JP6988185B2 - Antifungal agent, antifungal resin film, antifungal laminated film and antifungal packaging - Google Patents

Description

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

Various storage packages are used to contain and store the object. For example, when the object to be preserved is one that is orally ingested such as food, it is required that the object can be preserved while maintaining good quality, and a package for achieving such an object is required. It is disclosed (see Patent Document 1).

On the other hand, even if the package is manufactured and handled hygienically, mold adhering to the storage object and other objects that come into contact with the storage part of the package when the storage object is stored in the package. However, it may be taken into the storage space of the package. If it is desired to preserve the object to be preserved hygienically, such contamination of mold becomes a big problem.

In order to prevent the mold adhering to the storage object from being mixed into the storage space when the storage object is stored, for example, the molds such as heat treatment, chemical treatment, and ultraviolet irradiation treatment are killed. It is conceivable to store the processed object to be stored in a package. However, depending on the type of the object to be preserved, such as when it is orally ingested as described above, these treatments may not be possible, and this method cannot be said to be versatile. Therefore, it is more realistic and important to suppress the growth of mold in the storage space of the package during storage to the extent that it does not cause any problems. For this purpose, for example, the package should be provided with antifungal properties. It is conceivable to give it.

Japanese Unexamined Patent Publication No. 9-252718

However, when the object to be preserved is one that is orally ingested such as food, various restrictions are imposed on the package having antifungal properties. For example, it is necessary to continuously suppress the invasion of mold from the outside in the package after accommodating the storage object, and for that purpose, the package should be sealed to some extent with a resin film, a metal foil, or the like. Must be composed of materials that it has. Among them, the resin film is advantageous in that the stored object can be visually recognized from the outside of the package. In addition, when an antifungal agent that exhibits antifungal properties is used, such an antifungal agent has a certain level of safety to the human body in consideration of the possibility of its adhesion to the object to be preserved. You need to use something. It is desirable to refrain from using an antifungal agent having a strong odor because it is sensoryally unfavorable. Further, in order to continuously develop the antifungal effect for a certain period in the accommodation space of the package, for example, it is desirable to continuously supply the antifungal agent from the package itself into the accommodation space, and it is volatile. It is advantageous that the fungicide having a property can be supplied into the accommodation space as a gas. However, the package disclosed in Patent Document 1 does not enable all such measures.

The present invention has been made in view of the above circumstances, and uses an antifungal packaging body that can be used for storing foods and the like, an antifungal resin film suitable for constituting the same, and the antifungal resin film. It is an object of the present invention to provide a obtained antifungal laminated film and an antifungal agent suitable for forming the antifungal resin film.

In order to solve the above problems, the present invention adopts the following configuration.
[1]. An antifungal resin film containing an antifungal agent containing a compound represented by the following general formula (1) or a salt thereof as an active ingredient, and a resin.

（式中、Ｒ^１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_１は１〜３の整数であり；ｎ_１は０〜５の整数であり、ただしｍ_１＋ｎ_１は６以下であり、ｎ_１が２以上である場合、複数個のＲ^１は互いに同一でも異なっていてもよい。）

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms; m ₁ is an integer of _{1 to 3; n 1} is an integer of 0 to 5, but m. ₁ + _{n 1} is 6 or less, when _{n 1} is 2 or more, plural ^{R 1} may be the same or different from each other.)

[2]. The antifungal resin film according to [1], wherein m _{1 is 1.}
[3]. Antifungal resin film according to the _{n 1} is 0 or 1, [1] or [2].
[4]. As the resin, one or two selected from the group consisting of urethane-based adhesives, acrylic-based adhesives, titanate-based adhesives, imine-based adhesives, butadiene-based adhesives, polyester-based adhesives, and olefin-based adhesives. The antifungal resin film according to any one of [1] to [3], which comprises the above and has adhesiveness to the antifungal resin film.
[5]. The item according to any one of [1] to [4], further comprising another antifungal agent, which is different from the antifungal agent containing the compound represented by the general formula (1) or a salt thereof as an active ingredient. Antifungal resin film.
[6]. The antifungal resin film according to [5], wherein the other antifungal agent is a compound represented by the following general formula (9) or a salt thereof.

（式中、Ｘ^９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^９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_９は１〜３の整数であり、ｍ_９が２以上である場合、複数個のＸ^９は互いに同一でも異なっていてもよく；ｎ_９は０〜５の整数であり、ただしｍ_９＋ｎ_９は６以下であり、ｎ_９が２以上である場合、複数個のＲ^９は互いに同一でも異なっていてもよい。）

(In the formula, X ⁹ is a linear or branched alkylene group ^{having 1 to 3 carbon atoms; R 9} is a linear or branched alkyl group having 1 to 3 carbon atoms; m ₉ is an integer of 1 to 3, when _{m 9} is 2 or more, plural ^{X 9} may be the same or different; _{n 9} is an integer from 0 to 5, provided that _m 9 + _{n 9} is 6 or less, when n ₉ is 2 or more, a plurality of R ⁹ may be the same or different from each other.)

[7]. The antifungal resin film according to any one of [1] to [6], the first resin layer, and the second resin layer are provided, and the antifungal resin film includes the first resin layer and the first resin layer. Antifungal, which is arranged between the second resin layer and has an oxygen gas permeation amount of 3000 cm ³ / m ² · atm · day or more in an atmosphere of 25 ° C. and 65% RH of the first resin layer. Laminated film.
[8]. The antifungal laminated film according to [7], wherein the first resin layer contains low density polyethylene.
[9]. The antifungal laminated film according to [7] or [8], wherein the oxygen gas permeation amount of the second resin layer in an atmosphere of 25 ° C. and 65% RH is 3000 cm ³ / m ^{2 · atm · day or less.}
[10]. The antifungal laminated film according to any one of [7] to [9], wherein the second resin layer contains one or more selected from the group consisting of polyester, nylon and polypropylene.
[11]. An antifungal package obtained by using the antifungal laminated film according to any one of [7] to [10], and a part of the first resin layers is adhered to each other to form the antifungal package. An antifungal package having an accommodating space and having the antifungal resin film arranged on the accommodating space side with respect to the second resin layer.
[12]. An antifungal agent containing a compound represented by the following general formula (1) or a salt thereof as an active ingredient (excluding an antifungal agent containing benzoic acid or sodium benzoate as an active ingredient).

（式中、Ｒ^１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_１は１〜３の整数であり；ｎ_１は０〜５の整数であり、ただしｍ_１＋ｎ_１は６以下であり、ｎ_１が２以上である場合、複数個のＲ^１は互いに同一でも異なっていてもよい。）

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms; m ₁ is an integer of _{1 to 3; n 1} is an integer of 0 to 5, but m. ₁ + _{n 1} is 6 or less, when _{n 1} is 2 or more, plural ^{R 1} may be the same or different from each other.)

According to the present invention, an antifungal package that can be used for storing foods and the like, an antifungal resin film suitable for constituting the antifungal package, and an antifungal laminated film obtained by using the antifungal resin film. And an antifungal agent suitable for forming the antifungal resin film is provided.

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

<< Antifungal agent >>
The antifungal agent of the present invention contains a compound represented by the following general formula (1) or a salt thereof as an active ingredient (excluding the antifungal agent containing benzoic acid or sodium benzoate as an active ingredient).
The antifungal agent of the present invention suppresses the growth of mold in the object to be preserved by coexisting with the object to be preserved. In addition, in this specification, "mold generation" as described later means that the mold grows from the state where it cannot be visually confirmed to the extent that it can be visually confirmed.

（式中、Ｒ^１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_１は１〜３の整数であり；ｎ_１は０〜５の整数であり、ただしｍ_１＋ｎ_１は６以下であり、ｎ_１が２以上である場合、複数個のＲ^１は互いに同一でも異なっていてもよい。）

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms; m ₁ is an integer of _{1 to 3; n 1} is an integer of 0 to 5, but m. ₁ + _{n 1} is 6 or less, when _{n 1} is 2 or more, plural ^{R 1} may be the same or different from each other.)

<Compound (1)>
The compound represented by the general formula (1) (in this specification, may be referred to as “compound (1)”) has antifungal properties.
In the general formula (1), R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, and as such an alkyl group, more specifically, a methyl group (-CH ₃ ). Examples thereof include an ethyl group (-CH ₂ CH ₃ ), an n-propyl group (-CH ₂ CH ₂ CH ₃ ), and an isopropyl group (-CH (CH ₃ ) ₂ ).

In the general formula (1), m ₁ is an integer of 1 to 3 and indicates the number of carboxy groups (-C (= O) -OH) in one molecule of compound (1).

In the compound (1), regardless of the value of m _1, the bonding position of the benzene ring skeleton of the carboxy group is not particularly limited.
However, when m ₁ is 2, it is preferable that the two carbon atoms constituting the benzene ring skeleton to which the carboxy group is bonded are not adjacent to each other.
Further, when m ₁ is 3, it is preferable that at least two carbon atoms among the three carbon atoms constituting the benzene ring skeleton to which the carboxy group is bonded are not adjacent to each other. More preferably, all three carbon atoms are not adjacent to each other.

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

In compound (1), ^{the bond position of R 1 to} the benzene ring skeleton is not particularly limited regardless of the value of _{n 1.}
However, when n ₁ is 2, it is preferable that the two carbon atoms constituting the benzene ring skeleton to which ^{R 1 is bonded are not adjacent to each other.}
Further, when n ₁ is 3, it is preferable that at least two carbon atoms among the three carbon atoms constituting the benzene ring skeleton to which ^{R 1 is bonded are not adjacent to each other.} More preferably, all three carbon atoms are not adjacent to each other.
When n ₁ is 4, one carbon atom among the four carbon atoms constituting the benzene ring skeleton to which ^{R 1 is bonded is the remaining three carbon atoms.} It is preferable that neither is adjacent to each other.

Relationship relative binding positions of R ¹ and carboxyl group in the benzene ring skeleton is not particularly limited, for example, ortho, may be any of meta- and para-position.

As _{the compound (1) when m 1} is 1, a compound represented by the following general formula (1) -1A (in the present specification, it may be referred to as "compound (1) -1A") is used. Can be mentioned.

（式中、Ｒ^１は上記と同じであり、ｎ_１１は０〜５の整数である。）

(In the equation, R ¹ is the same as above, and n ₁₁ is an integer from 0 to 5.)

In the general formula (1) -1A, ^{R 1} is the same as ^{R 1} in general formula (1).
In the general formula (1) -1A, n ₁₁ is an integer of 0 to 5, which is the same as n ₁ in the general formula (1).

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

（式中、Ｒ^１は上記と同じであり、ｎ_１２は０〜４の整数である。）

(In the equation, R ¹ is the same as above, and n ₁₂ is an integer from 0 to 4.)

Formula (1) -2A～ formula (1) in -2C, ^{R 1} is the same as ^{R 1} in general formula (1).
In the general formulas (1) -2A to (1) -2C, n ₁₂ is an integer of 0 to 4, and is the same as _{n 1} in the general formula (1) except that it does not become 5. be.

Examples of the compound (1) in the case where m ₁ is 3 include a compound represented by the following general formula (1) -3A, a compound represented by the following general formula (1) -3B, and the following general formula (1). Compound represented by -3C (in the present specification, "Compound (1) -3A", "Compound (1) -3B", "Compound (1) -3C" corresponding to the reference numerals. (Sometimes referred to as).

（式中、Ｒ^１は上記と同じであり、ｎ_１３は０〜３の整数である。）

(In the equation, R ¹ is the same as above, and n ₁₃ is an integer from 0 to 3.)

Formula (1) -3A～ formula (1) in -3C, ^{R 1} is the same as ^{R 1} in general formula (1).
In the general formulas (1) -3A to (1) -3C, n _{13 is an integer of 0 to 3, and is the same as n 1} in the general formula (1) except that it does not become 4 and 5. It is a thing.

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

As _{the compound (1) when n 1} is 0, a compound represented by the following general formula (1) -0 (in the present specification, it may be referred to as “compound (1) -0”) is used. Can be mentioned.

（式中、ｍ_１０は１〜３の整数である。）

(In the formula, m ₁₀ is an integer of 1-3.)

In the general formula (1) -0, m ₁₀ is an integer of 1 to 3, which is the same as m ₁ in the general formula (1).

As _{the compound (1) when n 1} is 1, a compound represented by the following general formula (1) -1a (in the present specification, it may be referred to as "compound (1) -1a") is used. Can be mentioned.

（式中、Ｒ^１は上記と同じであり、ｍ_１１は１〜３の整数である。）

(In the equation, R ¹ is the same as above, and m ₁₁ is an integer of 1 to 3.)

In the general formula (1) -1a, ^{R 1} is the same as ^{R 1} in general formula (1).
In the general formula (1) -1a, m ₁₁ is an integer of 1 to 3, which is the same as m ₁ in the general formula (1).

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

（式中、Ｒ^１は上記と同じであり、ｍ_１２は１〜３の整数である。）

(In the equation, R ¹ is the same as above, and m ₁₂ is an integer of 1 to 3.)

Formula (1) -2A～ formula (1) in -2c, ^{R 1} is the same as ^{R 1} in general formula (1).
In the general formulas (1) -2A to (1) -2C, m ₁₂ is an integer of 1 to 3 and is the same as _{m 1 in the general formula (1).}

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

（式中、Ｒ^１は上記と同じであり、ｍ_１３は１〜３の整数である。）

(In the equation, R ¹ is the same as above, and m ₁₃ is an integer of 1 to 3.)

Formula (1) -3A～ formula (1) in -3c, ^{R 1} is the same as ^{R 1} in general formula (1).
In the general formulas (1) -3A to (1) -3C, m ₁₃ is an integer of 1 to 3 and is the same as _{m 1 in the general formula (1).}

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

（式中、Ｒ^１は上記と同じであり、ｍ_１４は１又は２である。）

(In the formula, R ¹ is the same as above, and m ₁₄ is 1 or 2.)

Formula (1) -4A～ formula (1) in -4C, ^{R 1} is the same as ^{R 1} in general formula (1).
In the general formulas (1) -4a to (1) -4c, m ₁₄ is 1 or 2, and is the same as _{m 1} in the general formula (1) except that it does not become 3.

As _{the compound (1) when n 1} is 5, a compound represented by the following general formula (1) -5a (in the present specification, it may be referred to as "compound (1) -5a") is used. Can be mentioned.

（式中、Ｒ^１は上記と同じである。）

(In the formula, R ¹ is the same as above.)

In the general formula (1) -5a, ^{R 1} is the same as ^{R 1} in general formula (1).
The compound represented by the general formula (1) -5a corresponds to the compound (1) in the case where _{m 1 in the general formula (1) is 1.}

In compound (1), n ₁ 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. Is particularly preferable. Such a compound (1) not only has an excellent antifungal effect, but can be produced more easily and inexpensively.

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

Among the compounds (1), for example, the compound represented by the following formula (1) -1A-0 (that is, benzoic acid, which may be referred to as "compound (1) -1A-0" in the present specification). , And the compound represented by the following general formula (1) -1A-1 (in the present specification, may be referred to as "compound (1) -1A-1") have particularly excellent antifungal properties. ..

（式中、Ｒ^１は上記と同じである。）

(In the formula, R ¹ is the same as above.)

<Salt of compound (1)>
The salt of compound (1) has antifungal properties.
The salt of compound (1), for example, carboxy group in the compounds (1) (-C (= O) -OH) is anionic (carboxylate anion, -C (= O) -O ^-) shall become (In the present specification, it may be referred to as "anion derived from compound (1)") and a salt formed by a cation.

The valence of the cation forming the salt of the compound (1) is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more. Usually, the cationic be a p ₁ monovalent (p ₁ is an integer of 1 or more), the number of the cation forming the salt of the compound (1) is 1 or more, the compound (1) from The number of anions is p ₁ or less.

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

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

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

Among the cations, examples of the organic cation include cations derived from amine compounds and quaternary ammonium cations.
Examples of the cation derived from the amine compound include cations in which a primary amine, a secondary amine or a tertiary amine is protonated.
Examples of the quaternary ammonium cation include a cation in which four monovalent hydrocarbon groups are bonded to one nitrogen atom.

The cation is preferably a cation represented by the following general formula (11).

（式中、Ｚ^１は、水素原子、アルキル基又はアリール基であり、複数個のＺ^１は互いに同一でも異なっていてもよく、２個以上のＺ^１がアルキル基である場合、これらアルキル基は相互に結合して環を形成していてもよい。）

(Wherein, Z ¹ represents a hydrogen atom, an alkyl group or an aryl group, a plurality of Z ¹ may be the same or different, when two or more Z ¹ is an alkyl group, the alkyl group May be coupled to each other to form a ring.)

In the general formula (11), Z ¹ is a hydrogen atom, an alkyl group or an aryl group.
In the general formula (11), Z ¹ may be the same or different from each other a plurality (i.e., four). That is, it may be all the plurality of Z ¹ are the same, may be different, all may be the same part only.

The ^{alkyl group in Z 1} may be linear, branched or cyclic, and when cyclic, it may be monocyclic or polycyclic.
The ^{aryl group in Z 1} may be either monocyclic or polycyclic.

The ^{linear or branched alkyl group in Z 1} preferably has 1 to 10 carbon atoms, and examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl. Group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group , 1-Methylpentyl group, 2-Methylpentyl group, 3-Methylpentyl group, 4-Methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2 , 3-Dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3 -Methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3 , 3-Dimethylpentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1 -Propylbutyl group, n-octyl group, isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2- Ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, Examples thereof include 5,5-dimethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, nonyl group and decyl group.
The ^{number of carbon atoms of the linear or branched alkyl group in Z 1} may be, for example, any of 1 to 8, 1 to 5, and 1 to 3, but these are examples.

The cyclic alkyl group in Z ¹ preferably has 3 to 10 carbon atoms, and examples of such an alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclo. Examples thereof include an octyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, a 2-adamantyl group, a tricyclodecyl group and the like.
The ^{number of carbon atoms of the cyclic alkyl group in Z 1} may be, for example, any of 3 to 8 and 3 to 6, but these are examples.

Two or more (i.e., 2, 3 or 4) when Z ¹ is an alkyl group, these two or more alkyl groups bonded to each other, the nitrogen atom to which they alkyl group is attached May form a ring with. In this case, the bonding positions of the two or more alkyl groups with each other are not particularly limited, and the ring formed may be either monocyclic or polycyclic.

The ^{aryl group in Z 1} preferably has 6 to 20 carbon atoms, and examples of such an aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-tolyl group, and m-. tolyl group, p- tolyl group, xylyl group (dimethylphenyl group), with one or more hydrogen atoms of these aryl groups may further and these aryl groups, also those substituted with the alkyl group in Z ¹ Can be mentioned. The aryl group having these substituents preferably has 6 to 20 carbon atoms including the substituent.

Among the salts of compound (1), for example, the salt of compound (1) -1A-0 (that is, benzoate) and the salt of compound (1) -1A-1 have particularly excellent antifungal properties.

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

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

Compound (1) and a salt thereof may be volatile. The volatile compound (1) and its salt become a gas at room temperature, which is advantageous for continuous action in the storage space of the package described later, and is excellent in the package. The mold effect can be maintained for a longer period of time.

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

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

It has not been conventionally known that among the compound (1) and its salts, compounds other than benzoic acid and sodium benzoate have antifungal properties.

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.

<Manufacturing method of compound (1)>
The compound (1) is, for example, a step of oxidizing a compound represented by the following general formula (101) (in this specification, it may be referred to as “compound (101)”) to obtain a compound (1). (In the present specification, it may be referred to as "compound (1) manufacturing step").

（式中、Ｒ^１、ｍ_１及びｎ_１は、上記と同じである。）

(In the formula, R ¹ , m ₁ and n ₁ are the same as above.)

The oxidation reaction in the compound (1) production step can be carried out by a known method, and the reaction conditions may be appropriately selected according to the type of the raw material used.

In the compound (1) production step, after the oxidation reaction of the compound (101) is completed, a post-treatment is performed as necessary by a known method, and the target compound (1) can be taken out. That is, after the reaction is completed, post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, and concentration are performed individually or in combination of two or more, if necessary, and concentration, crystallization, and reprecipitation are performed. , The compound (1) can be taken out by column chromatography or the like. Further, the extracted compound (1) is further subjected to operations such as crystallization, reprecipitation, column chromatography, extraction, and stirring and washing of crystals with a solvent, as necessary, alone or in combination of two or more. It may be purified by performing it more than once.
During the oxidation reaction of the compound (101), for example, by site untargeted such R ¹ is oxidized, by-products may occur. However, such by-products can be separated and removed from compound (1) during the above-mentioned post-treatment or removal of compound (1).
After completion of the reaction, compound (1) may be subjected to post-treatment as necessary and then continued to be used for the intended purpose without being taken out.

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

<Method for producing salt of compound (1)>
The salt of compound (1) can be produced by applying a known method for converting a carboxylic acid to a carboxylate to compound (1).
For example, a reaction (neutralization reaction) is carried out by allowing a base to act on the compound (1) in an isolated state or the compound (1) before removal in the above-mentioned method for producing the compound (1). Thereby, the salt of the compound (1) can be produced by a production method or the like having a step of obtaining the salt of the compound (1). As the compound (1) in the isolated state, a commercially available product may be used.

Examples of the base include a hydroxide of a metal that becomes a cation forming a salt of the compound (1), such as sodium hydroxide; a carbonate of the metal; a primary amine, a secondary amine, and a tertiary amine. Amine compounds such as amines; ammonia; quaternary ammonium halides such as tetra n-butylammonium fluoride and the like can be mentioned.

Further, the salt of the compound (1) can also be produced by exchanging the salt of the unintended compound (1) so as to become the salt of the target compound (1).

The salt of compound (1) may be taken out and used as in the case of compound (1), or may be used continuously for the intended purpose without being taken out.
The structure of the obtained salt of compound (1) can be confirmed by the same method as in the case of compound (1).

The fungicide of the present invention may contain other components in addition to compound (1) or a salt thereof.
The other components in the antifungal agent are not particularly limited as long as the effects of the present invention are not impaired, and can be arbitrarily selected.
For example, the compound (1) or a salt thereof may be either solid or liquid at room temperature and under normal pressure, and a compound having suitable properties may be selected according to the type of the antifungal resin film described later. Just do it. Then, compound (1) or a salt thereof may be used, for example, dissolved or dispersed in a solvent, or diluted with a solvent. That is, examples of the other components include a solvent and the like.
In addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

The solvent may be appropriately selected depending on the type of compound (1) or a salt thereof, and the type is not particularly limited.
Preferred solvents include, for example, organic solvents and water.

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

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

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

When the fungicide of the present invention contains other components other than the solvent, the content of the other components is not particularly limited as long as the effect of the present invention is not impaired, and is appropriately depending on the type of the other components. You can select it.
However, usually, in the antifungal agent of the present invention, the solvent with respect to the total content of the components other than the solvent (that is, the compound (1), the salt of the compound (1), and other components other than the solvent). The ratio of the content of other components other than the above is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, for example, 2% by mass or less. , 1% by mass or less, etc. may be used.

The microorganisms (molds) whose growth inhibitory effect (antifungal effect) is recognized by the use of the antifungal agent of the present invention are not generally limited to those in a specific range, but those having a high antifungal effect are considered. , 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, lysops. Examples thereof include microorganisms belonging to the genus (Rhizopus), microorganisms belonging to the genus Botrytis, and the like.
Among these, examples of microorganisms belonging to the genus Penicillium include Penicillium and Mildew. Examples of the microorganism belonging to the genus Aspergillus include Aspergillus niger and the like. Examples of microorganisms belonging to the genus Cladosporium include black mold and the like. Examples of microorganisms belonging to the genus Fusarium include Fusarium solani. Examples of the microorganism belonging to the genus Alternaria include Alternaria tenuis and the like. Examples of the microorganism belonging to the genus Rhizopus include Rhizopus niglicans and the like. Examples of the microorganism belonging to the genus Botrytis include Botrytis cinerea and the like.

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

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

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

<< Antifungal resin film >>
The antifungal resin film of the present invention contains an antifungal agent containing the compound (1) or a salt thereof as an active ingredient, and a resin. The antifungal resin film of the present invention also includes those containing an antifungal agent containing benzoic acid or sodium benzoate as an active ingredient.
The antifungal resin film of the present invention has excellent antifungal properties because it contains the antifungal agent.

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

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

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

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

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

In addition, in this specification, "(meth) acryloyl group" is a concept including both "acryloyl group" and "methacryloyl group".

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

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

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

(Other fungicides)
Preferred other components include, for example, other antifungal agents different from the antifungal agent containing compound (1) or a salt thereof as an active ingredient.
That is, as the preferable antifungal resin film, for example, a film further containing another antifungal agent different from the antifungal agent containing the compound (1) or a salt thereof as an active ingredient can be mentioned.
By further containing the other antifungal agent, the antifungal resin film may exhibit a synergistic effect in which the antifungal property is significantly higher than that in the case where the other antifungal agent is not contained.

The other antifungal agent is not particularly limited and may be appropriately selected depending on, for example, the type of the compound (1) to be used in combination or a salt thereof.
The other fungicide may be a known one or a new one.

Among them, preferable examples of the other fungicide include, for example, a compound represented by the following general formula (9) (in the present specification, it may be referred to as “compound (9)”) or a salt thereof. Be done.
That is, as the more preferable antifungal resin film, for example, as an antifungal agent, those further containing compound (9) or a salt thereof can be mentioned.

（式中、Ｘ^９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^９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_９は１〜３の整数であり、ｍ_９が２以上である場合、複数個のＸ^９は互いに同一でも異なっていてもよく；ｎ_９は０〜５の整数であり、ただしｍ_９＋ｎ_９は６以下であり、ｎ_９が２以上である場合、複数個のＲ^９は互いに同一でも異なっていてもよい。）

(In the formula, X ⁹ is a linear or branched alkylene group ^{having 1 to 3 carbon atoms; R 9} is a linear or branched alkyl group having 1 to 3 carbon atoms; m ₉ is an integer of 1 to 3, when _{m 9} is 2 or more, plural ^{X 9} may be the same or different; _{n 9} is an integer from 0 to 5, provided that _m 9 + _{n 9} is 6 or less, when n ₉ is 2 or more, a plurality of R ⁹ may be the same or different from each other.)

In the general formula (9), X ⁹ is a linear or branched alkylene group having 1 to 3 carbon atoms, and as such an alkylene group, more specifically, a methylene group (−CH ₂ −). , Ethylene group (-CH ₂ CH _2- ), propylene group (-CH (CH ₃ ) CH _2- , methylethylene group), trimethylene group (-CH ₂ CH ₂ CH _2- ).

In the general formula (9), R ⁹ is a linear or branched alkyl group having 1 to 3 carbon atoms, and is the same as R ¹ in the general formula (1).

In the general formula (9), m ₉ is an integer of 1 to 3, and the general formula "-O-X ^9- OH" in one molecule of the compound (9) (in the formula, X ⁹ is the same as above). Indicates the number of groups represented by.
When m ₉ is 2 or more (ie, 2 or 3), the plurality of (ie, 2 or 3) X ^9s may be the same or different from each other. That is, when m ₉ is 2 or more, all X ⁹ may be the same, may be different, all may be the same part only.

Regardless of the value of m ₉ , the bonding position of the group represented by the general formula "-O-X ^9- OH" to the benzene ring skeleton is not particularly limited.
However, when m ₉ is 2, the two carbon atoms constituting the benzene ring skeleton to which the group represented by the general formula "-OX ^{9-OH" is bonded are adjacent to each other.} It is preferable not to do so.
When m ₉ is 3, at least of the three carbon atoms constituting the benzene ring skeleton to which the group represented by the general formula "-OX ^{9-OH" is bonded.} It is preferable that the two carbon atoms are not adjacent to each other, and it is more preferable that all three carbon atoms are not adjacent to each other.

In compound (9), m ₉ is preferably 1 or 2, more preferably 1. Such compound (9) not only has an excellent antifungal effect, but can be produced more easily and inexpensively.

In the general formula (9), n ₉ is an integer of 0 to 5, and indicates the number ^{of R 9 in one molecule of compound (9).} However, m ₉ + n ₉ is 6 or less.
When n ₉ is 2 or more (ie, 2, 3, 4 or 5), the plurality of (ie, 2, 3, 4 or 5) R ^9s may be the same or different from each other. That is, when n ₉ is 2 or more, all R ⁹ may be the same, may be different, all may be the same part only.

Regardless of the value of n ₉ ^{, the binding position of R 9 to} the benzene ring skeleton is not particularly limited.
However, when n ₉ is 2, it is preferable that the two carbon atoms constituting the benzene ring skeleton to which ^{R 9 is bonded are not adjacent to each other.}
Further, when n ₉ is 3, it is preferable that at least two carbon atoms among the three carbon atoms constituting the benzene ring skeleton to which ^{R 9 is bonded are not adjacent to each other.} More preferably, all three carbon atoms are not adjacent to each other.
When n ₉ is 4, one carbon atom among the four carbon atoms constituting the benzene ring skeleton to which ^{R 9 is bonded is the remaining three carbon atoms.} It is preferable that neither is adjacent to each other.

^{The relationship between the relative bond positions of R 9} and the group represented by the general formula "-O-X ^9- OH" in the benzene ring skeleton is not particularly limited, and is, for example, the ortho-position, meta-position and para-position. It may be either.

In compound (9), n ₉ 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. Is particularly preferable. Such compound (9) not only has an excellent antifungal effect, but can be produced more easily and inexpensively.

In compound (9), _{both m 9} and n ₉ are preferably any of the above-mentioned preferable numerical values.
For example, in compound (9), _{m 9} is that the 1 or 2 and _{n 9} is an integer of 0 to 4 is preferable, _{m 9} is 1 or 2 and _{n 9} is an integer of from 0 to 3 It is more preferable that m ₉ is 1 or 2 and n ₉ is an integer of 0 to 2, and it is particularly preferable that _{m 9} is 1 and n _{9 is 0 or 1.}

The salt of compound (9), for example, groups anion represented by the formula in the compound (9) ^"-O-X 9 -OH" (i.e., formula ^"-O-X 9 -O ^-" in (wherein, X ⁹ is as defined above.), a group represented by (in this specification) and became as the may be referred to as "compound (9) anion derived from"), the cationic , And the salt formed by.

The valence of the cation forming the salt of the compound (9) is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more. Usually, the cationic be a p _9-valent (p ₉ is an integer of 1 or more), the number of the cation forming the salt of the compound (9) is 1 or more, the compound (9) from the number of anions is p ₉ below.

As described above, the number of cations constituting the salt of the single molecule compound (9) may be only one, two or more, and when two or more, these cations may be all the same. It may be all different, or only partly the same.
However, the salt of compound (9) 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 compound (9) are the same. Is preferable.

The cation forming the salt of the compound (9) together with the anion derived from the compound (9) is not particularly limited and may be either an inorganic cation or an organic cation.

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

In the antifungal resin film, the compound (9) or a salt thereof may be only one kind or two or more kinds, and when two or more kinds are used, the combination and ratio thereof may be arbitrary depending on the purpose. You can choose.
For example, the antifungal resin film may contain one or more of the compound (9) as the other antifungal agent, or one or more of the salt of the compound (9). It may be contained, or may contain one or more salts of compound (9) and compound (9), respectively.

The compound (9) and a salt thereof are preferably those that can be used as food additives. Here, "food additive" means an additive approved by the Ministry of Health, Labor and Welfare of Japan as of March 12, 2013.

The compound (9) and a salt thereof are preferably volatile. The volatile compound (9) and its salt change from a liquid to a gas at room temperature, which is advantageous for continuous action in the storage space of the package described later, and is excellent in the package. The antifungal effect can be maintained for a longer period of time.

The molecular weight of compound (9) and its salt is preferably 300 or less in that it is easily volatilized, and can be, for example, 250 or less, 200 or less, 150 or less, etc., but these are examples. Is. The lower limit of the molecular weight of compound (9) and its salt is not particularly limited.

The compound (9) and a salt thereof are preferably odorless or have a weak odor. Such a compound (9) and a salt thereof, even if they adhere to the object to be preserved, are functionally preferable because their existence is not or hardly recollected at the time of use of the object to be preserved.
The odorous compound (9) and its salt are preferably those that can be used as a fragrance. Examples of such a compound (9) and a salt thereof include those classified as natural flavors of food additives.

As described above, the compound (9) or a salt thereof, which can be used as a food additive, has volatility, is odorless or has a weak odor, is, for example, 2-phenoxyethanol represented by the following formula. Can be mentioned.

As the compound (9) and a salt thereof, a commercially available product may be used, or a product produced by a known method may be used.

The compound (9) is represented by, for example, a compound represented by the following general formula (901) (in the present specification, it may be referred to as “compound (901)”) and the following general formula (902). A step of reacting a compound (sometimes referred to as "compound (902)" in the present specification) to obtain a compound (9) (referred to as "compound (9) manufacturing step" in the present specification). It can be manufactured by a manufacturing method having (may be).

（式中、Ｘ^９、Ｒ^９、ｍ_９及びｎ_９は、上記と同じであり；Ｌｇは離脱基である。）

(In the formula, X ⁹ , R ⁹ , m ₉ and n ₉ are the same as above; Lg is a withdrawal group.)

The reaction in the compound (9) production step can be carried out by a known method, and the reaction conditions may be appropriately selected according to the type of the raw material used.
Examples of Lg include halogen atoms such as chlorine atom, bromine atom and iodine atom; alkylsulfonyloxy group; fluoroalkylsulfonyloxy group and the like.
In the compound (9) manufacturing process, for example, a group such as a hydroxyl group (-OH) in the compound (902) that may cause an unintended reaction in the raw material to be used is protected with a protecting group in advance. After that, the reaction may be carried out, and the compound (9) may be obtained by carrying out deprotection after the reaction is completed.
Compound (901) can be produced by applying a conventional method for producing sodium alkoxide. For example, a corresponding phenolic compound as a raw material, that is, a compound in which the ^{group represented by the formula "-O-} Na ⁺ " is replaced with the group represented by the formula "-OH" in the compound (901) is used. Compound (901) can be obtained by allowing metallic sodium, sodium hydride, or the like to act.
The compound (902) is a corresponding alcohol as a raw material, that is, ^{a compound represented by the general formula "HO-X 9-} OH (X ⁹ is the same as above)", or one of the hydroxyl groups is a protecting group. It can be produced by a method of introducing Lg using a protected compound. When a protecting group is used, the protecting group may be removed (deprotected) at an appropriate timing. However, the method for producing the compound (902) shown here is an example.

In the compound (9) production step, after the reaction of the compound (901) and the compound (902) is completed, post-treatment may be performed as necessary by a known method to take out the target compound (9). can. That is, after the reaction is completed, post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, and concentration are performed individually or in combination of two or more, if necessary, and concentration, crystallization, and reprecipitation are performed. , The compound (9) can be taken out by column chromatography or the like. Further, the extracted compound (9) is further subjected to operations such as crystallization, reprecipitation, column chromatography, extraction, and stirring and washing of crystals with a solvent, as necessary, alone or in combination of two or more. It may be purified by performing it more than once.
After completion of the reaction, compound (9) may be subjected to post-treatment as necessary and then continued to be used for the intended purpose without being taken out.

The obtained compound (9) is known, for example, nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), ultraviolet / visible spectroscopy (UV-VIS absorption spectrum), and the like. The structure can be confirmed by the method of.

The salt of compound (9) can be produced by applying a usual method for producing a metal alkoxide. For example, in the case of the sodium salt (sodium alkoxide) of the compound (9), the isolated compound (9) or the compound (9) before withdrawal in the above-mentioned method for producing the compound (9). The desired product can be obtained by applying the same method as in the case of producing the above-mentioned compound (901). As the isolated compound (9), a commercially available product may be used.
The salt of compound (9) may be taken out and used as in the case of compound (9), or may be used continuously for the intended purpose without being taken out.
The structure of the obtained salt of compound (9) can be confirmed by the same method as in the case of compound (9).

The microorganisms (molds) whose growth inhibitory effect (antifungal effect) is observed by the use of compound (9) or a salt thereof are not generally limited to those in a specific range, but are considered to have a high antifungal effect. Examples thereof include those in which the antifungal agent containing the above-mentioned compound (1) or a salt thereof as an active ingredient exhibits a high antifungal effect.

(Curing agent, cross-linking agent)
Examples of the other components in the antifungal resin film and the resin composition include, for example, a curing agent, a cross-linking agent, and the like, in addition to the other antifungal agents. These act on the resin.

The resin composition may contain other components that do not fall under any of the other fungicides, curing agents and cross-linking agents, if necessary, and the preferred other components in this case are Examples include solvents.

The solvent is for improving the handleability of the resin composition, and the type thereof is not particularly limited as long as the effect of the present invention is not impaired.
Examples of the solvent in the resin composition include the same solvents as those described above as those that may contain the fungicide of the present invention.

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

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

The content of the other components other than the solvent in the antifungal resin film (in other words, the ratio of the content of the other components other than the solvent to the total content of the components other than the solvent in the resin composition). May be appropriately selected depending on the type of the other components, and is not particularly limited.

For example, when the other component is the other antifungal agent, the content of the other antifungal agent with respect to the total content of the compound (1) and its salt in the antifungal resin film and the resin composition. Is preferably 15 to 85% by mass, more preferably 20 to 80% by mass, and particularly preferably 25 to 75% by mass. When the ratio is at least the lower limit value, the effect of using the other fungicide is more remarkable, and when the ratio is at least the upper limit, the overuse of the other fungicide is obtained. Is suppressed.

Further, for example, when the other component is the curing agent or the cross-linking agent, the ratio of the content of the other component to the content of the resin in the antifungal resin film and the resin composition is 10 to 10. It is preferably 40% by mass, more preferably 20 to 30% by mass. When the ratio is at least the lower limit, the effect of using the other components is more remarkable, and when the ratio is at least the upper limit, overuse of the other components is suppressed. ..

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

The content of the other components of the antifungal resin film, which do not fall under any of the other antifungal agents, curing agents, cross-linking agents and solvents, can be, for example, 0 to 10% by mass.

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

In the present specification, not only in the case of the antifungal resin film, but also in the case of "a plurality of layers may be the same or different from each other", "all layers may be the same or all layers may be the same". "The layers may be different, and only some of the layers may be the same", and "multiple layers are different from each other" means that "at least one of the constituent materials and thicknesses of each layer is different from each other". It means "different".

The thickness of the antifungal resin film may be appropriately selected depending on the intended use, and is not particularly limited.
When, for example, a bag-shaped package is produced using the antifungal resin film, the thickness of the antifungal resin film is preferably 0.5 to 15 μm, preferably 1 to 12 μm. It is more preferably 1.3 to 10 μm, and may be, for example, 1.3 to 7.5 μm.
When the antifungal resin film is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the above-mentioned preferable thickness of the antifungal resin film.

The compound (1) and a salt thereof are suitable for use as an antifungal resin film, but are also suitable for use in applications other than the antifungal resin film because they have an excellent antifungal effect. For example, the compound (1) or a salt thereof can also be used as a solid (for example, granular, block-like, etc.) antifungal material other than a film, an antifungal ink composition, an antifungal spray agent, and the like. As described above, when the compound (1) or a salt thereof is used for applications other than the antifungal resin film, in addition to the compound (1) or the salt thereof, a component necessary for obtaining the desired property in combination is used in combination. The prepared composition may be prepared, and the desired product may be produced using this composition.

<< Mold-proof laminated film >>
The antifungal laminated film of the present invention includes the above-mentioned antifungal resin film of the present invention, a first resin layer, and a second resin layer, and the antifungal resin film includes the first resin layer and the above. It is arranged between the second resin layer and the oxygen gas permeation amount of the first resin layer in an atmosphere of 25 ° C. and 65% RH is 3000 cm ³ / m ² · atm · day or more.
Since the antifungal laminated film of the present invention uses the antifungal resin film, it has excellent antifungal properties and is suitable for producing a package for accommodating and storing an object.

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

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

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

The oxygen gas permeation amount of the first resin layer 11 in an atmosphere of 25 ° C. and 65% RH (relative humidity) is 3000 cm ³ / m ² · atm · day or more, and ^{3000 to 10000 cm 3} / m ² · atm ·. is preferably day, more preferably ^{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 11 is at least the lower limit value, the compound (1) or a salt thereof that has migrated from the inside of the antifungal resin film 12 to the first resin layer 11 side is the first resin. It easily migrates to the outside (outside of the first resin layer 11 side of the antifungal laminated film 1) via the layer 11. As a result, the antifungal laminated film 1 exhibits an excellent antifungal effect.

The constituent material of the first resin layer 11 is not particularly limited as long as it satisfies the above-mentioned oxygen gas permeation amount, but preferred ones are, for example, low density polyethylene (LDPE) and linear low density polyethylene. (LLDPE), metallocene-catalyzed linear low-density polyethylene (metallocene LLDPE) and the like.
Further, as the constituent material of the first resin layer 11, synthetic resins other than these can also be mentioned.

The constituent material of the first resin layer 11 may be only one kind or two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be arbitrarily selected according to the purpose.

The first resin layer 11 preferably contains low-density polyethylene (LDPE), and the content of the low-density polyethylene in the first resin layer 11 is preferably 60% by mass or more, preferably 80% by mass or more. Is more preferable, and 90% by mass or more is particularly preferable, and for example, 99% by mass or more may be used, or 100% by mass or more may be used.

The first resin layer 11 may be composed of one layer (single layer) or may be composed of two or more layers. When the first resin layer 11 is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the first resin layer 11 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 11 is equal to or greater than the lower limit, the strength of the first resin layer 11 is further improved, and the antifungal agent is excessively transferred from the antifungal resin film 12 to the object to be stored. It is more suppressed. Further, when the thickness of the first resin layer 11 is not more than the upper limit value, the antifungal effect of the antifungal laminated film 1 is further improved.
When the first resin layer 11 is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the preferred thickness of the first resin layer 11.

The antifungal resin film 12 is the antifungal resin film of the present invention described above. Here, a detailed description of the antifungal resin film 12 will be omitted.

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

The oxygen gas permeation amount of the second resin layer 13 in an atmosphere of 25 ° C. and 65% RH (relative humidity) ^{is preferably 3000 cm 3} / m ² · atm · day or less, preferably 2500 cm ³ / m ² · atm. -It is more preferably less than or equal to day, and particularly preferably less than or equal to ^{2000 cm 3} / m ^{2 · atm · day.}
The smaller the upper limit of the oxygen gas permeation amount of the second resin layer 13, the more the compound (1) or a salt thereof is transferred from the inside of the antifungal resin film 12 to the second resin layer 13, and the second resin layer 13 is transferred. The migration to the outside (outside of the second resin layer 13 side of the antifungal laminated film 1) is effectively suppressed. Therefore, since the amount of the compound (1) or a salt thereof transferred from the inside of the antifungal resin film 12 to the storage object side can be maintained at an appropriate level for a long period of time, the antifungal laminated film 1 is more excellent in antifungal. It develops a mold effect. Further, for example, when the target product is contained in a bag-shaped package manufactured by using the antifungal laminated film 1 and sealed, the compound (1) or a salt thereof to the outside of the package is contained. The migration is suppressed and the use of compound (1) or a salt thereof is hardly or hardly reminiscent of the use of the compound (1) or a salt thereof at the time of storage of the object, which is functionally preferable.
Further, the smaller the upper limit of the oxygen gas permeation amount of the second resin layer 13, the more from the outside (outside of the second resin layer 13 side of the antifungal laminated film 1) to the inside via the second resin layer 13. , The transfer of oxygen gas is effectively suppressed. Therefore, the effect of preserving the target product without deteriorating the quality becomes higher.

On the other hand, the lower limit of the oxygen gas permeation amount of the second resin layer 13 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 ^{1000cm 3 / m 2 · atm ·} day can be any, which are an example.

The oxygen gas permeation amount of the first resin layer 11 and the second resin layer 13 is a value measured in accordance with JIS K7126B.

The constituent material of the second resin layer 13 may be appropriately selected depending on the intended purpose, and is not particularly limited, but it is easy to configure the second resin layer 13 so as to satisfy the above-mentioned oxygen gas permeation amount condition. In terms of points, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN); nylon; polypropylene (PP) and the like Can be mentioned.
Further, as the constituent material of the second resin layer 13, synthetic resins other than these can also be mentioned.

The constituent material of the second resin layer 13 may be only one kind or two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be arbitrarily selected according to the purpose.

The second resin layer 13 preferably contains one or more selected from the group consisting of polyester, nylon and polypropylene, and the total content of the polyester, nylon and polypropylene of the second resin layer 13 is 80 mass by mass. % Or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, for example, 99% by mass or more, or 100% by mass. good.

The second resin layer 13 may be composed of one layer (single layer) or may be composed of two or more layers. When the second resin layer 13 is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the second resin layer 13 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 13 is equal to or greater than the lower limit, the strength of the second resin layer 13 is further improved, and the same effect as when the oxygen gas permeation amount of the second resin layer 13 is reduced is the same. Is obtained more prominently. Further, when the thickness of the second resin layer 13 is not more than the upper limit value, it is possible to avoid an excessive thickness.
When the second resin layer 13 is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the preferred thickness of the second resin layer 13.

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

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

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

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

Next, the exposed surface of the antifungal resin film in the intermediate laminate (the surface on which the first resin layer or the second resin layer is not provided) and the other surface of either the first resin layer or the second resin layer (one surface). ) And are bonded together to form an antifungal laminated film. Here, "either the first resin layer or the second resin layer" means the second resin layer when the one laminated on the antifungal resin film in the intermediate laminate is the first resin layer. When the second resin layer is laminated on the antifungal resin film in the intermediate laminated body, it means the first resin layer.
The bonding of the intermediate laminate to the second resin layer or the first resin layer can be performed by applying various known laminating methods.

As described above, the antifungal laminated film can be obtained. However, in the case of producing the antifungal laminated film provided with other layers in addition to the first resin layer, the antifungal resin film and the second resin layer, the above-mentioned In the manufacturing method of the above, a step of forming the other layer may be added at an appropriate timing so that the other layer is arranged at a target laminated position.

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

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

Next, the release film is removed at an appropriate timing, the first resin layer is bonded to one surface of the antifungal resin film, and the second resin layer is bonded to the other surface of the antifungal resin film to laminate the antifungal layer. Form a film. One of the antifungal resin film and the first resin layer and the antifungal resin film and the second resin layer may be bonded first, and the other may be performed in sequence. However, it may be done at the same time.

<< Mold-proof packaging >>
The antifungal package of the present invention is an antifungal package obtained by using the above-mentioned antifungal laminated film of the present invention, and is formed by partially adhering a part of the first resin layers to each other. It has a space, and the antifungal resin film is arranged on the accommodation space side with respect to the second resin layer.
The antifungal package of the present invention has excellent antifungal properties by using the antifungal laminated film (antifungal resin film), and the growth of mold in the storage space during storage of the target object. Is remarkably suppressed.

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

In the antifungal package 10, the compound (1) or a salt thereof is easily transferred from the inside of the antifungal resin film 12 into the accommodation space S via the first resin layer 11. As a result, the antifungal package 10 can maintain the concentration of the compound (1) or a salt thereof in the accommodation space S at an appropriate level for a certain period of time, and exhibits an excellent antifungal effect.
Further, in the antifungal package 10, the first resin layer 11 prevents the object to be stored in the storage space S from coming into contact with the antifungal resin film 12, and prevents the antifungal resin film 12 from the object to be stored. Excessive transfer of fungicides is suppressed.

Further, in the antifungal package 10, as described above in the antifungal laminated film, by adjusting the composition of the second resin layer 13, the antifungal effect can be sustained and the object to be stored by oxygen gas from the outside. It is possible to further enhance the effect of suppressing deterioration of objects.
Further, by using the antifungal package 10 and adjusting the type of the compound (1) or a salt thereof, the object to be preserved at the time of use after storage can be the use of the compound (1) or a salt thereof (antifungal agent). Can also be sensually preferable so as not to remind us of any or little.

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

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

The antifungal package of the present invention can be produced by using the antifungal laminated film of the present invention and adhering a part of the first resin layers to each other so as to have a storage space.
Adhesion between the first resin layers can be performed, for example, by applying various known laminating methods.

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

<Manufacturing of antifungal laminated film>
[Example 1]
The antifungal laminated film having the structure shown in FIG. 1 was manufactured by the procedure shown below.
(Manufacturing of antifungal resin film)
Main agent (Mitsui Chemicals Co., Ltd. "Takelac (registered trademark) A620", solid content 50% by mass, ethyl acetate 50% by mass) (6 parts by mass), curing agent (Mitsui Chemicals Co., Ltd. "Takenate (registered trademark) A10" , 75% by mass of solid content, 25% by mass of ethyl acetate) (1 part by mass), and ethyl acetate (6 parts by mass) were mixed to prepare a polyurethane adhesive. In the obtained polyurethane adhesive, the total content of the solvent (ethyl acetate) is 71.2% by mass.
Next, sodium benzoate (2 parts by mass) is mixed with the total amount of the polyurethane adhesive obtained above, and the ratio of the content of sodium benzoate to the total content of the components other than the solvent is 35% by mass. A resin composition was obtained.
Next, the resin composition obtained above was applied to one surface of a PET film (thickness 25 μm) using a multicoater and dried at 80 ° C. to obtain a sodium benzoate content of 35. An antifungal resin film (thickness 4 μm) having a mass% was formed on the PET film. When the resin composition was applied, the depth of the gravure roll was set to 80 μm.

(Manufacturing of antifungal laminated film)
Further, by adhering the LDPE film (thickness 25 μm) to the surface of the antifungal resin film obtained above on the side opposite to the side on which the PET film is provided, the PET film, the antifungal resin film and the LDPE are attached. A transparent antifungal laminated film was obtained in which the films were laminated in this order.

The oxygen gas permeation amount of the LDPE film in an atmosphere of 25 ° C. and 65% RH measured in accordance with JIS K7126B was 5000 cm ³ / m ² · atm · day, and the PET film was 25 ° C. The oxygen gas permeation amount in the atmosphere of 65% RH was 80 cm ³ / m ² · atm · day.

<Manufacturing of laminated film>
[Comparative Example 1]
A resin composition was prepared without the use of sodium benzoate, and this resin composition was used to replace the antifungal resin film (thickness 4 μm) having a sodium benzoate content of 35% by mass. A transparent laminated film was obtained by the same method as in Example 1 except that a resin film (thickness 4 μm) having a content of 0% by mass was formed.

<Evaluation of antifungal laminated film and laminated film>
[Test Example 1]
(Confirmation of antifungal effect on strawberries)
Example 1 after 48 hours have passed after the application of the resin composition and after the aging of the above-mentioned antifungal resin film is completed (hereinafter, this state is referred to as "immediately after production" in the present specification). Two antifungal laminated films having a size of 15 cm × 15 cm were prepared. Then, immediately under the atmosphere, two ripe strawberries were sandwiched between these antifungal laminated films, and the peripheral portions of these films were overlapped with each other and heat-laminated. As described above, the above-mentioned two strawberries were housed in a transparent bag (packaging body) made from the antifungal laminated film of Example 1, and a sealed sample was prepared. A total of 24 such samples were prepared.
Similarly, 24 samples were prepared using the laminated film of Comparative Example 1.

Next, the sample obtained above was stored at 20 ° C. for 1 day, then the strawberries were taken out from the bag (packaging body), and the strawberries were visually observed to confirm the number of moldy strawberries. did. Then, the ratio of the number of strawberries with mold to the total number of strawberries (48) (that is, [the number of strawberries with mold] / 48 × 100) is defined as the “mold incidence rate (%)”. Calculated as.
As a result, the mold occurrence rate (%) was 12% when the antifungal laminated film of Example 1 was used, and 70% when the laminated film of Comparative Example 1 was used.

[Test Example 2]
(Confirmation of antifungal effect on rice cake)
A sample was prepared by the same method as in Test Example 1 except that one rice cake of 30 g was used instead of two ripe strawberries as a substance to be contained and sealed inside the bag (packaging body). .. The number of samples was one.
Next, the obtained sample was statically stored at 25 ° C., and during this period, the sealed rice cake was visually observed through the bag to confirm the number of days until mold was formed on the rice cake (the number of days when mold was generated).
As a result, the number of days for mold generation was 5 days when the antifungal laminated film of Example 1 was used, and 3 days when the laminated film of Comparative Example 1 was used.

[Test Example 3]
(Confirmation of antifungal effect on tomatoes)
A sample was prepared by the same method as in Test Example 1 except that one ripe tomato was used instead of two ripe strawberries as a substance to be contained and sealed inside the bag (packaging body). The number of samples was one.
Next, the obtained sample was allowed to stand at 25 ° C. for 2 days, and then the tomatoes were taken out from the bag (packaging body), and the tomatoes were visually observed to confirm the presence or absence of mold.
As a result, when the antifungal laminated film of Example 1 was used, no mold was generated on the tomatoes, whereas when the laminated film of Comparative Example 1 was used, the tomatoes were "septal". There were molds in multiple places.

[Test Example 4]
(Confirmation of antifungal effect on ginger)
A sample was prepared by the same method as in Test Example 1 except that 100 g of one ginger was used instead of two ripe strawberries as a substance to be contained and sealed inside the bag (packaging body). .. The number of samples was eight. All ginger was assumed to have a cut surface created by cutting with a cutting tool.

Next, the sample obtained above was stored at 30 ° C. for 4 days, then the ginger was taken out from the bag (packaging body), and the ginger was visually observed to confirm the number of moldy ginger. did. Then, the ratio of the number of moldy ginger to the total number of ginger (8) (that is, [the number of moldy ginger] / 8 × 100) is defined as the “mold occurrence rate (%)”. Calculated as.
As a result, the mold generation rate (%) was 25% when the antifungal laminated film of Example 1 was used, and 100% when the laminated film of Comparative Example 1 was used. In both the case where the antifungal laminated film of Example 1 was used and the case where the laminated film of Comparative Example 1 was used, mold was mainly generated at the cut end of ginger.

[Test Example 5]
(Confirmation of antifungal effect on medium)
A sterilized medium was prepared on a sterilized petri dish with a diameter of 10 cm. As the medium, a potato dextrose agar medium was used.
Then, Botrytis was inoculated at three sites on the medium.
Next, instead of the two ripe strawberries, the inoculated medium was housed in a bag (package) together with the petri dish and sealed, and a sample was prepared by the same method as in Test Example 1. The number of samples was one.
Next, the obtained sample was allowed to stand at 25 ° C. for 1 day, and then the petri dish was taken out from the bag (package) and the medium was visually observed to confirm the presence or absence of mold.
As a result, no growth of mold was observed on the medium when the antifungal laminated film of Example 1 was used, whereas when the laminated film of Comparative Example 1 was used, the growth of mold was not observed on the medium. The growth of mold was clearly observed.

INDUSTRIAL APPLICABILITY The present invention can be used for a package used for storage of foods and the like.

1 ... Antifungal laminated film 10 ... Antifungal packaging 11 ... First resin layer 12 ... Antifungal resin film 13 ... Second resin layer S ... Accommodating antifungal packaging space

Claims (7)

It is provided with an antifungal resin film, a first resin layer, and a second resin layer.
The antifungal resin film contains an antifungal agent and a resin.
The fungicide is selected from the group consisting of the compound represented by the following formula (1) -1A-0 and a salt thereof, and the compound represented by the following general formula (1) -1A-1 and a salt thereof. One or more of the active ingredients
The antifungal resin film is arranged between the first resin layer and the second resin layer.
The 25 ° C. of the first resin layer, the oxygen gas permeation amount in an atmosphere of RH 65% is ^state, and are ^{3000cm 3 / m 2 · atm ·} day or more,
The 25 ° C. of the second resin layer, the oxygen gas permeation amount in an atmosphere of RH 65% ^is, Ru Der below ^{2000cm 3 / m 2 · atm ·} day, antifungal laminated film.

(In the formula, R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms.) The antifungal resin film is selected from the group consisting of urethane-based adhesives, acrylic-based adhesives, titanate-based adhesives, imine-based adhesives, butadiene-based adhesives, polyester-based adhesives, and olefin-based adhesives as the resin. The antifungal laminated film according to claim 1, further comprising one or more of the following, wherein the antifungal resin film has adhesiveness. One or two selected from the group consisting of the compound represented by the formula (1) -1A-0 and a salt thereof, and the compound represented by the general formula (1) -1A-1 and a salt thereof. The antifungal laminated film according to claim 1 or 2, further comprising another antifungal agent different from the antifungal agent containing the above as an active ingredient. The antifungal laminated film according to claim 3, wherein the other antifungal agent is a compound represented by the following general formula (9) or a salt thereof.

(In the formula, X ⁹ Is a linear or branched alkylene group having 1-3 carbon atoms; ⁹ Is a linear or branched alkyl group having 1-3 carbon atoms; m ₉ Is an integer from 1 to 3 and m ₉ If is 2 or more, multiple Xs ⁹ May be the same or different from each other; n ₉ Is an integer from 0 to 5, but m ₉ + N ₉ Is 6 or less, n ₉ If is 2 or more, multiple Rs ⁹ May be the same or different from each other. ) The antifungal laminated film according to any one of claims 1 to 4, wherein the first resin layer contains low-density polyethylene. The antifungal laminated film according to any one of claims 1 to 5 , wherein the second resin layer contains one or more selected from the group consisting of polyester, nylon and polypropylene. An antifungal package obtained by using the antifungal laminated film according to any one of claims 1 to 6.
It has a storage space formed by partially adhering the first resin layers to each other.
An antifungal package in which the antifungal resin film is arranged on the accommodation space side of the second resin layer.

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