an excellent antifungal effect is exhibited.
Further, in the antifungal package 10, the first resin layer 11 prevents the object to be stored in the storage space S from coming into contact with the antifungal resin film 12, and the antifungal agent is excessively transferred to the object to be stored. Is suppressed.

Further, since the antifungal package 10 has the through hole, the oxygen concentration in the storage space S can be adjusted within an appropriate range, so that the freshness of the non-heat-treated food such as fruits and vegetables can be maintained.

Further, in the antifungal package 10, as described above in the antifungal laminated film, by adjusting the composition of the second resin layer 13, the antifungal effect can be sustained and the object to be stored by oxygen gas from the outside. It is possible to further enhance the effect of suppressing deterioration of objects. In addition, by adjusting the type of compound (1) or a salt thereof, the use of compound (1) or a salt thereof (antifungal agent) is hardly or hardly reminiscent of the use of the object to be preserved after storage. It can also be functionally preferable.

Up to this point, as the antifungal packaging of the present invention, the one using the antifungal laminated film 1 shown in FIG. 1 has been described, but the antifungal packaging of the present invention is the antifungal packaging of another embodiment of the present invention. It may be formed by using a laminated film.

The antifungal package of the present invention is not limited to the above-described embodiment, and a part of the configuration may be changed, deleted or added within a range not deviating from the gist of the present invention.
For example, the antifungal packaging body 10 shown in FIG. 2 uses a pair of antifungal laminated films 1 and 1 of the same type, but the antifungal packaging body of the present invention is a pair of different types of antifungal laminated films. It may be the one using a film.
Further, the antifungal package of the present invention may have other configurations other than the antifungal laminated film as long as the effects of the present invention are not impaired. The other configuration is not particularly limited, and may be appropriately selected depending on the intended purpose.

The antifungal package of the present invention can be produced by using the antifungal laminated film of the present invention and adhering a part of the first resin layers to each other so as to have a storage space.
Adhesion between the first resin layers can be performed, for example, by applying various known laminating methods.
When partially adhering the first resin layers to each other, it is preferable to avoid the region of the first resin layer (mold-proof laminated film) having through holes. By doing so, all the through holes in the antifungal laminated film can be effectively made to function even in the antifungal package.

As described above, the antifungal package of the present invention is preferably used for packaging non-heat-treated foods.
Preferred non-heat-treated foods include fruits and vegetables such as vegetables, fruits and grains.

Examples of vegetables include eggplant, ginger, tomato, pepper, red pepper, carrot, cabbage, hakusai, lettuce, radish, spinach, long onion, onion, broccoli, cauliflower, shiitake mushroom, and shimeji.
Fruits include, for example, oranges, navel oranges, oranges, lemons, kumquats, yuzus, grapefruits, apples, pears, pears, mangoes, figs, grapes, strawberries, pineapples, kiwis, blueberries, pomegranates, peaches, papayas, melons, etc. Examples include watermelon, banana, and avocado.
Examples of cereals include peas, dadacha beans, corn, potatoes, sweet potatoes and the like.

The antifungal package of the present invention is preferably for packaging fruits and vegetables, and more preferably for packaging citrus fruits such as oranges, navel oranges, oranges, lemons, kumquats, citrons, and grapefruits.

When the target object is contained and packaged in the accommodation space using the antifungal package of the present invention, the content of the antifungal agent per 100 g of the contained item (package) of the antifungal package is determined. It is preferably 0.001 to 0.1 g, more preferably 0.001 to 0.075 g, and particularly preferably 0.001 to 0.05 g. When the content of the antifungal agent is at least the above lower limit value, the antifungal effect of the antifungal package becomes higher. Further, when the content of the fungicide is equal to or less than the upper limit, excessive use of the fungicide is suppressed.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.

<Manufacturing of antifungal laminated film>
[Example 1]
An antifungal laminated film having the configuration shown in FIG. 1 was produced by the procedure shown below.

(Manufacturing of antifungal resin film)
Main agent (Mitsui Chemicals Co., Ltd. "Takelac (registered trademark) A620", solid content 50% by mass, ethyl acetate 50% by mass) (6 parts by mass), curing agent (Mitsui Chemicals Co., Ltd. "Takenate (registered trademark) A10" , 75% by mass of solid content, 25% by mass of ethyl acetate) (1 part by mass), and ethyl acetate (6 parts by mass) were mixed to prepare a polyurethane adhesive. In the obtained polyurethane adhesive, the total content of the solvent (ethyl acetate) is 71.2% by mass.
Next, 2-phenoxyethanol (2 parts by mass) was mixed with the total amount of the polyurethane adhesive obtained above, and the ratio of the content of 2-phenoxyethanol to the total content of the components other than the solvent was 34.8% by mass. A resin composition was obtained.

Next, the resin composition obtained above was coated on one surface of the PET film (thickness 12 μm) using a multicoater and dried at 80 ° C. to obtain a content of 2-phenoxyethanol of 35. An antifungal resin film (thickness 5.8 μm) of mass% was formed on the PET film. As described above, the first laminated body was produced.

(Manufacturing of antifungal laminated film)
Further, by laminating an LLDPE film (thickness 30 μm) on the surface of the first laminate obtained above on the side opposite to the side on which the PET film of the antifungal resin film is provided, the PET film, A transparent second laminated body having a size of 150 mm × 250 mm was obtained in which the antifungal resin film and the LLDPE film were laminated in this order.

Next, four through holes having an average diameter of 180 μm were formed in the second laminated body by piercing the needles into four sites sufficiently separated from each other in the second laminated body to obtain an antifungal laminated film. ..
The size of the obtained antifungal laminated film (mm × mm), the average diameter of the through holes (μm), the number of through holes (pieces / sheet), the number of through holes (pieces / m ² ), and the antifungal properties. ^{Table 1 shows the content (g / m 2} ) and thickness (μm) of the fungicide of the resin film. ^{In Table 1, the content (g / m 2} ) and the thickness (μm) of the antifungal agent of this antifungal resin film are shown in the content of the antifungal agent of the packaging film in the comparative example described later (g / m 2). In order to indicate in the same column as g / m ² ) and thickness (μm), the columns of "content of antifungal agent in resin film (g / m ² )" and "thickness of resin film (μm)" Is provided, and the corresponding numerical values are described here.

<Measurement of oxygen permeation of antifungal laminated film>
The amount of oxygen permeation of the antifungal laminated film obtained above was measured by the following method. The results are shown in Table 1.

(I) Preparation of bag
In the atmosphere, a bag was prepared by heat sealing using the above-mentioned antifungal laminated film and sealed.

(II) Filling the bag with nitrogen gas After degassing the inside of the bag until both sides of the bag stick to each other, the inside of the bag was filled with nitrogen gas having a purity of 99.9% or more. Deaeration and injection of nitrogen gas were performed by piercing the bag with an injection needle. The nitrogen gas filling amount V (cc) was measured as much as possible so that the film was not excessively tensioned and was slightly loosened, and was measured by the scale of the injection tube. When the injection needle was stabbed in the bag, a double-sided tape was attached to the corresponding portion of the film, and a polypropylene film adhesive tape (hereinafter abbreviated as "PP tape") was attached on the double-sided tape. After pulling out the needle, the needle hole was immediately closed with PP tape. The area of the PP tape was 4.5 cm ² or less. When the double-sided tape and the PP tape were applied, the through holes of the film were not blocked by these tapes.

(III) Initial oxygen concentration measurement A gas of 10 cc or less is sampled from the inside of the bag when the filling of nitrogen gas is completed (t = 0), and the initial oxygen concentration C ₀ (TCD) inside the bag is performed by gas chromatography (TCD). %) Was measured. In the present specification, the elapsed time from the completion of filling with nitrogen gas is t (hr), and the oxygen concentration inside the bag at this time _{is represented by "Ct} (%)". Since C ₀ is 0.2% or less, if it exceeds 0.2%, the above work is repeated. The injection amount of the sampling gas when performing gas chromatography was a fixed amount of about 1 cc. Further, gas chromatography was also performed on a standard gas having an oxygen concentration of about 1% and about 10%, which is at least two levels, and a calibration curve was prepared.

(IV) Storage of bags The bags whose initial oxygen concentration was measured were stored in a constant temperature and humidity chamber under the conditions of 20 ° C. and 80% RH. At this time, the bag was allowed to stand so that no object would be placed on the bag or the wind of the fan of the constant temperature and humidity chamber would hit the bag directly.

(V) Measurement of oxygen concentration inside the bag during storage and calculation of oxygen permeation amount After 3 hours or more (t ≧ 3) from the completion of nitrogen gas filling (t = 0), the oxygen concentration inside the bag becomes high. 1-7% of the made such including two or more timing range at the timing of 3-5 times in total, in the same way as when C ₀ measurements, sampling the gas from the interior of the bag, the oxygen concentration C _t (%) was measured. If a proportional relationship with a correlation coefficient of 0.98 or more was not established between t and C _{t, the test was to be repeated.} Then, for the case where t is the largest, the oxygen permeation amount F (g / m ² · day) was calculated by the following formula (i).
If the oxygen permeation amount of the film is too large and the oxygen concentration inside the bag rises too quickly and the above proportional relationship is not established, a part of the film is made of the same material as this film and is made of the same material. It was decided to bond a film having a known smaller oxygen permeation amount than the film, and to measure the oxygen concentration inside the bag with the improved bag obtained by the film in the same manner as described above. At this time, the area of the area where the film having the smaller oxygen permeation amount was bonded was subtracted from the surface area of the original bag, and the above-mentioned known oxygen permeation amount was subtracted from the oxygen permeation amount of the film in the improved bag. The value was decided to be the oxygen permeation amount of the target film.
F = 1.143 × (C _{t −} C ₀ ) × V / t ・ ・ ・ ・ (i)

<Measurement of water vapor permeation of antifungal laminated film>
With respect to the antifungal laminated film obtained above, the amount of water vapor permeation (g / m ² · day) in an atmosphere of 40 ° C. and 90% RH was measured in accordance with JIS K 7129B. The results are shown in Table 1.

[Example 2]
The antifungal laminated film is produced by the same method as in Example 1 except that the content and thickness of the antifungal agent of the antifungal resin film and the size of the antifungal laminated film are as shown in Table 1. Then, the amount of oxygen permeation and the amount of water vapor permeation were measured. The results are shown in Table 1.
The content of the antifungal agent (2-phenoxyethanol) in the antifungal resin film was adjusted by changing the amount of the antifungal agent used during the production of the resin composition. Further, the thickness of the antifungal resin film was adjusted by changing the coating amount of the resin composition. These are the same in other examples in which the content or thickness of the antifungal agent in the antifungal resin film is different from that in Example 1.

[Example 3]
An antifungal laminated film was produced by the same method as in Example 1 except that the size of the antifungal laminated film was set as shown in Table 1, and the oxygen permeation amount and the water vapor permeation amount were measured. The results are shown in Table 1.

[Example 4]
The antifungal laminated film is produced by the same method as in Example 1 except that the content and thickness of the antifungal agent of the antifungal resin film and the size of the antifungal laminated film are as shown in Table 2. Then, the amount of oxygen permeation and the amount of water vapor permeation were measured. The results are shown in Table 2.

[Example 5]
An antifungal laminated film was produced by the same method as in Example 1 except that the size of the antifungal laminated film was set as shown in Table 2, and the oxygen permeation amount and the water vapor permeation amount were measured. The results are shown in Table 2.

[Example 6]
Examples except that the content and thickness of the antifungal agent of the antifungal resin film, the size of the antifungal laminated film, the average diameter of the through holes, and the number of through holes are as shown in Table 3. An antifungal laminated film was produced by the same method as in 1, and the oxygen permeation amount and the water vapor permeation amount were measured. The results are shown in Table 3.

[Example 7]
Same as in Example 1 except that the content of the antifungal agent in the antifungal resin film, the size of the antifungal laminated film, the average diameter of the through holes, and the number of through holes are as shown in Table 3. By the method, an antifungal laminated film was produced, and the oxygen permeation amount and the water vapor permeation amount were measured. The results are shown in Table 3.

[Example 8]
The same method as in Example 1 was used except that the content and thickness of the antifungal agent in the antifungal resin film, the size of the antifungal laminated film, and the number of through holes were set as shown in Table 4. An antifungal laminated film was produced, and its oxygen permeation amount and water vapor permeation amount were measured. The results are shown in Table 4.

[Example 9]
Antifungal lamination by the same method as in Example 1 except that the content of the antifungal agent in the antifungal resin film, the size of the antifungal laminated film, and the number of through holes are as shown in Table 4. A film was produced and its oxygen permeation amount and water vapor permeation amount were measured. The results are shown in Table 4.

<Manufacturing of packaging film for comparison>
[Comparative Example 1]
A biaxially stretched transparent polypropylene (PP) film (OPP film) having a size of 150 mm × 250 mm and a thickness of 3.1 μm is pierced with a needle to make a through hole having an average diameter of 120 μm. 100,000 pieces were formed to obtain a packaging film for comparison.
Then, the oxygen permeation amount and the water vapor permeation amount of this packaging film were measured by the same method as in Example 1. The results are shown in Table 1.

[Comparative Examples 2-3]
A laminated packaging film for comparison was produced by the same method as in Example 1 except that the thickness of the resin film and the size of the film were set as shown in Table 1 or 2 without using an antifungal agent. Then, the amount of oxygen permeation and the amount of water vapor permeation were measured. The results are shown in Table 1 or 2. In other words, the packaging laminated film of Comparative Example 2 is the same as the antifungal laminated film of Example 2 except that no antifungal agent is used, and the packaging laminated film of Comparative Example 3 is antifungal. It is the same as the antifungal laminated film of Example 4 except that no agent is used.

[Comparative Example 4]
The same method as in Example 1 was used except that the thickness of the resin film, the size of the film, the average diameter of the through holes, and the number of through holes were set as shown in Table 3 without using an antifungal agent. , A laminated film for packaging for comparison was produced, and the oxygen permeation amount and the water vapor permeation amount were measured. The results are shown in Table 3. In other words, this laminated film for packaging is the same as the antifungal laminated film of Example 6 except that an antifungal agent is not used.

[Comparative Example 5]
For packaging for comparison, the same method as in Example 1 except that the thickness of the resin film, the size of the film, and the number of through holes were set as shown in Table 4 without using an antifungal agent. A laminated film was produced, and the oxygen permeation amount and the water vapor permeation amount were measured. The results are shown in Table 4. In other words, this laminated film for packaging is the same as the antifungal laminated film of Examples 8 to 9 except that it does not use an antifungal agent and the thickness of the resin film is different.

<Evaluation of antifungal packaging>
[Test Example 1]
(Confirmation of preservation effect on navel orange)
Two antifungal laminated films of Example 1 were prepared, and in the atmosphere, two navel oranges having an average mass of 403 g were sandwiched between the antifungal laminated films, and the peripheral portion of these antifungal laminated films. They were overlapped and heat laminated. As described above, the above-mentioned two navel oranges were contained in a transparent bag (antifungal packaging) made from the above-mentioned antifungal laminated film, and a sealed sample was prepared. A total of 6 such samples were prepared.
Similarly, 6 samples were prepared using the packaging film of Comparative Example 1.
Table 1 shows the content (g) of the antifungal agent per 100 g of the contained material in the obtained bag (antifungal package, comparative package).

Next, the sample obtained above was stored at 20 ° C. for 8 days, and during this period, the sealed navel orange was visually observed through the bag to confirm the number of storage days until mold was formed on the navel orange. did. In addition, with respect to the navel orange after storage, the degree of suppression of wilting was visually observed, the taste of the edible part was confirmed, and the evaluation was made according to the following evaluation criteria. The results are shown in Table 1. When both the suppression of wilting and the taste were "A", it was judged that the freshness of the contained material was maintained.
(Suppression of wilting)
A: No wilting was observed, and the state immediately after harvesting was maintained.
B: Withering is observed, and the state immediately after harvesting is not maintained.
(Taste)
A: You can feel the flavor immediately after harvesting, and there is no discomfort in the taste.
B: There is something wrong with the flavor, and there is something wrong with the taste.

As shown in Table 1, when the packaging film of Comparative Example 1 was used, mold was generated after one day of storage, the taste was poor, and the freshness was not maintained.
On the other hand, when the antifungal laminated film of Example 1 was used, the mold was generated at the stage of 4 days of storage, the wilting was suppressed, the taste was good, and the freshness was maintained. It was.

[Test Example 2]
(Confirmation of preservation effect on figs (1))
Two antifungal laminated films of Example 2 were prepared, and in the atmosphere, about 86 g of one fig was sandwiched between the antifungal laminated films, and the peripheral portions of the antifungal laminated films were sandwiched between the two films. Overlapping and heat laminating. As described above, the above-mentioned one fig was housed in a transparent bag (mold-proof package) made of the above-mentioned antifungal laminated film, and a sealed sample was prepared. A total of 5 such samples were prepared.
Similarly, using the antifungal laminated film of Example 3 and the packaging film of Comparative Example 2, five samples were prepared for each of these Examples or Comparative Examples.
Table 1 shows the content (g) of the antifungal agent per 100 g of the contained material in the obtained bag (antifungal package, comparative package).

The sample obtained above and one unpacked fig (ie, unwrapped sample) were then stored at 10 ° C. for 14 days, during which time the sealed figs were Was visually observed through the bag, and the unwrapped figs were visually observed directly to confirm the number of days of storage until the figs became moldy. In addition, with respect to figs after storage, the degree of suppression of wilting was visually observed, the taste of edible parts was confirmed, and the figs were evaluated in the same manner as in Test Example 1. The results are shown in Table 1.

As shown in Table 1, when the packaging film of Comparative Example 2 was used, mold was generated in less than 1 day of storage, the wilting was suppressed, the taste was poor, and the freshness was not maintained. It was.
On the other hand, when the antifungal laminated film of Example 2 was used, the mold was generated at the stage of 3 days of storage, the wilting was suppressed, the taste was good, and the freshness was maintained. It was.
When the antifungal laminated film of Example 3 was used, the mold was generated at the stage of 4 days of storage, the wilting was suppressed, the taste was good, and the freshness was maintained.
Since the unwrapped figs (unwrapped samples) were not sealed, the water content of the surrounding environment did not increase, and mold was generated at the stage of 11 days of storage. Since it was not packaged, the suppression of wilting and the taste were poor at this stage, and in the first place, wilting occurred from the initial stage of storage, and the freshness was not maintained.

[Test Example 3]
(Confirmation of preservation effect on figs (2))
Using the antifungal laminated film of Example 3 and the packaging film of Comparative Example 2, the sample and the unwrapped sample were stored at 20 ° C. for 7 days instead of being stored at 10 ° C. for 14 days. The evaluation was performed by the same method as in Test Example 2 except for the points. The results are shown in Table 2.

As shown in Table 2, when the packaging film of Comparative Example 2 was used, mold was generated at the stage of 1 day of storage.
On the other hand, when the antifungal laminated film of Example 3 was used, the mold was generated at the stage of 4 days of storage, the wilting was suppressed, the taste was good, and the freshness was maintained. It was.
The unwrapped figs (unwrapped samples) were not sealed, but the storage temperature was higher than that in Test Example 2, and mold was generated at the stage of 2 days of storage. Further, since this unwrapped sample was not packaged, the suppression of wilting and the taste were poor at this stage, and the wilting occurred from the initial stage of storage, and the freshness was not maintained.

[Test Example 4]
(Confirmation of preservation effect on mango)
Two antifungal laminated films of Example 4 were prepared, and in the atmosphere, about 335 g of one mango (Apple Mango, Tommy Atkins species) was sandwiched between the antifungal laminated films. The peripheral parts of the mold laminated film were overlapped with each other and heat-laminated. As described above, the above-mentioned one mango was contained in a transparent bag (antifungal packaging) made from the above-mentioned antifungal laminated film, and a sealed sample was prepared. A total of 7 such samples were prepared.
Similarly, using the antifungal laminated film of Example 5 and the packaging film of Comparative Example 3, seven samples were prepared for each of these Examples or Comparative Examples.
Table 2 shows the content (g) of the antifungal agent per 100 g of the contained material in the obtained bag (antifungal package, comparative package).

Next, the sample obtained above was stored at 20 ° C. for 14 days, and during this period, the sealed mango was visually observed through a bag to confirm the number of storage days until mold was formed on the mango. In addition, with respect to the mango after storage, the degree of suppression of wilting was visually observed, the taste of the edible part was confirmed, and the mango was evaluated in the same manner as in Test Example 1. The results are shown in Table 2.

As shown in Table 2, when the packaging film of Comparative Example 3 was used, mold was generated at the stage of storage for 4 days.
On the other hand, when the antifungal laminated films of Examples 4 to 5 were used, the molds were generated at the stage of 14 days of storage, the wilting was suppressed, the taste was good, and the freshness was good. Was retained.

[Test Example 5]
(Confirmation of preservation effect on eggplant (1))
Two antifungal laminated films of Example 6 were prepared, and in the atmosphere, three eggplants having an average mass of 418 g were sandwiched between the antifungal laminated films, and the peripheral portions of the antifungal laminated films were sandwiched between the two films. Was overlapped and heat-laminated. As described above, the above-mentioned three eggplants were housed in a transparent bag (mold-proof package) made of the above-mentioned antifungal laminated film, and a sealed sample was prepared. A total of 5 such samples were prepared.
Similarly, using the antifungal laminated film of Example 7 and the packaging film of Comparative Example 4, five samples were prepared for each of these Examples or Comparative Examples.
Table 3 shows the content (g) of the antifungal agent per 100 g of the contained material in the obtained bag (antifungal package, comparative package).

Next, the sample obtained above and three eggplants having an average mass of 418 g (that is, unwrapped samples) were stored at 10 ° C. for 14 days, and the sealed eggplants were stored during this period. This was visually observed through the bag, and the unwrapped eggplants were visually observed directly to confirm the number of days of storage until the eggplants became moldy. In addition, the eggplants after storage were visually observed for the degree of suppression of wilting and evaluated in the same manner as in Test Example 1. Since eggplants are not normally eaten without heat treatment, the taste was not confirmed, and it was judged that the freshness of the contained material was maintained when the suppression of wilting was "A". The results are shown in Table 3.

As shown in Table 3, when the packaging film of Comparative Example 4 was used, mold was generated at the stage of 7 days of storage.
On the other hand, when the antifungal laminated film of Example 6 was used, the mold was generated at the stage of 9 days of storage, the wilting was well suppressed, and the freshness was maintained.
When the antifungal laminated film of Example 7 was used, the mold was generated at the stage of 11 days of storage, the wilting was well suppressed, and the freshness was maintained.
The unwrapped eggplant (unwrapped sample) was not sealed, but mold was generated at the stage of 1 day of storage. Furthermore, since this unwrapped sample was not packaged, the suppression of wilting was poor at this stage, and wilting occurred from the initial stage of storage, and the freshness was not maintained.

[Test Example 6]
(Confirmation of preservation effect on eggplant (2))
Using the antifungal laminated film of Example 7 and the packaging film of Comparative Example 4, the sample and the unwrapped sample were stored at 20 ° C. for 14 days instead of being stored at 10 ° C. for 14 days. The evaluation was performed in the same manner as in Test Example 5 except for the points. The results are shown in Table 4.

As shown in Table 4, when the packaging film of Comparative Example 4 was used, mold was generated at the stage of 2 days of storage.
On the other hand, when the antifungal laminated film of Example 7 was used, the mold was generated at the stage of 4 days of storage, the wilting was well suppressed, and the freshness was maintained.
Since the unwrapped eggplant (unwrapped sample) was not sealed, the water content of the surrounding environment did not increase, and mold was generated at the stage of 7 days of storage. Since it was not packaged, the suppression of wilting was poor at this stage, and wilting occurred from the initial stage of storage, and the freshness was not maintained.

[Test Example 7]
(Confirmation of preservation effect on Dadacha beans)
Two antifungal laminated films of Example 8 were prepared, and in the atmosphere, peripheral portions of these antifungal laminated films were sandwiched between the antifungal laminated films having an average mass of 257 g. Was overlapped and heat-laminated. As described above, the above-mentioned 257 g of Dadacha beans were contained in a transparent bag (mold-proof package) made from the above-mentioned antifungal laminated film, and a sealed sample was prepared. A total of 6 such samples were prepared.
Similarly, using the antifungal laminated film of Example 9 and the packaging film of Comparative Example 5, 6 samples were prepared for each of these Examples or Comparative Examples.
Table 4 shows the content (g) of the antifungal agent per 100 g of the contained material in the obtained bag (antifungal package, comparative package).

Next, the sample obtained above was stored at 25 ° C. for 7 days, and during this period, the sealed Dadacha beans were visually observed through the bag until mold was formed on the Dadacha beans. I checked the number of days to save. In addition, the degree of suppression of wilting of the Dadacha beans after the storage was completed was visually observed, the taste of the edible portion was confirmed, and the evaluation was carried out in the same manner as in Test Example 1. The results are shown in Table 4.

As shown in Table 4, when the packaging film of Comparative Example 5 was used, mold was generated at the stage of 1 day of storage.
On the other hand, when the antifungal laminated films of Examples 8 to 9 were used, the molds were generated at the stage of 3 days of storage, the wilting was suppressed, the taste was good, and the freshness was good. Was retained.

The present invention can be used for packaging used for storing non-heat-treated foods such as fruits and vegetables.

1 ... Anti-mold laminated film 1a ... First surface of anti-mold laminated film 1b ... Second surface of anti-mold laminated film 10 ... Anti-mold packaging 11 ... First resin layer 11b ... .. Second surface of the first resin layer 12 ... Antifungal resin film 13 ... Second resin layer 13a ... First surface of the second resin layer 14 ... Through hole S ... Antifungal Packaging space

Claims (10)

An antifungal laminated film comprising an antifungal resin film, a first resin layer, and a second resin layer.
The antifungal resin film is arranged between the first resin layer and the second resin layer.
The antifungal resin film contains a fungicide containing 2-phenoxyethanol as an active ingredient and a resin.
The resin is a urethane-based adhesive, and the antifungal resin film has adhesiveness.
The antifungal laminated film, the average diameter has the following holes 8000Myuemu, and is 40 ° C., the water vapor permeation amount under an atmosphere of RH 90% is 5g ^/ m 2 · day or more, antifungal laminated film. The antifungal laminated film according to claim 1, wherein the oxygen permeation amount of the antifungal laminated film in an atmosphere of 20 ° C. and 80% RH is 2.0 × 10 ⁸ cc / m ^{2 · day or less.} The antifungal laminated film according to claim 1 or 2, wherein the antifungal laminated film has 40 to 400 through holes / m ^2. The antifungal laminated film according to any one of claims 1 to 3, wherein the content of the antifungal agent in the antifungal resin film is 0.02 to ^{2 g / m 2.} The antifungal laminated film according to any one of claims 1 to 4 , wherein the first resin layer contains linear low-density polyethylene. The antifungal laminated film according to any one of claims 1 to 5 , wherein the second resin layer contains one or more selected from the group consisting of polyester, nylon and polypropylene. An antifungal package obtained by using the antifungal laminated film according to any one of claims 1 to 6.
It has a storage space in which a part of the first resin layers is adhered to each other and is formed.
An antifungal packaging body in which the antifungal resin film is arranged on the accommodation space side of the second resin layer. The antifungal packaging according to claim 7 , which is used for packaging fruits and vegetables. The antifungal packaging according to claim 7 or 8 , which is used for packaging citrus fruits. A fungicide resin film containing a fungicide containing 2-phenoxyethanol as an active ingredient and a resin.
The resin is a urethane-based adhesive, and the antifungal resin film has adhesiveness.
The antifungal resin film is an antifungal resin film having 40 to 400 through holes having an average diameter of 8000 μm or less at a rate of 40 to 400 / m ^2.

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