JP2018168084A - Antifungal resin film, antifungal laminated film and antifungal package - Google Patents

Abstract

To provide an antifungal package which can maintain freshness of a non-heated food product such as vegetables and fruits and is excellent in a suppression effect on generation of mold, and to provide an antifungal resin film and an antifungal laminated film which suitably constitute the antifungal package.SOLUTION: The antifungal laminated film 1 is provide in which an antifungal resin film 12 is arranged between a first resin layer 11 and a second resin layer 13, the antifungal resin film 12 includes an antifungal agent containing a compound represented by formula (1) or its salt as an active ingredient and a resin, and the antifungal laminated film 1 has a through-hole 14 having an average diameter of 8,000 μm or less and a water vapor permeation amount under an atmosphere at 40°C and 90% RH of 5 g/mday or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a mold-proof resin film, a mold-proof laminated film, and a mold-proof package.

  In order to store and store the object, various storage packages are used. For example, when the object to be stored is taken orally such as food, the package is required to be able to store the object while maintaining good quality. For example, when food such as fruits and vegetables that has not been heat-treated is stored and stored, the package is required to maintain a fresh state without reducing the freshness of the food.

  When storing fruits and vegetables in a package, there is a problem that the concentration of oxygen and carbon dioxide in the package changes because the fruits and vegetables continue to breathe even during storage. . It is known that fruits and vegetables become exhausted and consumed when the oxygen concentration is high in the package. Therefore, in order to suppress consumption of fruits and vegetables and maintain freshness, it is advantageous to reduce the oxygen concentration in the package.

  Furthermore, when storing fruits and vegetables in a package, it is important to reduce the water content in the package. This is because when the amount of water in the package becomes excessive, mold is generated and the fruits and vegetables are damaged. However, the amount of water in the package is easily affected by the oxygen transmission rate of the package.

  On the other hand, as a package for vegetable materials such as vegetables, it has a specific range of water vapor permeability specific to the material of the film constituting the package, and further, the specific range is determined by the holes of the film. A package having oxygen permeability is disclosed (see Patent Document 1).

Japanese Examined Patent Publication No. 7-94263

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

  The present invention has been made in view of the above circumstances, and is capable of maintaining the freshness of non-heat-treated foods such as fruits and vegetables, and constituting the mold-proof package and the mold-proof package that are excellent in the effect of suppressing the occurrence of mold. It is an object to provide a suitable anti-mold resin film and anti-mold laminated film.

In order to solve the above problems, the present invention employs the following configuration.
[1]. An anti-mold laminated film comprising an anti-mold resin film, a first resin layer, and a second resin layer, wherein the anti-mold resin film includes the first resin layer, the second resin layer, The anti-mold resin film is disposed between the anti-mold resin film, the anti-mold agent having a compound represented by the following general formula (1) or a salt thereof as an active ingredient, and a resin. A mold-proof laminated film having through-holes having an average diameter of 8000 μm or less and having a water vapor transmission rate of 5 g / m ² · day or more in an atmosphere of 40 ° C. and 90% RH.

（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; And when m is 2 or more, a plurality of X may be the same or different from each other; n is an integer of 0 to 5, provided that m + n is 6 or less and n is 2 or more A plurality of R may be the same as or different from each other.)

[2]. The anti-mold laminate film according to [1], wherein the anti-mold laminate film has an oxygen permeation amount of 2.0 × 10 ⁸ cc / m ² · day or less in an atmosphere of 20 ° C. and 80% RH.
[3]. The anti-mold laminated film according to [1] or [2], wherein the number of the through holes of the anti-mold laminated film is 40 to 400 / m ² .
[4]. The antifungal laminated film according to any one of [1] to [3], wherein the antifungal agent content of the antifungal resin film is 0.02 to ² g / m2.
[5]. The anti-mold resin film is selected from the group consisting of urethane adhesive, acrylic adhesive, titanate adhesive, imine adhesive, butadiene adhesive, polyester adhesive and olefin adhesive as the resin. The mold prevention laminated film as described in any one of [1]-[4] containing 1 type or 2 or more types by which the said mold prevention resin film has adhesiveness.
[6]. The mold prevention laminated film according to any one of [1] to [5], wherein the first resin layer includes linear low-density polyethylene.
[7]. The mold-proof laminated film according to any one of [1] to [6], wherein the second resin layer includes one or more selected from the group consisting of polyester, nylon, and polypropylene.

[8]. It is an anti-mold packaging body obtained using the anti-mold laminated film according to any one of [1] to [7], and a part of the first resin layers are bonded and formed. An anti-mold package having an accommodating space, wherein the anti-mold resin film is disposed closer to the accommodating space than the second resin layer.
[9]. The mold-proof package according to [8], which is used for packaging fruits and vegetables.
[10]. The mold-proof package according to [8] or [9], which is for citrus packaging.
[11]. An antifungal resin film comprising an antifungal agent comprising 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. a through hole, having the number of 40 to 400 pieces / ^{m 2,} antifungal resin 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; And when m is 2 or more, a plurality of X may be the same or different from each other; n is an integer of 0 to 5, provided that m + n is 6 or less and n is 2 or more A plurality of R may be the same as or different from each other.)

  ADVANTAGE OF THE INVENTION According to this invention, the freshness of non-heat-processed foods, such as fruit and vegetables, can hold | maintain the mold prevention body excellent in the generation | occurrence | production suppression effect of mold | fungi, and the mold prevention resin film suitable for comprising the said mold prevention package body, and prevention A mold laminated film is provided.

It is sectional drawing which shows typically one Embodiment of the anti-mold laminated film of this invention. It is sectional drawing which shows typically one Embodiment of the anti-mold packaging body of this invention.

<< Anti-mold laminated film >>
The anti-mold laminate film of the present invention is an anti-mold laminate film comprising an anti-mold resin film, a first resin layer, and a second resin layer, wherein the anti-mold resin film is the first resin layer. And the second resin layer, and the anti-mold resin film is a compound represented by the following general formula (1) (in the present specification, referred to as “compound (1)”). Or a salt thereof as an active ingredient, and a resin, and the anti-mold laminated film has through-holes having an average diameter of 8000 μm or less and an atmosphere of 40 ° C. and 90% RH. The water vapor permeation amount at 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; And when m is 2 or more, a plurality of X may be the same or different from each other; n is an integer of 0 to 5, provided that m + n is 6 or less and n is 2 or more A plurality of R may be the same as or different from each other.)

The mold-proof laminated film of the present invention uses the mold-proof resin film, so that it has excellent mold-proof properties, and is used for the production of mold-proof package described below for storing and storing the object. Is preferred. Since such an anti-mold package has the said through-hole, since the oxygen concentration in accommodation space can be adjusted to an appropriate range, the freshness of non-heat-processed foods, such as fruit and vegetables, can be hold | maintained. In addition, such an anti-mold package has the through hole, so that the moisture content in the accommodation space can be further adjusted, and in addition, the anti-mold resin film is provided, In the accommodation space for accommodating this, the effect of suppressing the occurrence of mold is excellent.
In the present specification, “generation of mold” means that an object grows from a state where mold cannot be visually confirmed to a level where it can be visually confirmed.

First, the whole structure of the mold prevention laminated film of this invention is demonstrated.
FIG. 1 is a cross-sectional view schematically showing one embodiment of the anti-mold laminated film of the present invention. In addition, in order to make the features of the present invention easy to understand, the drawings used in the following description may show the main parts in an enlarged manner for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.

  The anti-mold laminated film 1 shown here includes an anti-mold resin film 12, a first resin layer 11, and a second resin layer 13. The anti-mold resin film 12 includes the first resin layer 11 and the second resin layer 11. It is arrange | positioned between resin layers 13 and is comprised roughly. That is, the anti-mold laminated film 1 is formed by laminating the first resin layer 11, the anti-mold resin film 12 and the second resin layer 13 in this order in the thickness direction, and the exposed surface of the first resin layer 11 is One surface is formed, and the exposed surface of the second resin layer 13 is the other surface.

The 1st resin layer 11 is a layer arrange | positioned rather than the anti-mold resin film 12 at this preservation | save object side, when preserve | saving an object using the anti-mold laminated film 1. FIG. For example, in a bag-like package manufactured using the mold-proof laminated film 1, the first resin layer 11 is disposed closer to the package space than the mold-proof resin film 12.
Therefore, for example, when the first resin layer 11 is one of the outermost layers of the anti-mold laminated film 1, the first resin layer 11 is a layer in contact with the storage object.
Thus, the 1st resin layer 11 prevents contact with the preservation | save object of the mold prevention resin film 12, and, thereby, suppresses the excessive transfer of the mold prevention agent to a preservation | save object.

The 2nd resin layer 13 is a layer arrange | positioned rather than this anti-mold resin film 12 on the opposite side to this preservation | save object side, when preserve | saving a target object using the anti-mold laminated film 1. FIG. For example, in a bag-like package manufactured using the mold-proof laminated film 1, the mold-proof resin film 12 is arranged closer to the housing space of the package than the second resin layer 13.
The second resin layer 13 has a function of protecting the anti-mold resin film 12.

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

<First resin layer>
The constituent material of the first resin layer is not particularly limited, but preferred examples include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and metallocene-catalyzed linear low-density polyethylene (metallocene LLDPE). ) And the like.
In addition, examples of the constituent material of the first resin layer include synthetic resins other than these.

  The constituent material of the first resin layer may be only one type or 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, and 80% by mass. More preferably, it is 90 mass% or more, for example, 99 mass% or more may be sufficient and 100 mass% may be sufficient.

The first resin layer, 25 ° C., the oxygen gas permeation amount in an atmosphere of 65% RH (relative humidity) ^is preferably at ^{3000cm 3 / m 2 · atm ·} day or more, 3000~10000cm 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 more than the lower limit value, the anti-mold agent that has migrated from the inside of the anti-mold resin film to the first resin layer side passes through the first resin layer to the outside ( It easily shifts to the outside (on the first resin layer side of the mold-proof laminated film). Thereby, the anti-mold laminated film exhibits an excellent anti-mold 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 as 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 limited to the case of the first resin layer, “a plurality of layers may be the same or different from each other” means “all layers may be the same or all layers. May be different, and only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means that“ at least one of the constituent material and thickness of each layer is different from each other ” "Means.

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 equal to or more than the lower limit value, the strength of the first resin layer is further improved, and excessive migration of the fungicide to the storage object is further suppressed. Moreover, when the thickness of the first resin layer is not more than the above upper limit value, the anti-mold effect of the anti-mold laminated film is further improved.
In the case where the first resin layer is composed of a plurality of layers, the total thickness of the plurality of layers may be set to the above-described preferable thickness of the first resin layer.

<Second resin layer>
The constituent material of the second resin layer may be appropriately selected according to the purpose, and is not particularly limited. However, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate ( PEN), polyesters such as polybutylene naphthalate (PBN); nylon; polypropylene (PP) and the like.
In addition, examples of the constituent material of the second resin layer include synthetic resins other than these.

  The constituent material of the second resin layer may be only one type or two or more types, and in the case of 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. Preferably, it is 90 mass% or more, more preferably 95 mass% or more, for example, 99 mass% or more, or 100 mass%.

The amount of oxygen gas permeation in the atmosphere of 25 ° C. and 65% RH (relative humidity) of the second resin layer is preferably 3000 cm ³ / m ² · atm · day or less, preferably 2500 cm ³ / m ² · atm ·. It is more preferably not more than day, and particularly preferably not more than 2000 cm ³ / m ² · atm · day.
As the upper limit value of the oxygen gas permeation amount of the second resin layer is smaller, the anti-fungal agent is transferred from the inside of the anti-mold resin film to the second resin layer and the outside (anti-mold) through the second resin layer. Transition to the outside (on the second resin layer side of the laminated film) is effectively suppressed. Therefore, since the amount of the anti-mold agent that moves from the inside of the anti-mold resin film to the object to be stored can be maintained at an appropriate level for a long period of time, the anti-mold laminated film exhibits a more excellent anti-mold effect. In addition, for example, when the object is accommodated and sealed in a bag-shaped package manufactured using a mold-proof laminated film, the migration of the mold-proofing agent to the outside of the package is suppressed, At the time of storage of the target product, the use of a fungicide is hardly recalled and is preferred in terms of functionality.
Furthermore, the smaller the upper limit value of the oxygen gas permeation amount of the second resin layer is, the more oxygen gas passes from the outside (the outside on the second resin layer side of the anti-mold laminated film) through the second resin layer to the inside. Migration is effectively suppressed. Therefore, the effect of preserving the object without degrading the quality is further enhanced.

On the other hand, the lower limit value 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. / M ² · atm · day and 1000 cm ³ / m ² · atm · day, which 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 amounts of the first resin layer and the second resin layer are both values measured according to 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 as 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 more 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. Is obtained. Moreover, when the thickness of the second resin layer is equal to or less than the upper limit value, an excessive thickness can be avoided.
When the second resin layer is composed of a plurality of layers, the total thickness of the plurality of layers may be set to the thickness of the preferable second resin layer.

<Anti-mold 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. The compound (1) and its salt will be described in detail later.
The anti-mold resin film has excellent anti-mold properties by including the anti-mold agent.

In the anti-mold resin film, the contained compound (1) or a salt thereof develops anti-mold properties by gradually shifting from the inside of the anti-mold resin film to the outside.
For example, when a volatile compound (1) or a salt thereof is used, this component can be transferred in the form of a gas to the outside of the anti-mold resin film.

The anti-mold resin film can be produced using a resin composition containing components for constituting the anti-mold resin film, such as the anti-mold agent and the resin. More specifically, the anti-mold resin film is obtained by applying the resin composition to the surface on which the anti-mold resin film is to be formed and drying it as necessary.
The anti-mold resin film composed of a plurality of layers as described later can be produced, for example, by preparing a plurality of single-layer (single layer) anti-mold resin films and bonding them together.

  The resin composition, for example, using various coaters such as spin coater, air knife coater, curtain coater, die coater, blade coater, roll coater, gate roll coater, bar coater, rod coater, gravure coater, multi-coater, etc. Can be applied.

[resin]
The resin is a component necessary for maintaining the shape of the anti-mold resin film. The resin is not particularly limited as long as it has such a function, and may be any of an adhesive resin (sometimes referred to as an “adhesive” in this specification) and a non-adhesive resin. Although it is good, it is preferably an adhesive resin. By using an adhesive resin (adhesive) as the resin, the anti-mold resin film can be made to have an adhesive property (that is, an adhesive anti-mold resin film). Without providing, the mold prevention laminated film mentioned later can be constituted.

  Preferred examples of the adhesive resin include urethane adhesives such as polyurethane (adhesive resins having urethane bonds); acrylic adhesives such as acrylic copolymer resins (adhesive resins having a (meth) acryloyl group); Titanate adhesive (adhesive resin obtained using titanate); imine adhesive (adhesive resin obtained using ethyleneimine); butadiene adhesive such as styrene-butadiene copolymer ( Adhesive resin obtained using butadiene as the 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) And an adhesive resin obtained using olefin as a component.

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

  The mold-proof resin film is selected from the group consisting of urethane adhesives, acrylic adhesives, titanate adhesives, imine adhesives, butadiene adhesives, polyester adhesives, and olefin adhesives as the resin. One having two or more kinds and having adhesiveness is preferable.

[Other ingredients]
The antifungal resin film and the resin composition may contain other components in addition to the antifungal agent and the resin.
The said other component in an anti-mold resin film and a resin composition is not specifically limited unless the effect of this invention is impaired, It can select arbitrarily.
In the anti-mold resin film and the resin composition, the other component may be one kind or two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected according to the purpose.

  As said other component in the said anti-mold resin film and resin composition, a hardening | curing agent, a crosslinking agent, etc. are mentioned, for example. These act on the resin.

  The resin composition may contain other components that do not correspond to either the curing agent or the crosslinking agent as necessary, and a preferable example of other components in this case includes a solvent.

The said solvent is for making the handleability of the said resin composition favorable, and the kind is not specifically limited in the range which does not impair the effect of this invention.
Preferred examples of the solvent include an organic solvent and water.

  Examples of the organic solvent include esters (carboxylate esters) such as ethyl acetate and butyl acetate; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, Examples include 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. .

  In the antifungal resin film and the resin composition, the solvent may be only one kind, or two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected according to the purpose. For example, when two or more solvents are used in combination, only two or more organic solvents may be used in combination, a mixed solvent of only the organic solvent may be used, or one or two or more organic solvents and water may be used in combination. 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. Particularly preferred is 5 g / m ² . When the content of the antifungal agent is not less than the lower limit, the antifungal effect of the antifungal laminated film becomes higher. Moreover, excessive use of a fungicide is suppressed because content of a fungicide is below the said upper limit.

  Total content of compound (1) of mold prevention resin film and salt thereof (in other words, ratio of total content of compound (1) and salt thereof to total content of components other than 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 the salt thereof is not less than the lower limit value, the antifungal effect of the antifungal laminate film is further increased. Moreover, compound (1) and its salt are more stably hold | maintained with high uniformity in a mold prevention resin film because the total content of a compound (1) and its salt is below the said upper limit.

  The content of the resin in the anti-mold resin film (in other words, the ratio of the content of the resin to the total content of components other than the solvent in the resin composition) is preferably 30 to 90% by mass. 40 to 75% by mass is more preferable, and 50 to 65% by mass is particularly preferable. When the content of the resin is equal to or higher than the lower limit value, the strength of the anti-mold resin film is further improved. Moreover, when the content of the resin is equal to or less than the upper limit, the anti-mold effect of the anti-mold resin film is further improved.

  The content of the other component of the anti-mold resin film (in other words, the ratio of the content of the other component to the total content of the components 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 said other component is the said hardening | curing agent or a crosslinking agent, in the anti-mold resin film and the said resin composition, the ratio of content of the said other component with respect to content of the said resin is 10-40 mass. %, And more preferably 20 to 30% by mass. When the ratio is equal to or higher than the lower limit value, the effect of using other components is more remarkably obtained. When the ratio is equal to or lower than the upper limit value, excessive use of other components is suppressed. .

  When the resin composition contains a solvent, the content of the solvent is preferably 10 to 80% by mass, and more preferably 40 to 70% by mass. When the content of the solvent is not less than the lower limit, the effect of using the solvent is more remarkably obtained, and when the content of the solvent is not more than the upper limit, excessive use of the solvent is suppressed. .

  Content of the other component which does not correspond to any of the said solvent, hardening | curing agent, and crosslinking agent of the said anti-mold resin film can be 0-10 mass%, for example.

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

What is necessary is just to select the thickness of the said mold prevention resin film suitably according to a use, and it does not specifically limit it.
For example, when producing a package body such as a bag shape using the anti-mold resin film, the thickness of the anti-mold resin film is preferably 0.1 to 15 μm, and preferably 0.2 to 12 μm. It is more preferable, and it is especially preferable that it is 0.3-10 micrometers, for example, 0.3-7.5 micrometers etc. may be sufficient.
In the case where the moldproof resin film is composed of a plurality of layers, the total thickness of the plurality of layers may be set to the thickness of the preferable moldproof resin film.

The anti-mold laminated film of the present invention may further include other layers in addition to the first resin layer, the anti-mold 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 purpose.

  However, the anti-mold laminated film of the present invention is preferably one in which the first resin layer, the anti-mold resin film and the second resin layer are laminated in direct contact with each other in this order. Thus, the mold-proof lamination of the present invention is not provided between the first resin layer and the mold-proof resin film and between the mold-proof resin film and the second resin layer, respectively. The film has a further excellent antifungal effect.

Moreover, it is preferable that the anti-mold laminated | multilayer film of this invention is not equipped with the said other layer on the opposite side to the side provided with the anti-mold resin film of the 1st resin layer. Thus, when the 1st resin layer serves as one outermost layer of the mold prevention multilayer film, the mold prevention multilayer film of the present invention becomes further excellent in the mold prevention effect.
When the mold prevention laminated film of this invention is equipped with the said other layer, it is preferable to provide the other layer on the opposite side to the side provided with the mold prevention resin film of the 2nd resin layer.

  The mold-proof laminated film of the present invention has a laminated structure as described above, and has an average diameter (average diameter) of 8000 μm or less (for example, the through-hole 14 in the mold-proof laminated film 1 shown in FIG. 1). Have

The shape of the opening of the through-hole on the surface of the anti-mold laminated film and the shape of the opening in the cross-section perpendicular to the longitudinal direction of the through-hole are not particularly limited. A polygonal shape such as a triangular shape or a quadrangular shape; a shape in which two or more types selected from the group consisting of a circular shape, an elliptical shape, and a polygonal shape are combined. However, the shape is preferably a circular shape from the viewpoint of easy formation of the through hole.
In the present specification, unless otherwise specified, the “opening portion of the through-hole” is perpendicular to the longitudinal direction of the through-hole opening portion and the through-hole on the surface of the above-mentioned anti-mold laminated film. Both the opening in a simple cross section shall be meant.

  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) among the lengths of line segments connecting two different points of the opening. 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, when storing the contents (non-heat-treated food) in the storage space of the package manufactured using the anti-mold laminated film, oxygen, dioxide The concentration of carbon and water vapor can be adjusted in a balanced manner to a more suitable range. Furthermore, manufacture of a mold prevention laminated film becomes easier because the average diameter of a through-hole is more than the said lower limit.

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 within such a range, oxygen and carbon dioxide can be stored when storing the contents (non-heat-treated food) in the accommodation space of the package produced using the mold-proof laminated film. In addition, the water vapor concentration can be adjusted in a balanced manner to a more suitable range.

The number of through-holes of the anti-mold laminated film, that is, the number of through-holes per unit area (1 m ² ) of the anti-mold laminated film is determined by the area of the anti-mold laminated film and the number of penetrations per mold-proof laminated film. It can be adjusted by adjusting either or both of the number of holes.

The area of the mold-proof laminated film may be appropriately adjusted according to the use of the mold-proof laminated film, and is not particularly limited, but is preferably 0.01 to 1.5 m ² , for example, 0.015 to ¹ . more preferably 2m is ^2, particularly preferably from 0.02～1M ^2, for ^{example, 0.02~0.5m 2, 0.02~0.3m 2,} and 0.02~0.1m Any of ² etc. may be sufficient.

  The number of through-holes per anti-mold laminate 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 use of the anti-mold laminate film. . For example, the number of through-holes per anti-mold laminated film is preferably 1 to 30, more preferably 1 to 25, and particularly preferably 1 to 20.

  The position of the through hole in the anti-mold laminated film is not particularly limited, but is preferably an area other than the adhesion area at the time of manufacturing the anti-mold package described below. By doing in this way, all the through-holes in a mold prevention laminated film can be functioned effectively also in a mold prevention package.

The moisture permeation amount of the anti-mold laminated film in an atmosphere of 40 ° C. and 90% RH is 5 g / m ² · day or more, preferably 7 g / m ² · day or more, and 8 g / m ² · day. More preferably, it is more preferably 10 g / m ² · day or more. When the water vapor permeation amount of the anti-mold laminated film is not less than the lower limit value, the occurrence of mold in the package is remarkably suppressed in the accommodation space of the package produced using the anti-mold laminated film. .

The upper limit value of the water vapor transmission amount of the anti-mold laminated film in an atmosphere of 40 ° C. and 90% RH is not particularly limited. However, in the storage space of the package produced using the anti-mold laminated film, the effect of suppressing drying and wilting of the contained items (non-heat-treated foods, in particular, fruits and vegetables) becomes higher. The water vapor transmission amount is preferably 50 g / m ² · day or less. The water vapor transmission amount of the anti-mold laminated film is set by appropriately combining any one of the above lower limit value and upper limit value. It is preferable to be within the range.

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

  The water vapor transmission amount of the mold prevention laminated film can be measured according to JIS K 7129B.

The oxygen permeation amount of the anti-mold 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 anti-mold laminated film is not more than the upper limit value, in the accommodation space of the package produced using the anti-mold laminated film, the contents (non-heat-treated food) are more preferable quality. Can be saved. In particular, when non-heat-treated foods are fruits and vegetables, the preserved fruits and vegetables breathe, but by suppressing the increase in oxygen concentration in the accommodation space, the breathing of fruits and vegetables is suppressed, and the consumption of fruits and vegetables is suppressed. Can preserve fruits and vegetables with higher freshness.

The lower limit value of the oxygen permeation amount of the anti-mold laminated film in an atmosphere of 20 ° C. and 80% RH is not particularly limited. However, the oxygen permeation amount of the anti-mold laminated film is 30 g / m in that the contained matter (non-heat-treated food, in particular, fruits and vegetables) suppresses oxygen deficiency in the accommodation space of the package. ^The oxygen permeation amount of the anti-mold laminated film is preferably within a range set by appropriately combining any one of the above lower limit value and upper limit value.

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

The oxygen permeation amount of the anti-mold laminated film can be measured, for example, by the following method.
That is, after producing a package using an anti-mold laminated film and sealing it in the atmosphere, the atmosphere in the packaging space is replaced with nitrogen gas of V (cc) having a purity of 99.9% or more. , T (hr) is the elapsed time from the completion of replacement with nitrogen gas, and t = 0 (that is, when replacement with nitrogen gas is completed), where the oxygen concentration inside the bag is C _t (%). 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 ) To calculate the oxygen transmission rate F (cc / m ² · day).
The atmosphere in the accommodation 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. C _t is obtained by preparing a calibration curve in advance and using this calibration curve.
F = 1.143 × (C _t −C ₀ ) × V / t (i)

<< An anti-mold resin film having a through hole >>
In the anti-mold laminated film, each of the layers (the first resin layer, the anti-mold resin film, the second resin layer, and the other layers provided as necessary) constituting the same is between adjacent layers. It has a through-hole formed continuously. Among these, the anti-mold resin film having a through-hole is a novel one, and it can be useful in applications other than the anti-mold laminated film.
That is, as a preferable antifungal resin film having such a through hole, for example, an antifungal resin film containing the antifungal agent and a resin, and the antifungal resin film has an average diameter. 8000μm following through-holes, those having the number of 40 to 400 pieces / ^{m 2,} and the like.

<< Method for Producing Mold-proof Multilayer Film >>
The mold prevention laminated film of this invention can be manufactured by applying the well-known manufacturing method of a multilayer lamination film using the above-mentioned resin composition for mold prevention resin films.
For example, the resin composition is applied to one surface (one side) of the first resin layer and the second resin layer, and dried as necessary to form a mold-proof resin film. A first laminate is formed by laminating the resin layer or the second resin layer and the anti-mold resin film. The formation method of the mold prevention resin film at this time is the same as the production method of the mold prevention resin film described above.

Next, the exposed surface of the mold-proof resin film in the first laminate (the surface where the first resin layer or the second resin layer is not provided) and the other surface (one surface) of the first resin layer and the second resin layer Are bonded together to form a second stacked body. Here, “the other of the first resin layer and the second resin layer” refers to the second resin layer in the case where what is laminated on the anti-mold resin film in the first laminate is the first resin layer. When the thing laminated | stacked on the anti-mold resin film in the said 1st laminated body is a 2nd resin layer, it means the 1st resin layer.
Bonding of the first laminate and the second resin layer or the first resin layer can be performed by applying various known laminating methods.

Next, a desired number of through-holes are formed at desired locations in the second laminate.
The through hole can be formed by a known method such as a method of piercing a needle or a method of irradiating a laser to the second laminate.

  Although the said anti-mold laminated film is obtained by the above, when manufacturing the anti-mold laminated film which comprises other layers other than the 1st resin layer, the anti-mold resin film, and the 2nd resin layer, it is the above-mentioned. In the manufacturing method of (1), an additional step of forming the other layer is performed at an appropriate timing so that the other layer is arranged at a target stacking position, or the other layer is formed in advance. What is necessary is just to add and paste. In this case, what is provided with the other layer is formed as the second laminated body, and a through hole may be formed for this.

  So far, as the method for producing a mold-proof laminated film, the one having the step of simultaneously forming the mold-proof resin film and the first laminate using the resin composition has been described. However, other methods may be used as a method for producing a mold-proof laminated film, for example, a production method including a step of forming a first laminate using a mold-proof resin film that has been formed in advance.

Thus, when using a pre-formed anti-mold resin film, for example, an anti-mold laminated film may be manufactured as follows.
First, an anti-mold resin film is formed on the release treatment surface of a release film having a release treatment surface using the resin composition. The formation method of the mold prevention resin film at this time is the same as the production method of the mold prevention resin film described above. The formed anti-mold resin film may be further provided with a release film on the surface not provided with the release film.

  Next, the release film is removed at an appropriate timing, the first resin layer is bonded to one surface of the anti-mold resin film, and the second resin layer is bonded to the other surface of the anti-mold resin film, whereby the second lamination Form the body. The bonding of the anti-mold resin film and the first resin layer and the bonding of the anti-mold resin film and the second resin layer may be performed sequentially by performing either one first and the other later. However, they may be performed at the same time.

Next, the mold-proof laminated film is obtained by forming the through-holes as many as the desired number in the desired location with respect to the second laminated body by the same method as described above.
Even in this method, when producing a mold-proof laminated film comprising the other layer, in the above-described production method, the other layer is disposed at a desired lamination position at an appropriate timing, and The step of forming other layers may be performed additionally, or pasting of the other layers that have been formed in advance may be added. In this case, what is provided with the other layer is formed as the second laminated body, and a through hole may be formed for this.

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

(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 an alkylene group, more specifically, a methylene group (—CH ₂ —), Examples include an ethylene group (—CH ₂ CH ₂ —), a propylene group (—CH (CH ₃ ) CH ₂ —, a methylethylene 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. As such an alkyl group, more specifically, a methyl group (—CH ₃ ), 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 General Formula (1), m is an integer of 1 to 3, and is represented by General Formula “—O—X—OH (wherein X is the same as above)” in one molecule of Compound (1). Indicates the number of groups to be made.
When m is 2 or more (that is, 2 or 3), a plurality of (that is, 2 or 3) Xs may be the same as or different from each other. That is, when m is 2 or more, all Xs may be 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 “—O—X—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 “—O—X—OH” is bonded are adjacent to each other. Preferably not.
When m is 3, at least two of the three carbon atoms constituting the benzene ring skeleton to which the group represented by the general formula “—O—X—OH” is bonded. Are preferably not adjacent to each other, more preferably all three carbon atoms are not adjacent to each other.

In general formula (1), n is an integer of 0 to 5, and represents 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) R may be the same as or different from each other. That is, when n is 2 or more, all Rs may be the same, all may be different, or only a part may be the same.

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

  The relationship of the relative bond position between R in the benzene ring skeleton and the group represented by the general formula “—O—X—OH” is not particularly limited.

  Examples of the compound (1) when m is 1 include compounds represented by the following general formula (1) -1A (in this specification, sometimes referred to as “compound (1) -1A”). It is 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 of 0 to 5.)

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

  As the compound (1) when m is 2, 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 this specification, “compound (1) -2A”, “compound (1) -2B”, “compound (1) -2C” and May be referred to).

（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 of 0 to 4.)

In General Formula (1) -2A to General Formula (1) -2C, X and R are the same as X and R in General Formula (1).
In General Formula (1) -2A to General Formula (1) -2C, n2 is an integer of 0 to 4, and is the same as n in General Formula (1) except that it is not 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 the present specification, “compound (1) -3A”, “compound (1) -3B”, “compound (1) -3C” May be referred to).

（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 of 0 to 3.)

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

  In the compound (1), m is preferably 1 or 2, and more preferably 1. Such a compound (1) not only has an excellent antifungal action, but can 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 this specification, sometimes referred to as “compound (1) -0”). It is 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 to 3.)

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

  Examples of the compound (1) when n is 1 include compounds represented by the following general formula (1) -1a (in this specification, sometimes referred to as “compound (1) -1a”). It is 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 general formula (1) -1a, X and R are the same as X and R in general formula (1).
In general formula (1) -1a, m1 is an integer of 1 to 3, and is the same as m in general formula (1).

  As the compound (1) when n is 2, 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)- The compounds represented by 2c (in the present specification, "compound (1) -2a", "compound (1) -2b", "compound (1) -2c" May be referred to).

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

  As the compound (1) when n 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)- The compound represented by 3c (in this specification, “compound (1) -3a”, “compound (1) -3b”, “compound (1) -3c” May be referred to).

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

  As the compound (1) when n is 4, 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)- 4c (in the present specification, "compound (1) -4a", "compound (1) -4b", "compound (1) -4c" May be referred to).

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

  Examples of the compound (1) when n is 5 include compounds represented by the following general formula (1) -5a (in this specification, sometimes referred to as “compound (1) -5a”). It is 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 general formula (1) -5a, X and R are the same as X and R in 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 the 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 0 or 1. Particularly preferred. Such a compound (1) not only has an excellent antifungal action, but can be produced more easily and inexpensively.

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

  As a particularly preferable compound (1), for example, a compound represented by the following general formula (1) -1A-0 (in this specification, it may be referred to as “compound (1) -1A-0”). And compounds represented by the following general formula (1) -1A-1 are preferred, and compound (1) -1A-0 is most preferred.

（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.
Examples of the salt of the compound (1) include a group represented by the general formula “—O—X—OH” in the compound (1) represented by an anion (that is, the general formula “—O—X—O ⁻ ”). Formed with a cation (in the present specification, sometimes referred to as “anion derived from compound (1)”) and a cation (wherein X is the same as above)) Salt.

  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 cations forming the salt of the compound (1) and the number of anions derived from the compound (1) are both 1. When the cation is p-valent (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 number of anions derived from the compound (1) The number is p or less, preferably p.

As described above, the cation constituting the salt of one molecule of the compound (1) may be only one, or two or more, and when there are two or more, these cations may be all the same. They may be all different, or only part of them may be the same.
However, the salt of the compound (1) is electrically neutral as a whole molecule, that is, the total value of the cation valence and the total value of the anion valence in one molecule of the compound (1) are the same. Is preferred.

  The cation that forms 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, inorganic cations include, for example, alkali metal ions such as lithium ions (Li ⁺ ), sodium ions (Na ⁺ ), and potassium ions (K ⁺ ); magnesium ions (Mg ²⁺ ), calcium ions (Ca ²⁺ ), ions of alkaline earth metals such as barium ions (Ba ²⁺ ); ions of typical metals such as aluminum ions (Al ³⁺ ), zinc ions (Zn ²⁺ ), tin ions (Sn ²⁺ , Sn ⁴⁺ ); copper ions ( Cu ⁺ , Cu ²⁺ ), iron ions (Fe ²⁺ , Fe ³⁺ ), manganese ions, transition metal ions such as nickel ions; non-metal ions such as ammonium ions (NH ₄ ⁺ ), and the like.

In the said fungicide, only 1 type may be sufficient as an active ingredient, and when it is 2 or more types, those combinations and ratios can be arbitrarily selected according to the objective.
For example, the fungicide may contain only one or more compounds (1) as active ingredients, or may contain only one or more salts of the compound (1). Alternatively, the compound (1) and the salt of the compound (1) may each contain one kind or two or more kinds.

  The compound (1) and its salt are preferably usable as food additives. As used herein, “food additive” means that the Ministry of Health, Labor and Welfare of Japan has approved its use as of March 12, 2013.

The compound (1) and its salt are preferably volatile. The compound (1) and its salt that have volatility is advantageous in that it becomes a gas from a liquid at room temperature, so that it acts continuously in the accommodation space of the package, which will be described later. The mold prevention effect can be maintained for a longer time.
In the present specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and includes a temperature of 15 to 25 ° C., for example.

  The molecular weight of the compound (1) and its salt is preferably 300 or less in terms of being easily volatilized, and may be any of 250 or less, 200 or less, 150 or less, etc. It is an example. In addition, the lower limit of the molecular weight of the compound (1) and its salt is not particularly limited.

Compound (1) and its salt are preferably odorless or have a weak odor. Such a compound (1) and a salt thereof are preferred in terms of functionality because even if they are attached to an object to be preserved, the presence of the object to be preserved is hardly or hardly reminded at the time of use.
The compound (1) and its salt having an odor is preferably usable as a fragrance. As such a compound (1) and its salt, what is classified into the natural fragrance | flavor of a food additive is mentioned, for example.

  Thus, the compound (1) or a salt thereof that can be used as a food additive, has volatility, is odorless, or has a weak odor, for example, corresponds to the compound (1) -1A-0 And 2-phenoxyethanol represented by the following formula.

  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.

<Method for Producing Compound (1)>
Compound (1) is represented, for example, by a compound represented by the following general formula (101) (sometimes referred to as “compound (101)” in this specification) and the following general formula (102): A step of reacting a compound (sometimes referred to as “compound (102)” in this specification) to obtain compound (1) (referred to as “compound (1) production step” in this specification). In some cases).

（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。）

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

The reaction in the production process of compound (1) is known, and the reaction conditions may be appropriately selected according to the type of 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 production process of compound (1), for example, a hydroxyl group (—OH) in compound (102) and the like that may cause an unintended reaction in the raw material used may be protected with a protecting group in advance. The compound (1) may be obtained by carrying out the reaction and deprotecting after completion of the reaction.
Compound (101) can be produced by applying a normal production method for sodium alkoxide. For example, using a corresponding phenol compound as a raw material, that is, a compound in which a group represented by the formula “—O ^— Na ⁺ ” is replaced with a group represented by the formula “—OH” in the compound (101), Compound (101) can be obtained by reacting metal sodium, sodium hydride and the like.
Compound (102) is a corresponding alcohol as a raw material, that is, a compound represented by the general formula “HO—X—OH (X is as defined above)”, or one of the hydroxyl groups thereof is protected with a protecting group. It can manufacture by the method of introduce | transducing Lg using the compound which was prepared. When a protecting group is used, the protecting group may be removed (deprotected) at an appropriate timing. However, the manufacturing method of the compound (102) shown here is an example.

In the production process of compound (1), after completion of the reaction of compound (101) and compound (102), the compound (1), which is the target product, can be obtained by performing post-treatment as necessary by a known method. it can. That is, after completion of the reaction, post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, concentration, etc. are carried out as needed, either alone or in combination of two or more to concentrate, crystallize, reprecipitate Compound (1) can be removed by column chromatography or the like. In addition, the taken out compound (1) is further subjected to operations such as crystallization, reprecipitation, column chromatography, extraction, stirring and washing of crystals with a solvent, if necessary, or a combination of two or more. You may refine | purify by performing it more than once.
The compound (1) may be used for the intended purpose without being taken out after being subjected to post-treatment as necessary after completion of the reaction.

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

<Method for producing salt of compound (1)>
The salt of compound (1) can be produced by applying a usual production method for metal alkoxide. For example, in the case of the sodium salt (sodium alkoxide) of the compound (1), the compound (1) in an isolated state or the compound (1) before extraction in the production method of the compound (1) described above Then, by applying the same method as in the production of the above compound (101), the target product is obtained. As the compound (1) in an isolated state, a commercially available product may be used.
The salt of the compound (1) may be taken out and used in the same manner as in the case of the compound (1), or may be continuously used for the intended use 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 antifungal agent may contain other components in addition to the compound (1) or a salt thereof.
The said other component in an antifungal agent is not specifically limited unless the effect of this invention is impaired, It can select arbitrarily.
For example, the compound (1) or a salt thereof may be either solid or liquid at normal temperature and normal pressure, and appropriately selected according to the type of the mold-proof resin film described later. That's fine. The compound (1) or a salt thereof may be used by, for example, being dissolved or dispersed in a solvent, or diluted with a solvent. That is, examples of the other components include a solvent.

What is necessary is just to select the said solvent suitably according to the kind of compound (1) or its salt, and the kind is not specifically limited.
As the preferable solvent, for example, the same solvent as the solvent that may be contained in the resin composition described above may be used.

When the said fungicide contains the said solvent, content of a solvent is not specifically limited, For example, it can be 10-90 mass%, but this is only an example.
In addition, the said anti-mold agent containing a solvent can be used as it is as the said resin composition for forming an anti-mold 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 according to the type of the other components. That's fine.
However, usually, in the antifungal agent, other than the solvent with respect to the total content of components other than the solvent (that is, the compound (1), the salt of the compound (1), and other components other than the solvent) The content ratio of the other components is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, for example, 2% by mass or less, Any of mass% or less etc. may be sufficient.

Microorganisms (molds) that exhibit growth inhibitory effects (antifungal effects) due to the use of the antifungal agent are not limited to specific ranges, but penicillium has high antifungal effects. Microorganisms belonging to the genus (Penicillium), microorganisms belonging to the genus Aspergillus, microorganisms belonging to the genus Cladosporium, microorganisms belonging to the genus Fusarium, microorganisms belonging to the genus Alternaria, Rhizopus ) Microorganisms belonging to the genus, microorganisms belonging to the genus Botrytis, and the like.
Among these, examples of microorganisms belonging to the genus Penicillium include blue mold and white mold. Examples of microorganisms belonging to the genus Aspergillus include Aspergillus niger. 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. Examples of microorganisms belonging to the genus Alternaria include Alternaria tenuis. Examples of microorganisms belonging to the genus Rhizopus include Rhizopus nigricans. Examples of microorganisms belonging to the genus Botrytis include gray mold.

  What contains 2 or more types of components among the said fungicides is obtained by mix | blending these components.

At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good.
The mixing method is not particularly limited. From a known method such as a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, a kneader or a bead mill; a method of mixing by applying ultrasonic waves What is necessary is just to select suitably.

  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.

<< Anti-mold packaging >>
The mold-proof package of the present invention is a mold-proof package obtained by using the mold-proof laminated film of the present invention described above, and is a container in which a part of the first resin layers are bonded and formed. It has space and the said mold prevention resin film is arrange | positioned rather than the said 2nd resin layer at the said accommodation space side.
The mold-proof package of the present invention uses the mold-proof laminated film (mold-resistant resin film), and thus has excellent mold-proof properties, and the growth of mold in the storage space during storage of the target product. 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 one embodiment of the anti-mold package of the present invention.
The anti-mold packaging body 10 shown here is formed using the anti-mold laminated film 1 shown in FIG. The anti-mold package 10 has a housing space S formed by bonding a part of the first resin layers 11 and 11 of the pair of anti-mold laminated films 1 and 1, and the anti-mold resin film 12. Is arranged closer to the accommodation space S than the second resin layer 13 and is schematically configured. That is, the pair of anti-mold laminated films 1 and 1 are arranged such that these first resin layers 11 and 11 face each other.
A target storage object (not shown) is stored in the storage space S of the anti-mold package 10.
In FIG. 2, illustration of the through hole is omitted.

In the anti-mold package 10, the compound (1) or a salt thereof easily migrates from the inside of the anti-mold resin film 12 into the accommodation space S through the first resin layer 11. Thereby, the mold prevention package 10 can maintain the density | concentration of the compound (1) in the accommodation space S or its salt at a suitable level for a fixed period, and expresses the outstanding mold prevention effect.
In addition, the mold-proof package 10 has an excellent mold-proof effect by having the through-hole so that the amount of moisture in the accommodation space S can be adjusted.
In addition, in the anti-mold package 10, the first resin layer 11 prevents contact between the storage object in the storage space S and the anti-mold resin film 12, and excessive migration of the anti-mold agent to the storage object. Is suppressed.

  Furthermore, since the mold-proof package 10 has the through-hole, the oxygen concentration in the accommodation space S can be adjusted to an appropriate range, so that the freshness of non-heat-treated foods such as fruits and vegetables can be maintained.

  Furthermore, in the anti-mold package 10, as described in the anti-mold laminated film, by adjusting the configuration of the second resin layer 13, the anti-mold effect can be maintained and the object to be stored by oxygen gas from the outside. It is possible to further increase the effect of suppressing deterioration of objects. In addition, by adjusting the type of the compound (1) or a salt thereof, the use of the compound (1) or a salt thereof (antifungal agent) is reminded at all or little when using the storage object after storage. It can also be preferred in terms of functionality.

  Up to this point, the anti-mold package of the present invention has been described using the anti-mold laminated film 1 shown in FIG. 1, but the anti-mold package of the present invention is the anti-mold of the other embodiment of the present invention. It may be formed using a laminated film.

The mold-proof 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 without departing from the spirit of the present invention.
For example, the moldproof package 10 shown in FIG. 2 uses a pair of mold-proof laminated films 1 and 1 of the same type, but the mold-proof package of the present invention has a pair of different mold-proof laminates. A film may be used.
Moreover, the anti-mold package of this invention may be equipped with other structures other than the anti-mold laminated film in the range which does not impair the effect of this invention. The other configurations are not particularly limited, and may be appropriately selected depending on the purpose.

The anti-mold package of the present invention can be produced by bonding a part of the first resin layers so as to have an accommodation space using the anti-mold laminated film of the present invention.
The adhesion between the first resin layers can be performed, for example, by applying various known laminating methods.
When bonding a part of the first resin layers, it is preferable to bond the first resin layers while avoiding a region having a through hole in the first resin layer (anti-mold laminated film). By doing in this way, all the through-holes in a mold prevention laminated film can be functioned effectively also in a mold prevention package.

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

Examples of vegetables include eggplant, ginger, tomato, bell pepper, red bell pepper, carrot, cabbage, potato, lettuce, radish, spinach, long onion, onion, broccoli, cauliflower, shiitake, shimeji and the like.
Examples of fruits include orange, navel orange, mandarin orange, lemon, kumquat, eggplant, grapefruit, apple, pear, pear, mango, fig, grape, strawberry, pineapple, kiwi, blueberry, pomegranate, peach, papaya, melon, Watermelon, banana, avocado, etc. are mentioned.
Examples of cereals include peas, dacha beans, corn, potatoes, and sweet potatoes.

  The mold-proof package of the present invention is preferably used for packaging fruits and vegetables, and more preferably used for packaging citrus fruits such as orange, navel orange, mandarin orange, lemon, kumquat, eggplant, and grapefruit.

  When the object product is accommodated and packaged in the accommodation space using the mold prevention package of the present invention, the content of the mold prevention agent per 100 g of the package (package) of the mold prevention package is as follows: 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 not less than the lower limit value, the antifungal effect of the antifungal package becomes higher. Moreover, the excessive use of a fungicide is suppressed because the said content of a fungicide is below the said upper limit.

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

<Manufacture of mold-proof laminated film>
[Example 1]
The mold prevention laminated film of the structure shown in FIG. 1 was manufactured with the procedure shown below.

(Manufacture of mold-proof resin film)
Main agent ("Takelac (registered trademark) A620" manufactured by Mitsui Chemicals, Inc., solid content 50% by mass, ethyl acetate 50% by mass) (6 parts by mass), curing agent ("Takenate (registered trademark) A10" manufactured by Mitsui Chemicals, Inc.) , 75 mass% solid content, 25 mass% ethyl acetate) (1 mass part), and ethyl acetate (6 mass parts) were mixed to prepare a polyurethane-based adhesive. In the obtained polyurethane adhesive, the total content of the solvent (ethyl acetate) is 71.2% by mass.
Subsequently, 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 components other than the solvent was 34.8% by mass. A resin composition was obtained.

  Next, the resin composition obtained above was applied to one surface of a PET film (thickness: 12 μm) using a multicoater and dried at 80 ° C., so that the content of 2-phenoxyethanol was 35. An anti-mold resin film (thickness 5.8 μm) having a mass% was formed on a PET film. Thus, the first laminate was produced.

(Manufacture of mold-proof laminated film)
Furthermore, by bonding the LLDPE film (thickness 30 μm) to the surface of the first laminate obtained above on the side opposite to the side on which the PET film of the anti-mold resin film is provided, the PET film, An antifungal resin film and LLDPE film were laminated in this order to obtain a transparent second laminate having a size of 150 mm × 250 mm.

Next, needles were pierced at four locations sufficiently separated from each other in the second laminate, thereby forming four through-holes having an average diameter of 180 μm in the second laminate to obtain a mold-proof laminated film. .
The size (mm × mm) of the obtained anti-mold laminated film, the average diameter (μm) of the through holes, the number of through holes (pieces / piece), the number of through holes (pieces / m ² ), and the mold prevention Table 1 shows the content (g / m ² ) and thickness (μm) of the fungicide of the resin film. In Table 1, the antifungal agent content (g / m ² ) and thickness (μm) of the antifungal resin film are the same as the antifungal agent content of the packaging film in Comparative Examples described later ( g / m ² ) and thickness (μm) in order to show in the same column, “resin film fungicide content (g / m ² )”, “resin film thickness (μm)” The corresponding numerical values are described here.

<Measurement of oxygen permeation rate of mold-proof laminated film>
About the anti-mold laminated film obtained above, the oxygen permeation amount was measured by the following method. The results are shown in Table 1.

(I) Production of bag
In the atmosphere, a bag was produced by heat sealing using the above-mentioned anti-mold laminated film and sealed.

(II) Encapsulation of nitrogen gas in the bag After degassing the inside of the bag until both sides of the bag adhered, the bag was filled with nitrogen gas having a purity of 99.9% or more. Deaeration and nitrogen gas injection were performed by inserting a needle into the bag. The filling amount V (cc) of the nitrogen gas was increased as much as possible so that the film was not excessively tensioned and slightly loosened, and was measured by the scale of the syringe barrel. When inserting the injection needle into the bag, a double-sided tape was affixed to the corresponding part of the film, and a polypropylene film adhesive tape (hereinafter abbreviated as “PP tape”) was affixed on the double-sided tape. Further, after removing the needle, the needle hole was immediately closed with PP tape. The area of the PP tape was 4.5 cm ² or less. In addition, when sticking a double-sided tape and PP tape, it was made not to block the through-hole of a film with these tapes.

(III) Measurement of Initial Oxygen Concentration 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 (inside the bag is measured by gas chromatography (TCD)). %). In the present specification, the elapsed time from the completion of the filling of nitrogen gas is t (hr), and the oxygen concentration inside the bag at this time is represented by “C _t (%)”. Since _C0 is 0.2% or less, when it exceeds 0.2%, the above operation is repeated. The amount of sampling gas injected when performing gas chromatography was a fixed amount of about 1 cc. Further, a standard curve having two or more levels including the case where the oxygen concentration was about 1% and about 10% was also subjected to gas chromatography to prepare a calibration curve.

(IV) Bag Storage The bag whose initial oxygen concentration was measured was 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 in such a manner that no object was placed on the bag or that the fan of the constant temperature and humidity chamber did not directly hit the bag.

(V) Measurement of oxygen concentration inside 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 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. In the case where a proportional relationship having a correlation coefficient of 0.98 or more is not established between t and C _t , the test was repeated. And when t was the largest, 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 this A film having a known small oxygen permeation amount than that of the film was bonded, and the oxygen concentration inside the bag was measured in the same manner as described above with the improved bag thus obtained. At this time, the area of the region where the film having the smaller oxygen transmission amount is bonded is subtracted from the surface area of the original bag, and the above known oxygen transmission amount is subtracted from the oxygen transmission amount of the film in the improved bag. The value was determined as the oxygen permeation amount of the target film.
F = 1.143 × (C _t −C ₀ ) × V / t (i)

<Measurement of water vapor transmission rate of mold-proof laminated film>
About the anti-mold laminated film obtained above, the water vapor transmission rate (g / m ² · day) in an atmosphere of 40 ° C. and 90% RH was measured according to JIS K 7129B. The results are shown in Table 1.

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

[Example 3]
A mold-proof laminated film was produced in the same manner as in Example 1 except that the size of the mold-proof laminated film was as shown in Table 1, and the oxygen transmission rate and water vapor transmission rate were measured. The results are shown in Table 1.

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

[Example 5]
Except that the size of the mold-proof laminated film was as shown in Table 2, a mold-proof laminated film was produced in the same manner as in Example 1, and the oxygen transmission rate and water vapor transmission rate were measured. The results are shown in Table 2.

[Example 6]
Except for the point that the content and thickness of the anti-mold agent of the anti-mold resin film and the size of the anti-mold laminated film, the average diameter of the through holes, and the number of the through holes are as shown in Table 3. 1 was used to produce a mold-proof laminated film, and the oxygen permeation amount and water vapor permeation amount were measured. The results are shown in Table 3.

[Example 7]
The same as in Example 1 except that the antifungal agent content 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 were as shown in Table 3. By the method, an anti-mold laminated film was produced, and its oxygen permeation amount and water vapor permeation amount were measured. The results are shown in Table 3.

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

[Example 9]
In the same manner as in Example 1, except that the antifungal agent content of 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 transmission rate and water vapor transmission rate were measured. The results are shown in Table 4.

<Manufacture of packaging film for comparison>
[Comparative Example 1]
By penetrating a needle into a biaxially stretched transparent polypropylene (PP) film (OPP film) having a size of 150 mm × 250 mm and a thickness of 3.1 μm, a through hole having an average diameter of 120 μm is universal. A comparative packaging film was obtained after forming 100,000 pieces.
And the oxygen permeation amount and 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 comparative packaging laminated film is produced in the same manner as in Example 1, except that the mold preventive agent is used and the thickness of the resin film and the size of the film are as shown in Table 1 or 2. The oxygen permeation amount and water vapor permeation amount were measured. The results are shown in Table 1 or 2. In other words, the laminated film for packaging of Comparative Example 2 is the same as the anti-mold laminated film of Example 2 except that no anti-fungal agent is used, and the laminated film for packaging of Comparative Example 3 is anti-mold. Except for not using the agent, it is the same as the mold-proof laminated film of Example 4.

[Comparative Example 4]
The same method as in Example 1 except that the antifungal agent was not used and 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 as shown in Table 3. Then, a laminated film for packaging for comparison was manufactured, and the oxygen permeation amount and the water vapor permeation amount were measured. The results are shown in Table 3. In other words, this packaging laminated film is the same as the mold-proof laminated film of Example 6 except that the mold-proofing agent is not used.

[Comparative Example 5]
For the comparative packaging, the same method as in Example 1, except that the mold preventive agent was used and the thickness of the resin film, the size of the film, and the number of through holes were as shown in Table 4. A laminated film was produced, and its oxygen transmission rate and water vapor transmission rate were measured. The results are shown in Table 4. In other words, the laminated film for packaging is the same as the anti-mold laminated film of Examples 8 to 9 except that the anti-mold agent is not used and the thickness of the resin film is different.

<Evaluation of anti-mold packaging>
[Test Example 1]
(Confirmation of preservation effect against Navel Orange)
Two anti-mold 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 anti-mold laminated films, and the periphery of these anti-mold laminated films They were overlapped and heat laminated. As described above, the above-mentioned two navel oranges were accommodated in a transparent bag (anti-mold package) made from the above-mentioned anti-mold laminated film, and a sealed sample was produced. A total of six such samples were produced.
Similarly, six samples were produced using the packaging film of Comparative Example 1.
Table 1 shows the content (g) of the antifungal agent per 100 g of the contents of the obtained bag (an antifungal package, a comparative package).

Next, the sample obtained above is stored at 20 ° C. for 8 days, and during this period, the sealed navel orange is visually observed through a bag to confirm the number of days until the navel orange is moldy. did. Moreover, about the navel orange after completion | finish of preservation | save, the degree of suppression of wilting was observed visually, the taste of the part which can be eaten was confirmed, and it evaluated in accordance with the following evaluation criteria. The results are shown in Table 1. When the suppression of wilting and the taste were both “A”, it was determined that the freshness of the contents was maintained.
(Suppression of wilting)
A: No wilting is observed, and the state immediately after harvesting is maintained.
B: Withering was observed, and the state immediately after harvesting was not maintained.
(Taste)
A: Flavor immediately after harvest is felt, and there is no sense of incongruity in the taste.
B: Abnormality is felt in the flavor, and the taste is uncomfortable.

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

[Test Example 2]
(Confirmation of preservation effect on fig (1))
Two anti-mold laminated films of Example 2 were prepared, and in the atmosphere, with one fig of about 86 g sandwiched between these anti-mold laminated films, the peripheral parts of these anti-mold laminated films were Laminated and heat laminated. As described above, the above-mentioned single fig was accommodated in a transparent bag (anti-mold package) made from the above-mentioned anti-mold laminated film, and a sealed sample was produced. A total of five such samples were produced.
Similarly, using the anti-mold laminated film of Example 3 and the packaging film of Comparative Example 2, five samples were produced for each of these Examples or Comparative Examples.
Table 1 shows the content (g) of the antifungal agent per 100 g of the contents of the obtained bag (an antifungal package, a comparative package).

  The sample obtained above and a single unwrapped fig (ie, unwrapped sample) (ie, unwrapped sample) are then stored at 10 ° C. for 14 days, during which the sealed fig is The figs that were not packaged were visually inspected directly to confirm the number of storage days until mold appeared on the figs. Moreover, about the fig after a preservation | save completion, the degree of suppression of wilting was observed visually, the taste of the part which can be eaten was confirmed, and it evaluated similarly to the case of 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 wrinkle suppression and taste were poor, and the freshness was not maintained. It was.
On the other hand, when the mold-proof laminated film of Example 2 was used, mold was generated at the stage of storage for 3 days, the suppression of wilting and the taste were good, and the freshness was maintained. It was.
When the mold-proof laminated film of Example 3 was used, mold was generated at the stage of 4 days of storage, suppression of wilting and taste were good, and freshness was maintained.
The unwrapped fig (unwrapped sample) is not sealed, so the moisture content in the surrounding environment does 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 beginning of storage, and the freshness was not maintained.

[Test Example 3]
(Confirmation of preservation effect on fig (2))
Using the mold-proof 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. Except for the points, evaluation was performed in the same manner as in Test Example 2. 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 one storage day.
On the other hand, when the mold-proof laminated film of Example 3 was used, mold was generated at the stage of storage for 4 days, suppression of wilting and taste were good, and freshness was maintained. It was.
In addition, although the fig (unwrapped sample) which was not packaged was not sealed, the storage temperature was higher than in the case of Test Example 2, and mold was generated at the stage of 2 days of storage. Furthermore, since the unwrapped sample was not packaged, the suppression of the wilting and the taste were poor at this stage. In the first place, the wilting occurred from the beginning of the storage, and the freshness was not maintained.

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

  Subsequently, the sample obtained above was stored at 20 ° C. for 14 days. During this period, the sealed mango was visually observed through a bag, and the number of storage days until mold was generated in the mango was confirmed. Moreover, about the mango after completion | finish of storage, the degree of suppression of wilting was observed visually, the taste of the part which can be eaten was confirmed, and it evaluated similarly to the case of 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 mold-proof laminated film of Examples 4 to 5 was used, mold was generated in all at the stage of 14 days of storage, suppression of wilting and taste were good, and freshness Was held.

[Test Example 5]
(Confirmation of preservation effect on eggplant (1))
Two anti-mold laminated films of Example 6 were prepared, and in the atmosphere, with three eggplants having an average mass of 418 g sandwiched between these anti-mold laminated films, the peripheral portions of these anti-mold laminated films were Were laminated together and heat laminated. As described above, the above-mentioned three eggplants were housed in a transparent bag (anti-mold package) made from the above-mentioned anti-mold laminated film, and a sealed sample was produced. A total of five such samples were produced.
Similarly, using the anti-mold 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 contents of the obtained bag (an antifungal package, a comparative package).

  Next, the sample obtained above and three eggplants with an average weight of 418 g (that is, an unwrapped sample) were stored at 10 ° C. for 14 days. This was visually observed through a bag, and eggplants that were not packaged were visually observed directly to confirm the number of storage days until mold was generated on the eggplant. Further, the eggplant after storage was visually observed for the degree of suppression of wilting and evaluated in the same manner as in Test Example 1. Since eggplants are not usually eaten without heat treatment, the taste was not confirmed, and when the suppression of wilting was “A”, it was determined that the freshness of the contents was maintained. 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 storage for 7 days.
On the other hand, when the mold-proof laminated film of Example 6 was used, mold was generated at the stage of storage for 9 days, the suppression of wilting was good, and the freshness was maintained.
When the mold-proof laminated film of Example 7 was used, mold was generated at the stage of storage for 11 days, the suppression of wilting was good, and the freshness was maintained.
Note that the unwrapped eggplant (unwrapped sample) was not sealed, but mold was generated at the stage of storage for 1 day. Further, since the unwrapped sample was not packaged, the suppression of wilting was poor at this stage, and in the first place, wilting occurred from the beginning of storage and the freshness was not maintained.

[Test Example 6]
(Confirmation of preservation effect on eggplant (2))
Using the anti-mold 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. Except for the points, evaluation was performed in the same manner as in Test Example 5. 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 storage for 2 days.
On the other hand, when the mold-proof laminated film of Example 7 was used, mold was generated at the stage of 4 days of storage, the suppression of wilting was good, and the freshness was maintained.
Note that the unwrapped eggplant (unwrapped sample) is not sealed, so the moisture content in the surrounding environment does not increase, and mold was generated at the stage of 7 days of storage, Due to the lack of packaging, the suppression of wilting was poor at this stage. In the first place, wilting occurred from the beginning of storage, and the freshness was not maintained.

[Test Example 7]
(Confirmation of preservation effect against dadacha beans)
Two anti-mold laminated films of Example 8 were prepared, and the peripheries of these anti-mold laminated films were placed in the air with the average mass of 257 g of dacha beans sandwiched between the anti-mold laminated films. Were laminated together and heat laminated. As described above, the above-described 257 g of dadacha beans were housed in a transparent bag (anti-mold package) made from the above-mentioned anti-mold laminated film, and a sealed sample was produced. A total of six such samples were produced.
Similarly, six samples were produced for each of these Examples or Comparative Examples using the mold-proof laminated film of Example 9 and the packaging film of Comparative Example 5.
Table 4 shows the content (g) of the fungicide per 100 g of the obtained bag (mold prevention package, comparative package).

  Next, the sample obtained above is stored at 25 ° C. for 7 days. During this time, the sealed dada beans are visually observed through a bag until mold is generated on the dada beans. The number of storage days was confirmed. Moreover, about the dacha beans after completion | finish of preservation | save, the degree of suppression of wilting was observed visually, the taste of the part which can be eaten was confirmed, and it evaluated similarly to the case of 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 storage for 1 day.
On the other hand, when the mold-proof laminated films of Examples 8 to 9 were used, mold was generated at all stages of storage for 3 days, the suppression of wilting and the taste were good, and the freshness Was held.

  INDUSTRIAL APPLICATION This invention can be utilized for the package used at the time of the preservation | save of non-heat-processed foods, such as fruit and vegetables.

DESCRIPTION OF SYMBOLS 1 ... Anti-mold laminated film 1a ... 1st surface of an anti-mold laminated film 1b ... 2nd surface of an anti-mold laminated film 10 ... Anti-mold package 11 ... 1st resin layer 11b. .... Second surface of first resin layer 12 ... Anti-mold resin film 13 ... Second resin layer 13a ... First surface of second resin layer 14 ... Through hole S ... Anti-mold Packaging space

Claims (11)

An anti-mold laminated film comprising an anti-mold resin film, a first resin layer, and a second resin layer,
The mold-proof resin film is disposed between the first resin layer and the second resin layer,
The anti-mold resin film includes an anti-mold agent having a compound represented by the following general formula (1) or a salt thereof as an active ingredient, and a resin.
The mold-proof multilayer film has a through-hole having an average diameter of 8000 μm or less, and has a water vapor transmission rate of 5 g / m ² · day or more in an atmosphere of 40 ° C. and 90% RH.

(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; And when m is 2 or more, a plurality of X may be the same or different from each other; n is an integer of 0 to 5, provided that m + n is 6 or less and n is 2 or more A plurality of R may be the same as or different from each other.) The anti-mold laminate film according to claim 1, wherein the anti-mold laminate film has an oxygen permeation amount of 2.0 × 10 ⁸ cc / m ² · day or less in an atmosphere of 20 ° C. and 80% RH. The anti-number of the through-hole mold laminated film has is a 40 to 400 pieces / m ^2, antifungal laminate film according to claim 1 or 2. The anti-mold laminated film according to any one of claims 1 to 3, wherein a content of the anti-mold agent in the anti-mold resin film is 0.02 to ² g / m ² .   The anti-mold resin film is selected from the group consisting of urethane adhesive, acrylic adhesive, titanate adhesive, imine adhesive, butadiene adhesive, polyester adhesive and olefin adhesive as the resin. The mold prevention laminated film as described in any one of Claims 1-4 containing the 1 type (s) or 2 or more types by which the said mold prevention resin film has adhesiveness.   The mold prevention laminated film as described in any one of Claims 1-5 in which the said 1st resin layer contains a linear low density polyethylene.   The anti-mold laminated film according to any one of claims 1 to 6, wherein the second resin layer contains one or more selected from the group consisting of polyester, nylon, and polypropylene. It is an anti-mold package obtained using the anti-mold laminated film according to any one of claims 1 to 7,
A part of the first resin layers are bonded to each other, and has an accommodation space formed;
The anti-mold packaging body in which the anti-mold resin film is disposed closer to the housing space than the second resin layer.   The mold-proof package according to claim 8, which is used for packaging fruits and vegetables.   The anti-mold package of Claim 8 or 9 which is an object for packaging of citrus fruits. An antifungal resin film comprising an antifungal agent comprising a compound represented by the following general formula (1) or a salt thereof as an active ingredient, and a resin,
The anti-mold resin film is an anti-mold resin film having through-holes having an average diameter of 8000 μm or less at a number of 40 to 400 / m ² .

(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; And when m is 2 or more, a plurality of X may be the same or different from each other; n is an integer of 0 to 5, provided that m + n is 6 or less and n is 2 or more A plurality of R may be the same as or different from each other.)

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