JP6897031B2 - Antifungal agent, antifungal resin film, antifungal laminated film and antifungal packaging - Google Patents

Description

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

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

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

When accommodating an object to be preserved, in order to prevent the mold adhering to the object to be preserved from being mixed into the accommodating space, for example, molds such as heat treatment, chemical treatment, and ultraviolet irradiation treatment are killed. It is conceivable to store the processed object to be stored in a package. However, depending on the type of the object to be preserved, such as when the object to be preserved is ingested orally as described above, these treatments may not be possible, and this method cannot be said to be versatile. Therefore, it is more realistic and important to suppress the growth of mold in the storage space of the package during storage to the extent that no problem occurs. For that purpose, for example, the package must be provided with antifungal properties. It is conceivable to give it.

Japanese Unexamined Patent Publication No. 9-252718

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

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

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

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

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

[2]. The antifungal agent according to [1], wherein m is 1.
[3]. The fungicide according to [1] or [2], wherein n is 0 or 1.
[4]. An antifungal resin film containing the antifungal agent according to any one of [1] to [3] and a resin.
[5]. As the resin, one or two selected from the group consisting of urethane-based adhesives, acrylic-based adhesives, titanate-based adhesives, imine-based adhesives, butadiene-based adhesives, polyester-based adhesives, and olefin-based adhesives. The antifungal resin film according to [4], which includes the above and has adhesiveness to the antifungal resin film.
[6]. The antifungal resin film according to [4] or [5], the first resin layer, and the second resin layer are provided, and the antifungal resin film includes the first resin layer and the second resin layer. An antifungal laminated film arranged between the first resin layer and the first resin layer having an oxygen gas permeation amount of 3000 cm ³ / m ² · atm · day or more in an atmosphere of 25 ° C. and 65% RH.
[7]. The antifungal laminated film according to [6], wherein the first resin layer contains low-density polyethylene.
[8]. The antifungal laminated film according to [6] or [7], wherein the oxygen gas permeation amount of the second resin layer in an atmosphere of 25 ° C. and 65% RH is 3000 cm ³ / m ^{2 · atm · day or less.}
[9]. The antifungal laminated film according to any one of [6] to [8], wherein the second resin layer contains one or more selected from the group consisting of polyester, nylon and polypropylene.
[10]. An antifungal package obtained by using the antifungal laminated film according to any one of [6] to [9], and a part of the first resin layers is adhered to each other to form the antifungal package. An antifungal package having an accommodating space and the antifungal resin film being arranged closer to the accommodating space than the second resin layer.

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

It is sectional drawing which shows typically one Embodiment of the antifungal laminated film of this invention. It is sectional drawing which shows typically one Embodiment of the antifungal package of this invention. It is a graph which shows the transition of the mold occurrence rate (%) in Test Example 1. It is a graph which shows the transition of the mold occurrence rate (%) in Test Example 2. It is a graph which shows the transition of the mold occurrence rate (%) in Test Example 3. It is a graph which shows the transition of the mold occurrence rate (%) in Test Example 4. It is a graph which shows the transition of the mold occurrence rate (%) in Test Example 5. It is a graph which shows the transition of the mold occurrence rate (%) in Test Example 6. It is a graph which shows the transition of the mold occurrence rate (%) in Test Example 7.

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

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

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

<Compound (1)>
The compound represented by the general formula (1) (sometimes referred to as “compound (1)” in the present specification) has antifungal properties.
In the general formula (1), X is a linear or branched alkylene group having 1 to 3 carbon atoms, as such alkylene groups, and more specifically, a methylene group (-CH 2 _-), Examples thereof include an ethylene group (-CH ₂ CH _2- ), a propylene group (-CH (CH ₃ ) CH _2- , a methyl ethylene group), and a trimethylene group (-CH ₂ CH ₂ CH _2- ).

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

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

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

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

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

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

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

（式中、Ｘ及びＲは上記と同じであり、ｎ１は０〜５の整数である。）

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

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

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

（式中、Ｘ及びＲは上記と同じであり、ｎ２は０〜４の整数である。）

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

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

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

（式中、Ｘ及びＲは上記と同じであり、ｎ３は０〜３の整数である。）

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

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

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

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

（式中、Ｘ及びＲは上記と同じであり、ｍ０は１〜３の整数である。）

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

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

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

（式中、Ｘ及びＲは上記と同じであり、ｍ１は１〜３の整数である。）

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

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

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

（式中、Ｘ及びＲは上記と同じであり、ｍ２は１〜３の整数である。）

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

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

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

（式中、Ｘ及びＲは上記と同じであり、ｍ３は１〜３の整数である。）

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

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

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

（式中、Ｘ及びＲは上記と同じであり、ｍ４は１又は２である。）

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

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

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

（式中、Ｘ及びＲは上記と同じである。）

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

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

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

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

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

（式中、Ｘ及びＲは上記と同じである。）

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

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

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

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

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

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

In the fungicide 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 an object.
For example, the fungicide of the present invention may contain only one or two or more compounds (1) as an active ingredient, or may contain only one or two or more salts of compound (1). It may contain one or more salts of compound (1) and compound (1), respectively.

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

The compound (1) and a salt thereof are preferably volatile. The volatile compound (1) and its salt are advantageous in the continuous action in the storage space of the package described later by changing from a liquid to a gas at room temperature, and are excellent in the package. The antifungal effect can be maintained for a longer period of time.

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

The compound (1) and a salt thereof are preferably odorless or have a weak odor. Such a compound (1) and a salt thereof, even if they adhere to the object to be preserved, are functionally preferable because they hardly or hardly remind the existence of the object to be preserved when used.
The odorous compound (1) and a salt thereof are preferably those that can be used as a fragrance. Examples of such a compound (1) and a salt thereof include those classified as natural flavors of food additives.

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

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

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

（式中、Ｘ、Ｒ、ｍ及びｎは、上記と同じであり；Ｌｇは離脱基である。）

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<< Antifungal resin film >>
The antifungal resin film of the present invention contains the above-mentioned antifungal agent of the present invention and a resin.
The antifungal resin film of the present invention has excellent antifungal properties because it contains the antifungal agent.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As described above, the antifungal agent of the present invention is suitable for use as an antifungal resin film, but since it has an excellent antifungal effect, it is also suitable for use in applications other than the antifungal resin film. .. For example, the antifungal agent of the present invention can also be used as a solid (for example, granular, block-like, etc.) antifungal agent other than a film, an antifungal ink composition, an antifungal spray agent, and the like. When the antifungal agent of the present invention is used for applications other than such an antifungal resin film, in addition to the compound (1) or a salt thereof, a component necessary for obtaining the desired product into a desired property is used in combination. A composition may be prepared, and the desired product may be produced using this composition.

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

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

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

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

The oxygen gas permeation amount of the first resin layer 11 in an atmosphere of 25 ° C. and 65% RH (relative humidity) is 3000 cm ³ / m ² · atm · day or more, and ^{3000 to 10000 cm 3} / m ² · atm ·. is preferably day, more preferably ^{3000~8000cm 3 / m 2 · atm ·} day, and particularly preferably ^{3000~6000cm 3 / m 2 · atm ·} day. When the oxygen gas permeation amount of the first resin layer 11 is equal to or higher than the lower limit value, the compound (1) or a salt thereof that has migrated from the inside of the antifungal resin film 12 to the first resin layer 11 side is the first resin. It easily migrates to the outside (outside of the first resin layer 11 side of the antifungal laminated film 1) via the layer 11. As a result, the antifungal laminated film 1 exhibits an excellent antifungal effect.

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

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

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

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

The thickness of the first resin layer 11 is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 150 μm, and particularly preferably 15 to 100 μm. When the thickness of the first resin layer 11 is at least the lower limit value, the strength of the first resin layer 11 is further improved, and the excessive transfer of the fungicide to the storage object is further suppressed. Further, when the thickness of the first resin layer 11 is not more than the upper limit value, the antifungal effect of the antifungal laminated film 1 is further improved.
When the first resin layer 11 is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the above-mentioned preferable thickness of the first resin layer 11.

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

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

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

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

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

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

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

The second resin layer 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 by mass. % Or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, for example, 99% by mass or more, or 100% by mass. Good.

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

The thickness of the second resin layer 13 is not particularly limited, but is preferably 2 to 100 μm, more preferably 5 to 70 μm, and particularly preferably 8 to 40 μm. When the thickness of the second resin layer 13 is equal to or greater than the lower limit, the strength of the second resin layer 13 is further improved, and the same effect as when the oxygen gas permeation amount of the second resin layer 13 is reduced is the same. Is obtained more prominently. Further, when the thickness of the second resin layer 13 is not more than the upper limit value, it is possible to avoid an excessive thickness.
When the second resin layer 13 is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the above-mentioned preferable thickness of the second resin layer 13.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Manufacturing of antifungal laminated film>
[Example 1]
An antifungal laminated film having the configuration shown in FIG. 1 was produced by the procedure shown below.
(Manufacturing of antifungal resin film)
Main agent (Mitsui Chemicals Co., Ltd. "Takelac (registered trademark) A620", solid content 50% by mass, ethyl acetate 50% by mass) (6 parts by mass), curing agent (Mitsui Chemicals Co., Ltd. "Takenate (registered trademark) A10" , 75% by mass of solid content, 25% by mass of ethyl acetate) (1 part by mass), and ethyl acetate (6 parts by mass) were mixed to prepare a polyurethane adhesive. In the obtained polyurethane adhesive, the total content of the solvent (ethyl acetate) is 71.2% by mass.
Next, 2-phenoxyethanol (2 parts by mass) was mixed with the total amount of the polyurethane-based adhesive obtained above, and the ratio of the content of 2-phenoxyethanol to the total content of the components other than the solvent was 35% by mass. A resin composition was obtained.
Next, the resin composition obtained above was coated on one surface of the PET film (thickness 12 μm) using a multicoater and dried at 80 ° C. to obtain a content of 2-phenoxyethanol of 35. An antifungal resin film (thickness 3.1 μm) of mass% was formed on the PET film. When the resin composition was applied, the depth of the gravure roll was set to 80 μm.

(Manufacturing of antifungal laminated film)
Further, by laminating the LDPE film (thickness 30 μm) on the surface of the antifungal resin film obtained above on the side opposite to the side on which the PET film is provided, the PET film, the antifungal resin film and the LDPE A transparent antifungal laminated film was obtained in which the films were laminated in this order.

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

[Example 2]
When the resin composition is applied, the depth of the gravure roll is 70 μm instead of 80 μm to form an antifungal resin film having a thickness of 2.5 μm instead of 3.1 μm, as shown in Table 1. A transparent antifungal laminated film was obtained in the same manner as in Example 1 except for the above points.

[Example 3]
When the resin composition is applied, the depth of the gravure roll is set to 60 μm instead of 80 μm to form an antifungal resin film having a thickness of 2.1 μm instead of 3.1 μm, as shown in Table 1. A transparent antifungal laminated film was obtained in the same manner as in Example 1 except for the above points.

[Example 4]
As shown in Table 1, the amount of 2-phenoxyethanol used at the time of preparing the resin composition was increased by 0.5 times, and the depth of the gravure roll was changed to 60 μm instead of 80 μm at the time of coating the resin composition, as shown in Table 1. , 2-Phenoxyethanol content is 35% by mass, instead of the antifungal resin film (thickness 3.1 μm), 2-Phenoxyethanol content is 21% by mass, antifungal resin film (thickness 2.1 μm) ) Was formed, and a transparent antifungal laminated film was obtained in the same manner as in Example 1.

[Comparative Example 1]
By preparing the resin composition without using 2-phenoxyethanol and setting the depth of the gravure roll to 60 μm instead of 80 μm at the time of coating the resin composition, as shown in Table 1, 2-phenoxyethanol Instead of the antifungal resin film (thickness 3.1 μm) having a content of 35% by mass, an antifungal resin film (thickness 2.1 μm) having a content of 2-phenoxyethanol of 0 mass% was formed. A transparent laminated film was obtained in the same manner as in Example 1 except for the above.

<Evaluation of antifungal laminated film>
[Test Example 1]
(Confirmation of antifungal effect on rice cake)
Antifungal agent of Example 2 48 hours after coating of the resin composition and after the aging of the antifungal resin film is completed (hereinafter, this state is referred to as "immediately after production" in the present specification). Two laminated films having a size of 10 cm × 10 cm were prepared. Then, immediately in the atmosphere, the peripheral portions of the antifungal laminated films were laminated and heat-laminated with one 30 g of rice cake sandwiched between the antifungal laminated films. As described above, the above-mentioned one rice cake was contained in a transparent bag (packaging body) made of the above-mentioned antifungal laminated film, and a sealed sample was prepared. A total of 24 such samples were prepared.
Similarly, using the antifungal laminated films of Examples 3 to 4 and the laminated film of Comparative Example 1, 24 samples were prepared for each of these Examples or Comparative Examples.

Next, the sample obtained above was stored at 25 ° C. for 26 days, and during this period, the sealed rice cake was visually observed through the bag to confirm the number of samples in which mold was generated on the rice cake. .. Then, the ratio of the number of samples in which mold is generated on the rice cake to the total number of samples (24) (that is, [the number of samples in which mold is generated on the rice cake] / 24 × 100) is set to “mold generation rate (%)). It was calculated as. A graph showing the transition of the mold occurrence rate (%) at this time is shown in FIG.

As is clear from FIG. 3, when the laminated film of Comparative Example 1 was used, the mold occurrence rate increased with the lapse of storage days and reached about 54%.
On the other hand, when the antifungal laminated films of Examples 2 to 4 were used, the increase in the mold occurrence rate was suppressed, and the mold occurrence rate was only about 17% at the maximum. On the other hand, a significant difference was shown. In particular, when the antifungal laminated film of Example 2 was used, no mold was observed until the end (the mold occurrence rate was 0%). From the results of Examples 2 and 3, it was confirmed that when the content of the compound (1) of the antifungal resin film is the same, the thicker the antifungal resin film, the higher the antifungal effect. It was. Further, from the results of Examples 3 to 4, when the thickness of the antifungal resin film is the same, the higher the content of the compound (1) of the antifungal resin film, the higher the antifungal effect tends to be. confirmed.
Comparing at the stage where the increase in the mold incidence rate was almost or completely stopped and the storage period was 26 days, the mold incidence rate was higher than that in the case where the antifungal laminated film of the present invention was used. It was possible to suppress about 54% at the maximum.

Examples of molds that are likely to occur in rice cakes include Penicillium (a mold belonging to the genus Penicillium), Aspergillus niger (Aspergillus niger), and Kurokawa mold (a mold belonging to the genus Cladosporium). The mold confirmed in this test example was also one of these.

[Test Example 2]
(Confirmation of antifungal effect on ginger)
As the antifungal laminated film of Example 1 immediately after production, two films having a size of 15 cm × 15 cm were prepared. Then, immediately in the atmosphere, with one 100 g of ginger sandwiched between these antifungal laminated films, the peripheral portions of these antifungal laminated films were laminated and heat-laminated. As described above, the above-mentioned one ginger was contained in a transparent bag (packaging body) made of the above-mentioned antifungal laminated film, and a sealed sample was prepared. A total of 26 such samples were prepared.
Similarly, using the antifungal laminated films of Examples 2 to 4 and the laminated film of Comparative Example 1, 26 samples were prepared for each of these Examples or Comparative Examples.

Next, the sample obtained above was stored at 30 ° C. for 12 days, and during this period, the sealed ginger was visually observed through the bag to confirm the number of samples in which the ginger had mold. .. Then, the ratio of the number of samples with mold on ginger to the total number of samples (26) (that is, [the number of samples with mold on ginger] / 26 × 100) is set to “mold occurrence rate (%)). It was calculated as. A graph showing the transition of the mold occurrence rate (%) at this time is shown in FIG.

As is clear from FIG. 4, when the laminated film of Comparative Example 1 was used, the mold occurrence rate increased with the lapse of storage days and reached about 93%.
On the other hand, when the antifungal laminated films of Examples 1 to 4 were used, the increase in the mold occurrence rate was suppressed, and the mold occurrence rate was only about 59% at the maximum. On the other hand, a significant difference was shown. In particular, when the antifungal laminated films of Examples 1 and 2 were used, the mold occurrence rate was only about 36%, and the antifungal effect was the highest. From the results of Examples 1 to 3, it was confirmed that when the content of the compound (1) of the antifungal resin film is the same, the thicker the antifungal resin film, the higher the antifungal effect. It was. Further, from the results of Examples 3 to 4, when the thickness of the antifungal resin film is the same, the higher the content of the compound (1) of the antifungal resin film, the higher the antifungal effect tends to be. confirmed.
Comparing at the stage where the increase in the mold incidence rate was almost or completely stopped and the storage period was 12 days, the mold incidence rate was higher than that in the case where the antifungal laminated film of the present invention was used. It was possible to suppress about 57% at the maximum.

Examples of molds that are likely to occur in ginger include white molds (white molds of the genus Penicillium). The mold confirmed in this test example was also mildew.

[Test Example 3]
(Confirmation of antifungal effect on bread)
As the antifungal laminated film of Example 1 immediately after production, two films having a size of 20 cm × 20 cm were prepared. Then, immediately in the atmosphere, the peripheral portions of the antifungal laminated films were laminated and heat-laminated with one 65 g of bread sandwiched between the antifungal laminated films. As described above, the above-mentioned one piece of bread was housed inside the transparent bag (packaging body) made of the above-mentioned antifungal laminated film, and a sealed sample was prepared. A total of 24 such samples were prepared.
Similarly, using the antifungal laminated films of Examples 2 to 4 and the laminated film of Comparative Example 1, 24 samples were prepared for each of these Examples or Comparative Examples.

Next, the sample obtained above was stored at 25 ° C. for 28 days, and during this period, the sealed bread was visually observed through the bag to confirm the number of samples in which the bread had mold. .. Then, the ratio of the number of samples with mold on the bread to the total number of samples (24) (that is, [the number of samples with mold on the bread] / 24 × 100) is set to “mold occurrence rate (%)). It was calculated as. A graph showing the transition of the mold occurrence rate (%) at this time is shown in FIG.

As is clear from FIG. 5, when the laminated film of Comparative Example 1 was used, the mold occurrence rate increased with the lapse of storage days and reached about 87%.
On the other hand, the mold occurrence rate when the antifungal laminated film of Example 4 was used showed the same tendency as that of Comparative Example 1. Further, the mold occurrence rate when the antifungal laminated film of Example 3 was used was about 83%, which was lower than that when the laminated film of Comparative Example 1 was used. The mold occurrence rate when the antifungal laminated films of Examples 1 and 2 were used was only about 59% at the maximum, showing a significant difference from Comparative Example 1. From the results of Examples 1 to 3, it was confirmed that when the content of the compound (1) of the antifungal resin film is the same, the thicker the antifungal resin film, the higher the antifungal effect. It was. Further, from the results of Examples 3 to 4, when the thickness of the antifungal resin film is the same, the higher the content of the compound (1) of the antifungal resin film, the higher the antifungal effect tends to be. confirmed.
Comparing at the stage where the increase in the mold incidence rate was almost or completely stopped and the storage period was 28 days, the mold incidence rate was higher than that in the case where the antifungal laminated film of the present invention was used. It was possible to suppress by about 28% at the maximum.

Examples of molds that are likely to occur in bread include Penicillium (a mold belonging to the genus Penicillium), Aspergillus niger (Aspergillus niger), and Kurokawa mold (a mold belonging to the genus Cladosporium). The mold confirmed in this test example was also one of these.

[Test Example 4]
(Confirmation of antifungal effect on rice cake when using antifungal laminated film after storage (1))
In the atmosphere, the antifungal laminated film of Example 2 immediately after production was placed in an aluminum bag, and the bag was heat-sealed to seal it. In this sealed state, the antifungal laminated film was stored at 25 ° C. for 21 days.
Next, the antifungal laminated film after storage was taken out from the aluminum bag, and two films having a size of 10 cm × 10 cm were cut out.
Next, using these two sheets of the antifungal laminated film after storage, one rice cake was formed inside a transparent bag (packaging body) made from the antifungal laminated film by the same method as in Test Example 1. Contained and sealed samples were made. A total of 20 such samples were prepared.

Separately, a total of 20 samples were prepared in the same manner as when the above-mentioned post-storage antifungal laminated film was used, except that the antifungal laminated film of Example 2 was used without being stored as described above. Made. That is, here, the antifungal laminated film of Example 2 immediately after production is cut out to the above size to prepare a transparent bag (packaging body), and one rice cake is housed in the bag and sealed. , As a sample.
After that, the mold incidence rate was calculated by the same method as in Test Example 1 except that the storage period of the sample was changed to 19 days instead of 26 days. FIG. 6 shows a graph showing the transition of the mold occurrence rate (%) at this time. In FIG. 6, the result when the antifungal laminated film of Example 2 after storage was used is described as "Example 2 (S1)", and the antifungal laminated film of Example 2 which was not stored was used. The results of the cases are described as "Example 2 (NS1)" and shown respectively.

As is clear from FIG. 6, when the antifungal laminated film of Example 2 which was not stored before the production of the bag (packaging) was used, the increase in the mold occurrence rate was remarkably suppressed. The mold incidence rate was only about 4%.
On the other hand, when the antifungal laminated film of Example 2 which was stored before the preparation of the bag (packaging) was used, the mold occurrence rate increased with the lapse of the storage days of the sample. , Only about 36%.
As described above, it was confirmed that the antifungal effect can be obtained even when the antifungal laminated film after storage is used.

[Test Example 5]
(Confirmation of antifungal effect on rice cake when using antifungal laminated film after storage (2))
In the atmosphere, the antifungal laminated film of Example 2 immediately after production was placed in an aluminum bag, and the bag was heat-sealed to seal it. In this sealed state, the antifungal laminated film was stored at 25 ° C. for 42 days. Next, the antifungal laminated film after storage was taken out from the aluminum bag, and thereafter, in the same method as in the case of Test Example 4, 1 was placed inside the transparent bag (package) made from the antifungal laminated film. A total of 20 sealed samples were prepared in which the molds were housed.
After that, the mold incidence rate was calculated by the same method as in Test Example 1 except that the storage period of the sample was 15 days instead of 26 days. A graph showing the transition of the mold occurrence rate (%) at this time is shown in FIG. In FIG. 7, the result when the antifungal laminated film after storage is used is described as "Example 2 (S2-AL)".

In the atmosphere, the antifungal laminated film of Example 4 immediately after production was placed in an aluminum bag, and the bag was heat-sealed to seal it. In this sealed state, the antifungal laminated film was stored at 25 ° C. for 42 days. Next, the antifungal laminated film after storage was taken out from the aluminum bag, and thereafter, in the same method as in the case of Test Example 4, 1 was placed inside the transparent bag (package) made from the antifungal laminated film. A total of 20 sealed samples were prepared in which the molds were housed.
After that, the mold incidence rate was calculated by the same method as in Test Example 1 except that the storage period of the sample was 15 days instead of 26 days. A graph showing the transition of the mold occurrence rate (%) at this time is shown in FIG. In FIG. 7, the result when the antifungal laminated film after storage is used is described as "Example 4 (S2-AL)".

In the atmosphere, the antifungal laminated film of Example 4 immediately after production was placed in a polyethylene bag, and the bag was heat-sealed to seal the bag. In this sealed state, the antifungal laminated film was stored at 25 ° C. for 42 days. Next, the antifungal laminated film after storage was taken out from the polyethylene bag, and thereafter, in the same method as in Test Example 4, 1 was placed inside the transparent bag (package) made from the antifungal laminated film. A total of 20 sealed samples were prepared in which the molds were housed.
After that, the mold incidence rate was calculated by the same method as in Test Example 1 except that the storage period of the sample was 15 days instead of 26 days. A graph showing the transition of the mold occurrence rate (%) at this time is shown in FIG. In FIG. 7, the result when the antifungal laminated film after storage is used is described as "Example 4 (S2-PE)".

In the air, the laminated film of Comparative Example 1 immediately after production was stored as it was at 25 ° C. for 42 days. Next, using the laminated film after storage, one rice cake is housed and sealed inside a transparent bag (packaging body) made from the laminated film by the same method as in the case of Test Example 4. A total of 20 samples were prepared.
After that, the mold incidence rate was calculated by the same method as in Test Example 1 except that the storage period of the sample was 15 days instead of 26 days. A graph showing the transition of the mold occurrence rate (%) at this time is shown in FIG. In FIG. 7, the result when the laminated film after storage is used is described as "Comparative Example 1 (S2)".

As is clear from FIG. 7, when the laminated film of Comparative Example 1 stored before the preparation of the bag (packaging body) was used, the mold occurrence rate increased with the lapse of the storage days of the sample, and the mold occurrence rate increased to about. It reached 90%.
On the other hand, when the antifungal laminated film of Example 4 which was stored in a polyethylene bag before the preparation of the bag (packaging body) was used, the laminated film of Comparative Example 1 after the above storage was used. The incidence of mold was lower than it was, but reached about 70%.
On the other hand, when the antifungal laminated film of Example 4 stored in an aluminum bag was used before the bag (packaging body) was manufactured, mold was generated as compared with the above case stored in a polyethylene bag. The rate was low, only about 51%.
Further, when the antifungal laminated film of Example 2 stored in an aluminum bag was used before the bag (packaging body) was produced, the mold occurrence rate was the lowest and remained at about 31%.
As described above, when the antifungal laminated films of Examples 2 and 4 are used after storage in an aluminum bag, the mold generation rate is lower, and when the laminated film of Comparative Example 1 after storage is used. On the other hand, a significant difference was shown.
Comparing the samples when the storage period of the sample was 15 days, when the increase in the mold occurrence rate was almost or completely stopped, the antifungal laminated film of the present invention stored in the aluminum bag was used, so that the bag was not used. Compared with the case of using the stored laminated film, the mold occurrence rate could be suppressed by about 59% at the maximum.

<Manufacturing of antifungal laminated film>
[Example 5]
Except for increasing the production scale, making the width of the antifungal laminated film four times that of Example 4, and setting the depth of the gravure roll to 80 μm instead of 60 μm when applying the resin composition. A transparent antifungal laminated film was obtained in the same manner as in Example 4. The thickness of the antifungal resin film having a content of 2-phenoxyethanol of 21% by mass was 3.1 μm.

[Example 6]
By increasing the amount of 2-phenoxyethanol used at the time of preparing the resin composition by 1.5 times, as shown in Table 2, the antifungal resin film having a 2-phenoxyethanol content of 21% by mass (thickness 3. A transparent antifungal laminated film by the same method as in Example 5 except that an antifungal resin film (thickness 3.1 μm) having a 2-phenoxyethanol content of 28% by mass was formed instead of 1 μm). Got

[Example 7]
When the resin composition is applied, the depth of the gravure roll is set to 110 μm instead of 80 μm to form an antifungal resin film having a thickness of 5.8 μm instead of 3.1 μm, as shown in Table 2. A transparent antifungal laminated film was obtained in the same manner as in Example 5 except for the above points.

[Example 8]
As shown in Table 2, the amount of 2-phenoxyethanol used at the time of preparing the resin composition was increased by 1.5 times, and the depth of the gravure roll was changed to 110 μm instead of 80 μm at the time of coating the resin composition, as shown in Table 2. , 2-A transparent antifungal laminated film was obtained in the same manner as in Example 5 except that an antifungal resin film (thickness 5.8 μm) having a content of 28% by mass of phenoxyethanol was formed.

[Example 9]
As shown in Table 2, the amount of 2-phenoxyethanol used at the time of preparing the resin composition was increased by 2.0 times, and the depth of the gravure roll was changed to 110 μm instead of 80 μm at the time of coating the resin composition, as shown in Table 2. , 2-A transparent antifungal laminated film was obtained in the same manner as in Example 5 except that an antifungal resin film (thickness 5.8 μm) having a content of 35% by mass of phenoxyethanol was formed.

[Example 10]
As shown in Table 2, the amount of 2-phenoxyethanol used at the time of preparing the resin composition was increased by 1.5 times, and the depth of the gravure roll was changed to 160 μm instead of 80 μm at the time of coating the resin composition, as shown in Table 2. , 2-A transparent antifungal laminated film was obtained by the same method as in Example 5 except that an antifungal resin film (thickness 8.6 μm) having a content of 28% by mass of phenoxyethanol was formed.

[Comparative Example 2]
A resin composition was prepared without using 2-phenoxyethanol, and this was used to make a mold-proof resin film (thickness 3.1 μm) having a 2-phenoxyethanol content of 21% by mass, as shown in Table 2. Instead, a transparent laminated film was obtained by the same method as in Example 5 except that an antifungal resin film (thickness 3.1 μm) having a 2-phenoxyethanol content of 0% by mass was formed.

<Evaluation of antifungal laminated film>
[Test Example 6]
(Confirmation of antifungal effect on rice cake)
As the antifungal laminated film immediately after production, the ones of Example 7 and Comparative Example 2 were used instead of those of Example 2, and the transparent film produced from these antifungal laminated films was produced by the same method as in the case of Test Example 1. One rice cake was contained in the bag (packaging body), and a total of 18 sealed samples were prepared.
Then, in the same manner as in Test Example 1, these samples were allowed to stand at 25 ° C. for 18 days, and during this period, the sealed rice cake was visually observed through the bag, and the sample in which mold was generated on the rice cake was observed. I checked the number. Then, the ratio of the number of samples in which mold is generated on the rice cake to the total number of samples (18) (that is, [the number of samples in which mold is generated on the rice cake] / 18 × 100) is set to “mold generation rate (%)). It was calculated as. FIG. 8 shows a graph showing the transition of the mold occurrence rate (%) at this time.

As is clear from FIG. 8, when the laminated film of Comparative Example 2 was used, the mold occurrence rate increased with the lapse of storage days and reached about 84%.
On the other hand, when the antifungal laminated film of Example 7 was used, the increase in the mold occurrence rate was suppressed, and the mold occurrence rate was only about 34%, which was a significant difference from Comparative Example 2. showed that.
Comparing at the stage where the increase in the mold incidence rate was almost or completely stopped and the storage period was 18 days, the mold incidence rate was determined by using the antifungal laminated film of the present invention as compared with the case where it was not used. It was possible to suppress about 50%.

[Test Example 7]
(Confirmation of antifungal effect on ginger)
As the antifungal laminated film immediately after production, instead of the one of Example 1, those of Example 5, Example 7 and Comparative Example 2 were used, and from these antifungal laminated films in the same manner as in the case of Test Example 2. One ginger was contained in the prepared transparent bag (packaging body), and a total of 20 sealed samples were prepared.
Then, in the same manner as in Test Example 2, these samples were stored at 30 ° C. for 6 days, and during this period, the sealed ginger was visually observed through the bag, and the ginger was moldy. I checked the number. Then, the ratio of the number of samples with mold on ginger to the total number of samples (20) (that is, [the number of samples with mold on ginger] / 18 × 100) is set to “mold occurrence rate (%)). It was calculated as. FIG. 9 shows a graph showing the transition of the mold occurrence rate (%) at this time.

As is clear from FIG. 9, when the laminated film of Comparative Example 2 was used, the mold occurrence rate increased with the lapse of storage days and reached about 25%.
On the other hand, when the antifungal laminated films of Examples 5 and 7 were used, the increase in the mold occurrence rate was suppressed, and the mold occurrence rates were only about 10% and about 4%, respectively. A significant difference was shown compared to Example 2. From the results of Examples 5 and 7, it was confirmed that when the content of the compound (1) of the antifungal resin film is the same, the thicker the antifungal resin film, the higher the antifungal effect. It was.
Comparing the storage days at the stage of 6 days, by using the antifungal laminated film of the present invention, the mold occurrence rate could be suppressed by about 21% at the maximum as compared with the case where it was not used.

[Test Example 8]
(Measurement of odor value)
Using the antifungal laminated film obtained in Examples 5 to 10 and the laminated film obtained in Comparative Example 2, a bag (packaging body) was prepared in the same manner as in Test Example 6, and then these bags were immediately prepared. Was stored at 25 ° C. for 24 hours in the air.
The odor values of these bags after storage were measured using an odor measuring device (“portable odor sensor mini” manufactured by Shin-Cosmos Electric Co., Ltd.). The results are shown in Table 3.

As shown in Table 3, in the antifungal laminated films of Examples 5 to 10, the odor value was 300 or more and 490 or less. In particular, in Examples 5 to 7, the odor value was within the range of 300 to 400.
When the content of the compound (1) of the antifungal resin film is the same (in the case of Example 5 and Example 7, in the case of Example 6, Example 8 and Example 10), the antifungal resin film It was confirmed that the thinner the thickness, the smaller the odor value. When the thickness of the antifungal resin film is the same (in the case of Example 5 and Example 6, in the case of Example 7, Example 8 and Example 9), the compound of the antifungal resin film (1). It was confirmed that the lower the content of), the smaller the odor value.

The antifungal laminated films obtained in Examples 6 and 8 to 10 are different from the antifungal laminated films obtained in Examples 5 and 7, and are considered to be 2-phenoxyethanol from the cut portion at the time of cutting. Exudation of liquid matter was observed. The amount of the antifungal laminated film of Examples 9 to 10 was larger than that of the antifungal laminated film of Examples 6 and 8. As described above, the antifungal laminated films obtained in Examples 5 and 7 were most excellent in production suitability.

The present invention can be used for packaging used for storage of foods and the like.

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

Claims (7)

A mold-proof resin film, a first resin layer, and a second resin layer are provided.
The antifungal resin film contains an antifungal agent containing a compound represented by the following general formula (1) or a salt thereof as an active ingredient, and a resin.
The antifungal resin film is arranged between the first resin layer and the second resin layer.
The 25 ° C. of the first resin layer, the oxygen gas permeation amount in an atmosphere of RH 65% ^{is, 3000cm 3 / m 2 · atm} · day or more ^{6000cm 3 / m 2 · atm ·} day or less,
25 ° C. of the second resin layer, the oxygen gas permeation amount in an atmosphere of RH 65% is, I ^{50cm 3 / m 2 · atm ·} day or more ^{2500cm 3 / m 2 · atm ·} day or less der,
The first resin layer is made of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), or metallocene-catalyzed linear low-density polyethylene (metallocene LLDPE) as a constituent material.
The second resin layer is made of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), nylon, polypropylene (PP). Anti-mold laminated film used as a constituent material.

(In the formula, X is a linear or branched alkylene group having 1 to 3 carbon atoms; R is a linear or branched alkyl group having 1 to 3 carbon atoms; m is 1 to 1. If it is an integer of 3 and m is 2 or more, the plurality of Xs may be the same or different from each other; n is an integer of 0 to 5, where m + n is 6 or less and n is 2 or more. If, the plurality of Rs may be the same or different from each other.) The antifungal laminated film according to claim 1, wherein m is 1. The antifungal laminated film according to claim 1 or 2, wherein n is 0 or 1. As the resin, one or two selected from the group consisting of urethane-based adhesives, acrylic-based adhesives, titanate-based adhesives, imine-based adhesives, butadiene-based adhesives, polyester-based adhesives, and olefin-based adhesives. The antifungal laminated film according to any one of claims 1 to 3, wherein the antifungal resin film has adhesiveness including the above. The antifungal laminated film according to any one of claims 1 to 4, wherein the first resin layer contains low-density polyethylene. The antifungal laminated film according to any one of claims 1 to 5, wherein the second resin layer contains one or more selected from the group consisting of polyester, nylon and polypropylene. An antifungal package obtained by using the antifungal laminated film according to any one of claims 1 to 6.
It has a storage space in which a part of the first resin layers is adhered to each other and is formed.
An antifungal packaging body in which the antifungal resin film is arranged on the accommodation space side of the second resin layer.

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