JP2019001755A - Antifungal agent, antifungal resin film, antifungal laminate film and antifungal package - Google Patents

Abstract

To provide an antifungal package capable of being used for storage of foods or the like, an antifungal resin film suitable for constituting the same, an antifungal laminate film obtained by using the antifungal resin film and an antifungal agent suitable for constituting the antifungal resin film.SOLUTION: In an antifungal laminate film 1 having an antifungal resin film 12, a first resin layer 11 and a second resin layer 13, where the antifungal resin film 12 is arranged between the first resin layer 11 and the second resin layer 13, the first resin layer 11 has an oxygen gas permeability amount under atmosphere of 25°C and 65%RH of 3000 cm/matm day, the antifungal resin film 12 contains an antifungal agent and a resin and the antifungal agent contains a compound represented by general formula (1) and a salt thereof as an essential component.SELECTED DRAWING: Figure 1

Description

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

  In order to store and store the object, various storage packages are used. For example, when the object to be stored is to be taken orally such as food, it is required that the object can be stored 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 in a sanitary manner, when the object to be stored is stored in the package, the mold adheres to the object to be stored such as the object to be stored in contact with the storage part of the package. May be taken into the housing space of the package. When it is desired to store the storage object in a sanitary manner, such mold contamination becomes a big problem.

  In order to prevent mold adhering to the storage object from being mixed into the storage space when storing the storage object, for example, molds such as heat treatment, chemical treatment, and ultraviolet irradiation treatment are killed. It is conceivable to store the object to be stored after processing in a package. However, depending on the type of storage object to be taken orally as described above, these treatments may not be performed, and this method is not versatile. Therefore, it is more realistic and important to suppress the growth of mold within the storage space of the package during storage so as not to cause problems. It is possible to grant.

JP-A-9-252718

  However, when the storage object is taken orally, such as food, various restrictions are imposed on the mold-proof package. For example, the package after storing the object to be stored needs to continuously suppress the invasion of mold from the outside. For that purpose, the package has a certain degree of sealing performance such as a resin film or a metal foil. It is necessary to be comprised with the material which has. Especially, the resin film is advantageous at the point which can visually observe the stored preservation | save object from the exterior of a package. In addition, when a fungicide that exhibits fungicidal properties is used, such a fungicide has a certain level of safety to the human body in consideration of the possibility of adhesion to the storage object. It is necessary to use something. And it is desirable to refrain from using an antifungal agent having a strong odor because it is not desirable in terms of functionality. In order to continuously exhibit the antifungal effect for a certain period in the housing space of the package, for example, it is desirable to continuously supply the antifungal agent from the package itself into the housing space. It is advantageous if the fungicide having a property can be supplied as a gas into the housing space. 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 package that can be used for storage of food, etc., an antifungal resin film suitable for constituting the same, and the antifungal resin film. It is an object of the present invention to provide an antifungal laminated film and an antifungal agent suitable for constituting the antifungal resin film.

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

（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, provided that m ₁ + n ₁ is 6 or less, and when n ₁ is 2 or more, a plurality of R ¹ may be the same or different from each other.

[2]. The mold prevention resin film according to [1], wherein the m ₁ is 1.
[3]. The anti-mold resin film according to [1] or [2], wherein the n ₁ is 0 or 1.
[4]. One or two selected from the group consisting of urethane adhesives, acrylic adhesives, titanate adhesives, imine adhesives, butadiene adhesives, polyester adhesives, and olefin adhesives as the resin. The anti-mold resin film according to any one of [1] to [3], including the above, wherein the anti-mold resin film has adhesiveness.
[5]. The antifungal agent comprising the compound represented by the general formula (1) or a salt thereof as an active ingredient and further containing another antifungal agent, according to any one of [1] to [4]. Anti-mold 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, and when m ₉ is 2 or more, the plurality of X ⁹ may be the same or different; n ₉ is an integer of 0 to 5, provided that m ₉ + n ₉ is When it is 6 or less and n ₉ is 2 or more, a plurality of R ⁹ may be the same as or different from each other.)

[7]. [1] to [6] The moldproof resin film according to any one of [1] to [6], a first resin layer, and a second resin layer, wherein the moldproof resin film includes the first resin layer, An antifungal agent disposed between the second resin layer and having an oxygen gas permeation rate 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 anti-mold laminated film according to [7], wherein the first resin layer contains low density polyethylene.
[9]. The anti-mold laminated film according to [7] or [8], wherein the second resin layer has an oxygen gas permeation amount of 3000 cm ³ / m ² · atm · day or less in an atmosphere of 25 ° C. and 65% RH.
[10]. The antifungal laminated film according to any one of [7] to [9], wherein the second resin layer includes one or more selected from the group consisting of polyester, nylon, and polypropylene.
[11]. [7] to [10] A mold-proof package obtained by using the mold-proof laminated film according to any one of [7] to [10], wherein a part of the first resin layers are bonded and formed. An anti-mold package having an accommodating space, wherein the anti-mold resin film is disposed closer to the accommodating space than the second resin layer.
[12]. An antifungal agent comprising a compound represented by the following general formula (1) or a salt thereof as an active ingredient (excluding an antifungal agent comprising 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, provided that m ₁ + n ₁ is 6 or less, and when n ₁ is 2 or more, a plurality of R ¹ may be the same or different from each other.

  According to the present invention, an antifungal package that can be used for storage of food, etc., an antifungal resin film suitable for constituting the same, an antifungal laminated film obtained using the antifungal resin film, And an antifungal agent suitable for constituting the antifungal resin film.

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

<< Anti-mold agent >>
The antifungal agent of the present invention comprises 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).
The antifungal agent of the present invention coexists with the target storage object, thereby suppressing the growth of mold in the storage object. In the present specification, “generation of mold” as described later means that the object grows from a state where mold cannot be visually confirmed to a level where 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, provided that m ₁ + n ₁ is 6 or less, and when n ₁ is 2 or more, a plurality of R ¹ may be the same or different from each other.

<Compound (1)>
The compound represented by the general formula (1) (sometimes referred to as “compound (1)” in this specification) has antifungal properties.
In the general formula (1), R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms. As such an alkyl group, more specifically, a methyl group (—CH ₃ ), 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 general formula (1), m1 is an integer of ₁ to 3, and represents the number of carboxy groups (—C (═O) —OH) in one molecule of compound (1).

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

In the general formula (1), _{n 1} is an integer of 0-5, the number of ^{R 1} in compound (1) in one molecule. 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 (that is, 2, 3, 4, or 5) of R ¹ may be the same as or different from each other. That is, when n ₁ is 2 or more, all R ^{1 s} may be the same, all may be different, or only a part may be the same.

In compound (1), the bonding 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.
When n ₁ is 3, it is preferable that at least two carbon atoms out of the three carbon atoms constituting the benzene ring skeleton to which R ¹ is bonded are not adjacent to each other. More preferably, all three carbon atoms are not adjacent to one another.
Further, when n ₁ is 4, one carbon atom of 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 none of them are adjacent to each other.

The relationship of the relative bonding position between R ¹ and the carboxy group in the benzene ring skeleton is not particularly limited, and may be any of the ortho position, the meta position, and the para position, for example.

The compound (1) when m ₁ is 1 is a compound represented by the following general formula (1) -1A (in this specification, it may be referred to as “compound (1) -1A”). 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 formula, R ¹ is the same as above, and n ₁₁ is an integer of 0 to 5.)

In 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, is similar to the _{n 1} in formula (1).

As the compound (1) when m ₁ is 2, the compound represented by the following general formula (1) -2A, the compound represented by the following general formula (1) -2B, and the following general formula (1) -C (compound (1) -2A, "compound (1) -2B", "compound (1) -2C" corresponding to the reference numerals in the present specification, respectively) May be referred to).

（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 formula, R ¹ is the same as above, and n ₁₂ is an integer of 0 to 4.)

In General Formula (1) -2A to General Formula (1) -2C, R ¹ is the same as R ¹ in General Formula (1).
Formula (1) -2A～ formula (1) in _{-2C, n 12} is an integer from 0 to 4, except that not a 5, similar to the _{n 1} in the general formula (1) is there.

As the compound (1) when m ₁ is 3, the compound represented by the following general formula (1) -3A, the compound represented by the following general formula (1) -3B, and the following general formula (1) -3C compounds (in the present specification, "compound (1) -3A", "compound (1) -3B", "compound (1) -3C" May be referred to).

（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 formula, R ¹ is the same as above, and n ₁₃ is an integer of 0 to 3.)

In General Formula (1) -3A to General Formula (1) -3C, R ¹ is the same as R ¹ in General Formula (1).
In General Formula (1) -3A to General Formula (1) -3C, n ₁₃ is an integer of 0 to 3, and is the same as n ₁ in General Formula (1) except that it is not 4 or 5. Is.

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

As compound (1) when n ₁ is 0, a compound represented by the following general formula (1) -0 (in this specification, sometimes referred to as “compound (1) -0”) Can be mentioned.

（式中、ｍ_１０は１〜３の整数である。）

_{(Wherein, m 10} is an integer of 1-3.)

In the Formula (1) _{-0, m 10} is an integer of 1 to 3, is similar to the _{m 1} in the general formula (1).

As compound (1) when n ₁ is 1, a compound represented by the following general formula (1) -1a (in this specification, sometimes referred to as “compound (1) -1a”) 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 formula, R ¹ is the same as above, and m ₁₁ is an integer of 1 to 3.)

In 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, is similar to the _{m 1} in the general formula (1).

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

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

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

As compound (1) when n ₁ is 3, 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) -3c (in the present specification, “compound (1) -3a”, “compound (1) -3b”, “compound (1) -3c” May be referred to).

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

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

As compound (1) when n ₁ is 4, the compound represented by the following general formula (1) -4a, the compound represented by the following general formula (1) -4b, and the following general formula (1) -4c (in the present specification, “compound (1) -4a”, “compound (1) -4b”, “compound (1) -4c” May be referred to).

（式中、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.)

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

The compound (1) when n ₁ is 5 is a compound represented by the following general formula (1) -5a (in this specification, sometimes referred to as “compound (1) -5a”). Can be mentioned.

（式中、Ｒ^１は上記と同じである。）

(Wherein R ¹ is the same as above)

In 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) when m ₁ in the general formula (1) is 1.

In the 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 preferred. Such a compound (1) not only has an excellent antifungal action, but can be produced more easily and inexpensively.

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

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

（式中、Ｒ^１は上記と同じである。）

(Wherein R ¹ is the same as above)

<Salt of Compound (1)>
The salt of compound (1) has antifungal properties.
As a salt of compound (1), for example, a carboxyl group (—C (═O) —OH) in compound (1) becomes an anion (carboxylate anion, —C (═O) —O ⁻ ). (In this specification, a salt formed by a cation and a “anion derived from the compound (1)”) and a cation may be mentioned.

The valence of the cation forming the salt of compound (1) is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more. 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 cation constituting the salt of one molecule of the compound (1) may be only one, or two or more, and when there are two or more, these cations may be all the same. They may be all different, or only part of them may be the same.
However, the salt of the compound (1) is electrically neutral as a whole molecule, that is, the total value of the cation valence and the total value of the anion valence in one molecule of the compound (1) are the same. Is preferred.

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

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

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 a cation obtained by protonating a primary amine, a secondary amine, or a tertiary amine.
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 is a hydrogen atom, an alkyl group or an aryl group, and a plurality of Z ¹ may be the same or different from each other, and when two or more Z ¹ are an alkyl group, these alkyl groups May be bonded 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), a plurality (that is, four) of Z ¹ may be the same as or different from each other. That is, the plurality of Z ¹ may all be the same, may all be different, or may be the same in only a part.

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

The linear or branched alkyl group in Z ¹ preferably has 1 to 10 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and 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-methyl Heptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethyl Xyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1-propylpentyl group, 2 -A propylpentyl group, a nonyl group, a decyl group, etc. are mentioned.
The number of carbon atoms of straight-chain or branched-chain of the alkyl group in Z ¹ may be, for example, either 1～8,1～5 and 1-3, but these examples.

The cyclic alkyl group in Z ¹ preferably has 3 to 10 carbon atoms. Examples of such an alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclo Examples include an octyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, a 2-adamantyl group, and a tricyclodecyl group.
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.

When two or more (that is, two, three, or four) Z ¹ is the alkyl group, the two or more alkyl groups are bonded to each other to form a nitrogen atom to which the alkyl group is bonded. And may form a ring. In this case, the bonding position of two or more alkyl groups is not particularly limited, and the formed ring may be either monocyclic or polycyclic.

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

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

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

  Compound (1) and a salt thereof may have volatility. The volatile compounds (1) and salts thereof are advantageous in that they become gas at room temperature, so that they continuously act in the packaging space to be described later. The mold effect can be maintained for a longer time.

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

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

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

<Method for Producing Compound (1)>
Compound (1) is, for example, a step of obtaining compound (1) by oxidizing a compound represented by the following general formula (101) (in this specification, sometimes referred to as “compound (101)”) (In this specification, it can be produced by a production method having “compound (1) production process”).

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

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

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

<Method for producing salt of compound (1)>
The salt of compound (1) can be produced by applying a known method for converting carboxylic acid to carboxylate to compound (1).
For example, a reaction (neutralization reaction) is performed by allowing a base to act on compound (1) in an isolated state or compound (1) before extraction in the above-described method for producing compound (1). By the manufacturing method etc. which have the process of obtaining the salt of compound (1), the salt of compound (1) can be manufactured. As the compound (1) in an 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, a tertiary Amine compounds such as amine; ammonia; quaternary ammonium halides such as tetra n-butylammonium fluoride.

  The salt of the compound (1) can also be produced by subjecting the salt of the non-target compound (1) to salt exchange so that it becomes the salt of the target compound (1).

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

The antifungal agent of the present invention may contain other components in addition to the compound (1) or a salt thereof.
The said other component in an antifungal agent is not specifically limited unless the effect of this invention is impaired, It can select arbitrarily.
For example, the compound (1) or a salt thereof may be either solid or liquid at normal temperature and normal pressure, and appropriately selected according to the type of the mold-proof resin film described later. That's fine. The compound (1) or a salt thereof may be used by, for example, being dissolved or dispersed in a solvent, or diluted with a solvent. That is, examples of the other components include a solvent.
In the present specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and includes a temperature of 15 to 25 ° C., for example.

What is necessary is just to select the said solvent suitably according to the kind of compound (1) or its salt, and the kind is not specifically limited.
Preferred examples of the solvent include an organic solvent and water.

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

  In the antifungal agent of the present invention, the solvent may be used alone or in combination of two or more, and when there are two or more, their combination and ratio can be arbitrarily selected according to the purpose. For example, when two or more solvents are used in combination, only two or more organic solvents may be used in combination, a mixed solvent of only the organic solvent may be used, or one or two or more organic solvents and water may be used in combination. An aqueous mixed solvent may be used.

When the antifungal agent of this invention contains the said solvent, content of a solvent is not specifically limited, For example, it can be 10-90 mass%, but this is only an example.
In addition, the antifungal agent of this invention containing a solvent can be used as it is as a resin composition for forming the anti-mold resin film mentioned later.

When the antifungal agent 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 effects of the present invention are not impaired, and is appropriately determined according to the type of the other components. Just choose.
However, normally, in the antifungal agent of the present invention, the solvent relative to the total content of components other than the solvent (that is, the compound (1), the salt of the compound (1), and other components other than the solvent). The 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. Any of 1 mass% or less etc. may be sufficient.

Microorganisms (molds) that have an anti-proliferative effect (anti-mold effect) by use of the anti-fungal agent of the present invention are not generally limited to those in a specific range, but those having a high anti-mold effect Microorganisms belonging to the genus Penicillium, microorganisms belonging to the genus Aspergillus, microorganisms belonging to the genus Cladosporium, microorganisms belonging to the genus Fusarium, microorganisms belonging to the genus Alternaria, Rhizopus Examples 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 blue mold and white mold. Examples of microorganisms belonging to the genus Aspergillus include Aspergillus niger. Examples of microorganisms belonging to the genus Cladosporium include black mold and the like. Examples of microorganisms belonging to the genus Fusarium include Fusarium solani. Examples of microorganisms belonging to the genus Alternaria include Alternaria tenuis. Examples of microorganisms belonging to the genus Rhizopus include Rhizopus nigricans. Examples of microorganisms belonging to the genus Botrytis include Botrytis cinerea.

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

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

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

<< Anti-mold resin film >>
The antifungal resin film of the present invention comprises an antifungal agent containing the compound (1) or a salt thereof as an active ingredient, and a resin. The fungicide resin film of the present invention includes those containing a fungicide containing benzoic acid or sodium benzoate as an active ingredient.
The anti-mold resin film of the present invention has excellent anti-mold properties by including the anti-mold agent.

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

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

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

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

  Preferred examples of the adhesive resin include urethane adhesives such as polyurethane (adhesive resins having a urethane bond); acrylic adhesives such as acrylic copolymer resins (adhesive resins having a (meth) acryloyl group), Titanate adhesives (adhesive resins obtained using titanate esters), imine adhesives (adhesive resins obtained using ethyleneimine), butadiene adhesives such as styrene-butadiene copolymers ( Adhesive resin obtained using butadiene as the monomer component), polyester-based adhesives such as polyvinyl acetate (adhesive resins having ester bonds), and olefin-based adhesives such as isobutene / maleic anhydride copolymer resins (monomers) And an adhesive resin obtained using olefin as a component.

  In the present specification, “(meth) acryloyl group” is a concept including both “acryloyl group” and “methacryloyl group”.

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

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

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

(Other fungicides)
Preferable other components include, for example, other antifungal agents different from the antifungal agent containing the compound (1) or a salt thereof as an active ingredient.
That is, as a preferable said anti-mold resin film, for example, a film further including another anti-mold agent different from the anti-mold agent containing the compound (1) or a salt thereof as an active ingredient can be mentioned.
As described above, the mold-resin film may further exhibit a synergistic effect in which the mold-proof property is remarkably higher than the case where the mold-proof resin film is not included in other mold-proofing agents by further including other mold-proofing agents.

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

Among these, other preferable antifungal agents include, for example, a compound represented by the following general formula (9) (sometimes referred to as “compound (9)” in this specification) or a salt thereof. It is done.
That is, as a more preferable said anti-mold resin film, what further contains a compound (9) or its salt as an anti-mold agent is mentioned, for example.

（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, and when m ₉ is 2 or more, the plurality of X ⁹ may be the same or different; n ₉ is an integer of 0 to 5, provided that m ₉ + n ₉ is When it is 6 or less and n ₉ is 2 or more, a plurality of R ⁹ may be the same as 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. 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 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 General Formula (1).

In General Formula (9), m ₉ is an integer of 1 to 3, and General Formula “—O—X ⁹ —OH in one molecule of Compound (9) (wherein X ⁹ is the same as above). The number of groups represented by
When m ₉ is 2 or more (that is, 2 or 3), a plurality (that is, 2 or 3) of X ⁹ may be the same as or different from each other. That is, when m ₉ is 2 or more, all X ⁹ may be the same, all may be different, or only a part may be the same.

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, two carbon atoms constituting the benzene ring skeleton to which a group represented by the general formula “—O—X ⁹ —OH” is bonded are adjacent to each other. Preferably not.
In addition, when m ₉ is 3, at least three carbon atoms constituting the benzene ring skeleton to which a group represented by the general formula “—O—X ⁹ —OH” is bonded. Two carbon atoms are preferably not adjacent to each other, more preferably all three carbon atoms are not adjacent to each other.

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

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

Regardless of the value of n ₉ , the bonding 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.
When n ₉ is 3, it is preferable that at least two carbon atoms out of the three carbon atoms constituting the benzene ring skeleton to which R ⁹ is bonded are not adjacent to each other. More preferably, all three carbon atoms are not adjacent to one another.
Further, when n ₉ is 4, one carbon atom of 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 none of them are adjacent to each other.

The relationship of the relative bonding position between R ⁹ in the benzene ring skeleton and the group represented by the general formula “—O—X ⁹ —OH” is not particularly limited, and examples thereof include ortho-position, meta-position and para-position. Either may be sufficient.

In the 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 preferred. Such a compound (9) not only has an excellent antifungal action, but can be produced more easily and inexpensively.

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

As a salt of compound (9), for example, a group represented by general formula “—O—X ⁹ —OH” in compound (9) is an anion (that is, general formula “—O—X ⁹ —O ⁻ ”). A group represented by the formula (wherein X ⁹ is the same as above)) (sometimes referred to herein as “anion derived from compound (9)”), a cation, , And the salt formed.

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

As described above, the cation constituting the salt of one molecule of the compound (9) may be only one, may be two or more, and when there are two or more, these cations may be all the same. They may be all different, or only part of them may be the same.
However, the salt of the compound (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 the compound (9) are the same. Is preferred.

  The said cation which forms the salt of a compound (9) with the anion derived from a compound (9) is not specifically limited, Any of an inorganic cation and an organic cation may be sufficient.

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

In the antifungal resin film, the compound (9) or a salt thereof may be only one kind or two kinds or more, and when there are two kinds or more, the combination and ratio thereof are arbitrarily selected according to the purpose. You can choose.
For example, the anti-mold resin film may contain only one or more compounds (9) as the other anti-fungal agent, or one or more salts only of the compound (9). One or two or more of the salt of the compound (9) and the compound (9) may be contained.

  Compound (9) and salts thereof are preferably usable as food additives. As used herein, “food additive” means that the Ministry of Health, Labor and Welfare of Japan has approved its use as of March 12, 2013.

  The compound (9) and its salt are preferably volatile. The volatile compound (9) and its salt is advantageous for continuously acting in the accommodation space of the packaging body described later by converting from liquid to gas at normal temperature. The mold prevention effect can be maintained for a longer time.

  The molecular weight of the compound (9) and the salt thereof is preferably 300 or less in view of being easily volatilized, and can be any of 250 or less, 200 or less, 150 or less, and the like. It is. In addition, the lower limit of the molecular weight of the compound (9) and its salt is not particularly limited.

The compound (9) and its salt are preferably odorless or have a weak odor. Even if such a compound (9) and a salt thereof are attached to the storage object, they are not functionally preferred because they hardly or hardly remind the presence of the storage object when used.
As the compound (9) and its salt, those having an odor are preferably usable as perfumes. As such a compound (9) and its salt, what is classified into the natural fragrance | flavor of a food additive is mentioned, for example.

  Thus, the compound (9) or a salt thereof that can be used as a food additive, has volatility, is odorless, or has a weak odor, for example, 2-phenoxyethanol represented by the following formula, etc. Is 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.

  Compound (9) is represented, for example, by a compound represented by the following general formula (901) (sometimes referred to as “compound (901)” in this specification) and the following general formula (902). A step of reacting a compound (sometimes referred to as “compound (902)” in this specification) to obtain compound (9) (referred to as “compound (9) production step” in this specification). In some cases).

（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。）

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

The reaction in the production step of compound (9) can be carried out by a known method, and the reaction conditions may be appropriately selected according to the type of raw material used.
Examples of Lg include halogen atoms such as chlorine atom, bromine atom and iodine atom; alkylsulfonyloxy group; fluoroalkylsulfonyloxy group and the like.
In the production process of compound (9), for example, a hydroxyl group (—OH) in compound (902) and the like that may cause an unintended reaction in the raw material used may be protected with a protecting group in advance. The compound (9) may be obtained by carrying out the reaction and deprotecting after completion of the reaction.
Compound (901) can be produced by applying the usual method for producing sodium alkoxide. For example, using a corresponding phenol compound as a raw material, that is, a compound in which a group represented by the formula “—O ^— Na ⁺ ” is replaced with a group represented by the formula “—OH” in the compound (901), Compound (901) can be obtained by reacting sodium metal, sodium hydride, or the like.
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 as defined above)”, or one of the hydroxyl groups is a protecting group. It can manufacture by the method of introduce | transducing Lg using the protected compound. When a protecting group is used, the protecting group may be removed (deprotected) at an appropriate timing. However, the manufacturing method of the compound (902) shown here is an example.

In the production step of compound (9), after completion of the reaction of compound (901) and compound (902), the compound (9), which is the target product, can be obtained by performing post-treatment as necessary by a known method. it can. That is, after completion of the reaction, post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, concentration, etc. are carried out as needed, either alone or in combination of two or more to concentrate, crystallize, reprecipitate Compound (9) can be removed by column chromatography or the like. In addition, the taken out compound (9) may be further used as needed either by crystallization, reprecipitation, column chromatography, extraction, stirring and washing of crystals with a solvent, or a combination of two or more. You may refine | purify by performing it more than once.
Compound (9) may be used for the intended purpose without being taken out after being subjected to post-treatment as necessary after completion of the reaction.

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

The salt of compound (9) can be produced by applying a usual production method for metal alkoxides. For example, in the case of the sodium salt (sodium alkoxide) of the compound (9), the compound (9) in an isolated state or the compound (9) before extraction in the production method of the compound (9) described above By applying the same method as in the production of the above-mentioned compound (901), the target product can be obtained. As the compound (9) in an isolated state, a commercially available product may be used.
The salt of the compound (9) may be taken out and used in the same manner as in the case of the compound (9), or may be used continuously for the intended use without taking out.
The structure of the obtained salt of compound (9) can be confirmed by the same method as in the case of compound (9).

  Microorganisms (mold) in which the growth inhibitory effect (antifungal effect) is recognized by the use of compound (9) or a salt thereof are not generally limited to a specific range, but have a high antifungal effect. Are the same as those having a high antifungal effect with the antifungal agent comprising the above-mentioned compound (1) or a salt thereof as an active ingredient.

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

  The resin composition may contain other components that do not fall under any of the other antifungal agents, curing agents, and crosslinking agents, if necessary. A solvent is mentioned.

The said solvent is for making the handleability of the said resin composition favorable, and the kind is not specifically limited in the range which does not impair the effect of this invention.
As said solvent in a resin composition, the thing similar to the solvent demonstrated previously as what the anti-mold agent of this invention may contain is mentioned, for example.

  The total content of compound (1) and its salt in the mold-proof resin film (in other words, the ratio of the total content of compound (1) and its salt to the total content of components other than the solvent in the resin composition ) Is preferably 10 to 44% by mass, more preferably 14 to 40% by mass, and particularly preferably 18 to 36% by mass. When the total content of the compound (1) and the salt thereof is not less than the lower limit value, the antifungal effect when the antifungal resin film is used is further increased. Moreover, compound (1) and its salt are more stably hold | maintained with high uniformity in a mold prevention resin film because the total content of a compound (1) and its salt is below the said upper limit.

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

  Content of the other components other than the solvent in the anti-mold 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) Is 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 equal to or higher than the lower limit, the effect of using other antifungal agents can be obtained more remarkably, and when the ratio is equal to or lower than the upper limit, excessive use of other antifungal agents. Is suppressed.

  Moreover, for example, when the other component is the curing agent or the crosslinking agent, in the anti-mold resin film and the resin composition, the ratio of the content of the other component to the content of the resin is 10 to 10%. It is preferable that it is 40 mass%, and it is more preferable that it is 20-30 mass%. When the ratio is equal to or higher than the lower limit value, the effect of using other components is more remarkably obtained. When the ratio is equal to or lower than the upper limit value, excessive use of other components is suppressed. .

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

  The content of other components that do not correspond to any of the other antifungal agents, curing agents, crosslinking agents, and solvents of the antifungal resin film can be set to, for example, 0 to 10% by mass.

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

  In the present specification, not only in the case of the anti-mold resin film, but “a plurality of layers may be the same or different from each other” means “all layers may be the same or all The layers may be different, and only some of the layers may be the same, and “a plurality of layers are different from each other” means “at least one of the constituent materials and thicknesses of each layer is mutually different. Means different.

What is necessary is just to select the thickness of the said mold prevention resin film suitably according to a use, and it does not specifically limit it.
For example, when producing a package body such as a bag using the anti-mold resin film, the thickness of the anti-mold resin film is preferably 0.5 to 15 μm, and preferably 1 to 12 μm. More preferably, it is 1.3-10 micrometers, for example, 1.3-7.5 micrometers etc. may be sufficient.
In the case where the moldproof resin film is composed of a plurality of layers, the total thickness of the plurality of layers may be set to the thickness of the preferable moldproof resin film.

  The compound (1) and salts thereof are suitable for use as an antifungal resin film, but since they have an excellent antifungal effect, they are also suitable for use in applications other than the antifungal resin film. For example, the compound (1) or a salt thereof can be used as a solid (for example, granular, block, etc.) anti-mold material other than a film, an anti-mold ink composition, an anti-mold spray agent, and the like. As described above, when the compound (1) or a salt thereof is used for applications other than the mold-proof resin film, in addition to the compound (1) or a salt thereof, components necessary for making the target product have desired properties are used in combination. What is necessary is just to prepare the target composition using this composition.

<< Anti-mold laminated film >>
The anti-mold laminated film of the present invention comprises the above-described anti-mold resin film of the present invention, a first resin layer, and a second resin layer, and the anti-mold resin film includes the first resin layer and the first resin layer. And an oxygen gas permeation amount in an atmosphere of 25 ° C. and 65% RH of the first resin layer is 3000 cm ³ / m ² · atm · day or more.
The mold-proof laminated film of the present invention uses the mold-proof resin film, so that it has excellent mold-proof properties and is suitable for the production of a package for storing and storing a target product.

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

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

The 1st resin layer 11 is a layer arrange | positioned rather than the anti-mold resin film 12 at this preservation | save object side, when preserve | saving an object using the anti-mold laminated film 1. FIG. For example, in a bag-like package manufactured using the mold-proof laminated film 1, the first resin layer 11 is disposed closer to the package space than the mold-proof resin film 12.
Therefore, for example, when the first resin layer 11 is one of the outermost layers of the anti-mold laminated film 1, the first resin layer 11 is a layer in contact with the storage object.
In this way, the first resin layer 11 prevents the anti-mold resin film 12 from contacting the storage object, thereby suppressing excessive migration of the anti-mold agent from the anti-mold resin film 12 to the storage object. To 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, 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 equal to or greater than the lower limit, the compound (1) or a salt thereof transferred from the inside of the anti-mold resin film 12 to the first resin layer 11 side is the first resin. The layer 11 is easily transferred to the outside (the outside on the first resin layer 11 side of the anti-mold laminated film 1). Thereby, the anti-mold laminated film 1 exhibits an excellent anti-mold 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 conditions. Preferred examples include low-density polyethylene (LDPE) and linear low-density polyethylene. (LLDPE), metallocene catalyst linear low density polyethylene (metallocene LLDPE) and the like.
Moreover, as a constituent material of the 1st resin layer 11, synthetic resins other than these are also mentioned.

  The constituent material of the 1st resin layer 11 may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be arbitrarily selected according to the objective.

  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, and 80% by mass or more. Is more preferably 90% by mass or more, for example, 99% by mass or more, or 100% by mass.

  The 1st resin layer 11 may consist of one layer (single layer), and may consist of two or more layers. When the 1st resin layer 11 consists of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited unless the effect of this invention is impaired.

Although the thickness of the 1st resin layer 11 is not specifically limited, It is preferable that it is 5-200 micrometers, It is more preferable that it is 10-150 micrometers, It is especially preferable that it is 15-100 micrometers. When the thickness of the first resin layer 11 is equal to or more than the lower limit value, the strength of the first resin layer 11 is further improved, and an excessive migration of the antifungal agent from the antifungal resin film 12 to the storage object is performed. More suppressed. Moreover, when the thickness of the first resin layer 11 is equal to or less than the upper limit value, the anti-mold effect of the anti-mold laminated film 1 is further improved.
When the first resin layer 11 includes a plurality of layers, the total thickness of the plurality of layers may be set to the preferable thickness of the first resin layer 11 described above.

  The anti-mold resin film 12 is the anti-mold resin film of the present invention described above. Here, detailed description of the anti-mold resin film 12 is omitted.

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

The amount of oxygen gas permeation in the atmosphere of 25 ° C. and 65% RH (relative humidity) of the second resin layer 13 is preferably 3000 cm ³ / m ² · atm · day or less, preferably 2500 cm ³ / m ² · atm. More preferably, it is not more than day, and particularly preferably not more than 2000 cm ³ / m ² · atm · day.
The smaller the upper limit value of the oxygen gas permeation amount of the second resin layer 13 is, the more the compound (1) or its salt is transferred from the inside of the anti-mold resin film 12 to the second resin layer 13 and the second resin layer 13. Transition to the outside (outside of the mold preventive laminated film 1 on the second resin layer 13 side) via the sheet is effectively suppressed. Therefore, since the amount of the compound (1) or the salt thereof transferred from the inside of the anti-mold resin film 12 to the storage object side can be maintained at an appropriate level for a long period of time, the anti-mold laminated film 1 is more excellent Expresses mold effect. Further, for example, when the target object is accommodated and sealed in a bag-shaped package produced using the mold-proof laminated film 1, the compound (1) or a salt thereof to the outside of the package is contained. Migration is suppressed, and the use of the compound (1) or a salt thereof is hardly or hardly reminded at the time of storage of the target product, which is functionally preferable.
Furthermore, the smaller the upper limit value of the oxygen gas permeation amount of the second resin layer 13 is, the smaller is the distance from the outside (the outside on the second resin layer 13 side of the mold prevention laminated film 1) through the second resin layer 13 to the inside. The oxygen gas migration is effectively suppressed. Therefore, the effect of preserving the object without degrading the quality is further enhanced.

On the other hand, the lower limit value of the oxygen gas permeation amount in the atmosphere of 25 ° C. and 65% RH (relative humidity) of the second resin layer 13 is not particularly limited, and is, for example, 50 cm ³ / m ² · atm · day, 500 cm. ³ / m ² · atm · day and 1000 cm ³ / m ² · atm · day, which are examples.

  The oxygen gas permeation amounts of the first resin layer 11 and the second resin layer 13 are both values measured in accordance with JIS K7126B.

The constituent material of the second resin layer 13 may be appropriately selected according to the purpose and is not particularly limited, but it is easy to configure the second resin layer 13 so as to satisfy the above-described oxygen gas permeation amount condition. In terms of polyester, such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN); nylon; polypropylene (PP), etc. Can be mentioned.
Moreover, as a constituent material of the 2nd resin layer 13, synthetic resins other than these are also mentioned.

  The constituent material of the 2nd resin layer 13 may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be arbitrarily selected according to the objective.

  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 polyester, nylon and polypropylene in the second resin layer 13 is 80 mass. % Or more, more preferably 90% by weight or more, particularly preferably 95% by weight or more, for example, 99% by weight or more, or 100% by weight. 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 2nd resin layer 13 consists of multiple layers, these multiple layers may mutually be same or different, and the combination of these multiple layers is not specifically limited unless the effect of this invention is impaired.

Although the thickness of the 2nd resin layer 13 is not specifically limited, It is preferable that it is 2-100 micrometers, It is more preferable that it is 5-70 micrometers, It is especially preferable that it is 8-40 micrometers. 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 more prominently obtained. Moreover, when the thickness of the second resin layer 13 is equal to or less than the upper limit value, an excessive thickness can be avoided.
When the second resin layer 13 includes a plurality of layers, the total thickness of the plurality of layers may be set to the preferable thickness of the second resin layer 13 described above.

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

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

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

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

Next, the exposed surface of the anti-mold resin film in the intermediate laminate (the surface where the first resin layer or the second resin layer is not provided) and the other surface (one surface) of the first resin layer and the second resin layer ), And an anti-mold laminated film is formed. Here, the “one of the first resin layer and the second resin layer” is the second resin layer when the intermediate laminate is laminated on the anti-mold resin film as the first resin layer. When the thing laminated | stacked on the anti-mold resin film in the said intermediate | middle laminated body is a 2nd resin layer, it means the 1st resin layer.
Bonding of the intermediate laminate and the second resin layer or the first resin layer can be performed by applying various known laminating methods.

  Although the said anti-mold laminated film is obtained by the above, when manufacturing the anti-mold laminated film which comprises other layers other than the 1st resin layer, the anti-mold resin film, and the 2nd resin layer, it is the above-mentioned. In this manufacturing method, a step of forming the other layer may be added at an appropriate timing so that the other layer is disposed at a target stacking position.

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

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

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

<< Anti-mold packaging >>
The mold-proof package of the present invention is a mold-proof package obtained by using the mold-proof laminated film of the present invention described above, and is a container in which a part of the first resin layers are bonded and formed. It has space and the said mold prevention resin film is arrange | positioned rather than the said 2nd resin layer at the said accommodation space side.
The mold-proof package of the present invention uses the mold-proof laminated film (mold-resistant resin film), and thus has excellent mold-proof properties, and the growth of mold in the storage space during storage of the target product. Is significantly suppressed.

FIG. 2 is a cross-sectional view schematically showing one embodiment of the anti-mold package of the present invention.
The anti-mold packaging body 10 shown here is formed using the anti-mold laminated film 1 shown in FIG. The anti-mold package 10 has a housing space S formed by bonding a part of the first resin layers 11 and 11 of the pair of anti-mold laminated films 1 and 1, and the anti-mold resin film 12. Is arranged closer to the accommodation space S than the second resin layer 13 and is schematically configured. That is, the pair of anti-mold laminated films 1 and 1 are arranged such that these first resin layers 11 and 11 face each other.
A target storage object (not shown) is stored in the storage space S of the anti-mold package 10.

In the anti-mold package 10, the compound (1) or a salt thereof easily migrates from the inside of the anti-mold resin film 12 into the accommodation space S through the first resin layer 11. Thereby, the mold prevention package 10 can maintain the density | concentration of the compound (1) in the accommodation space S or its salt at a suitable level for a fixed period, and expresses the outstanding mold prevention effect.
Further, in the moldproof package 10, the first resin layer 11 prevents contact between the storage object in the storage space S and the moldproof resin film 12, and prevents the moldproof resin film 12 from protecting the storage object. Excess migration of mold is suppressed.

Furthermore, in the anti-mold package 10, as described in the anti-mold laminated film, by adjusting the configuration of the second resin layer 13, the anti-mold effect can be maintained and the object to be stored by oxygen gas from the outside. It is possible to further increase the effect of suppressing deterioration of objects.
In addition, by using the anti-mold package 10 and adjusting the kind of the compound (1) or a salt thereof, the storage object at the time of use after the storage is used as the compound (1) or a salt thereof (an anti-mold agent). It is also possible to make it functionally preferable so that it is not recollected at all or hardly.

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

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

The anti-mold package of the present invention can be produced by bonding a part of the first resin layers so as to have an accommodation space using the anti-mold laminated film of the present invention.
The adhesion between the first resin layers can be performed, for example, by applying various known laminating methods.

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

<Manufacture of mold-proof laminated film>
[Example 1]
The mold prevention laminated film of the structure shown in FIG. 1 was manufactured with the procedure shown below.
(Manufacture of mold-proof resin film)
Main agent ("Takelac (registered trademark) A620" manufactured by Mitsui Chemicals, Ltd., solid content 50 mass%, ethyl acetate 50 mass%) (6 parts by mass), curing agent ("Takenate (registered trademark) A10" manufactured by Mitsui Chemicals, Inc.) , 75 mass% solid content, 25 mass% ethyl acetate) (1 mass part), and ethyl acetate (6 mass parts) were mixed to prepare a polyurethane-based adhesive. In the obtained polyurethane adhesive, the total content of the solvent (ethyl acetate) is 71.2% by mass.
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 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 multi-coater and dried at 80 ° C., so that the content of sodium benzoate was 35. An anti-mold resin film (thickness 4 μm) having a mass% was formed on a PET film. In addition, the depth of the gravure roll was 80 micrometers at the time of application | coating of a resin composition.

(Manufacture of mold-proof laminated film)
Furthermore, by bonding an LDPE film (thickness 25 μm) to the surface of the anti-mold resin film obtained above opposite to the side where the PET film is provided, the PET film, the anti-mold resin film and the LDPE A transparent anti-mold laminated film obtained by laminating films in this order was obtained.

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

<Manufacture of laminated film>
[Comparative Example 1]
A resin composition was prepared without using sodium benzoate. By using this resin composition, sodium benzoate was used in place of an antifungal resin film (thickness 4 μm) having a sodium benzoate content of 35% by mass. A transparent laminated film was obtained in the same manner as in Example 1 except that a resin film (thickness: 4 μm) having a content of 0% by mass was formed.

<Evaluation of mold-proof laminated film and laminated film>
[Test Example 1]
(Confirmation of mold prevention effect on strawberry)
Example 1 after 48 hours had elapsed after application of the resin composition and after aging of the above-mentioned antifungal resin film was completed (hereinafter, this state is referred to as “immediately after production”). Two anti-mold laminated films having a size of 15 cm × 15 cm were prepared. Then, immediately in the atmosphere, the peripheral portions of these films were superposed and heat-laminated in a state where two ripe strawberries were sandwiched between these anti-mold laminated films. By the above, the above-mentioned two strawberries were accommodated in the inside of the transparent bag (packaging body) produced from the anti-mold laminated film of Example 1, and the sealed sample was produced. A total of 24 such samples were produced.
Similarly, 24 samples were produced using the laminated film of Comparative Example 1.

Next, after the sample obtained above was stored at 20 ° C. for one day, the strawberry was taken out from the bag (packaging body), and this strawberry was visually observed to confirm the number of strawberry in which mold was generated. did. The ratio of the number of strawberries in which mold is generated to the total number of strawberries (48) (that is, [number of strawberries in which mold is generated] / 48 × 100) is “mold generation rate (%)”. Calculated as
As a result, the mold generation rate (%) was 12% when the mold-proof laminated film of Example 1 was used, and 70% when the laminated film of Comparative Example 1 was used.

[Test Example 2]
(Confirmation of fungicidal effect against cocoons)
A sample was prepared in the same manner as in Test Example 1 except that one strawberry of 30 g was used instead of two fully-ripened strawberries as a container (packed body) for containing and sealing. . The number of samples was one.
Next, the obtained sample was stored at 25 ° C., and during this period, the sealed ridge was visually observed through a bag, and the number of days until mold was generated on the ridge (mold generation days) was confirmed.
As a result, the number of mold generation days was 5 days when the mold-proof 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 mold prevention effect on tomato)
A sample was prepared in the same manner as in Test Example 1 except that one ripe tomato was used instead of two ripe strawberries as a package (package) to be contained and sealed. The number of samples was one.
Next, after the sample obtained was stored at 25 ° C. for 2 days, the tomato was taken out from the bag (packaging body), and the tomato was visually observed to confirm the presence or absence of mold.
As a result, when the mold-proof laminated film of Example 1 was used, no mold was generated on the tomato, whereas when the laminated film of Comparative Example 1 was used, the tomato “sweet” Mold was generated in several places.

[Test Example 4]
(Confirmation of mold prevention effect against ginger)
A sample was prepared in the same manner as in Test Example 1 except that one ginger of 100 g was used instead of two fully-ripened strawberries as a container (package) to be contained and sealed. . The number of samples was 8. In addition, all the ginger shall have the cut end produced by the cutting | disconnection with a blade.

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

[Test Example 5]
(Confirmation of fungicidal effect in the medium)
A sterilized medium was prepared on a sterilized petri dish having a diameter of 10 cm. As the medium, potato dextrose agar medium was used.
Next, Botrytis bacteria were inoculated at three locations on the medium.
Next, a sample was prepared in the same manner as in Test Example 1 except that the inoculated medium was housed and sealed in a bag (packaging body) with the petri dish instead of the two ripe strawberries. The number of samples was one.
Next, after the sample obtained was stored at 25 ° C. for 1 day, the petri dish was taken out from the bag (packaging body), and the medium was visually observed to check for the occurrence of mold.
As a result, when the mold-proof laminated film of Example 1 was used, mold growth was not observed on the medium, whereas when the laminated film of Comparative Example 1 was used, The growth of mold was clearly recognized.

  The present invention can be used for a package used for storing food or the like.

DESCRIPTION OF SYMBOLS 1 ... Mold-proof laminated film 10 ... Mold-proof packaging body 11 ... 1st resin layer 12 ... Mold-proof resin film 13 ... 2nd resin layer S ... Storage of mold-proof packaging body space

Claims (12)

An antifungal resin film comprising an antifungal agent comprising a compound represented by the following general formula (1) or a salt thereof as an active ingredient and a resin.

(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, provided that m ₁ + n ₁ is 6 or less, and when n ₁ is 2 or more, a plurality of R ¹ may be the same or different from each other. The anti-mold resin film according to claim 1, wherein m ₁ is 1. The anti-mold resin film according to claim 1 or 2, wherein the n ₁ is 0 or 1.   One or two selected from the group consisting of urethane adhesives, acrylic adhesives, titanate adhesives, imine adhesives, butadiene adhesives, polyester adhesives, and olefin adhesives as the resin. The mold prevention resin film according to any one of claims 1 to 3, comprising the above, wherein the mold prevention resin film has adhesiveness.   The antifungal agent according to any one of claims 1 to 4, further comprising another antifungal agent different from the antifungal agent comprising the compound represented by the general formula (1) or a salt thereof as an active ingredient. Resin film. The anti-mold resin film according to claim 5, wherein the other anti-mold 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 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, and when m ₉ is 2 or more, the plurality of X ⁹ may be the same or different; n ₉ is an integer of 0 to 5, provided that m ₉ + n ₉ is When it is 6 or less and n ₉ is 2 or more, a plurality of R ⁹ may be the same as or different from each other.) An antifungal resin film according to any one of claims 1 to 6, a first resin layer, and a second resin layer,
The mold-proof resin film is disposed between the first resin layer and the second resin layer;
The anti-mold laminated film in which the first resin layer 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.   The anti-mold laminated film according to claim 7, wherein the first resin layer contains low-density polyethylene. The mold prevention laminated film of Claim 7 or 8 whose oxygen gas permeation amount in 25 degreeC and 65% RH atmosphere of the said 2nd resin layer is 3000 cm < ³ > / m < ² > * atm * day or less.   The mold prevention laminated film as described in any one of Claims 7-9 in which the said 2nd resin layer contains the 1 type (s) or 2 or more types selected from the group which consists of polyester, nylon, and a polypropylene. A mold-proof package obtained by using the mold-proof laminated film according to any one of claims 7 to 10,
A part of the first resin layers are bonded to each other, and has an accommodation space formed;
The anti-mold packaging body in which the anti-mold resin film is disposed closer to the housing space than the second resin layer. An antifungal agent comprising a compound represented by the following general formula (1) or a salt thereof as an active ingredient (excluding an antifungal agent comprising benzoic acid or sodium benzoate as an active ingredient).

(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, provided that m ₁ + n ₁ is 6 or less, and when n ₁ is 2 or more, a plurality of R ¹ may be the same or different from each other.

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