JP2016183229A - Acetic acid adsorptive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acetic acid adsorptive film that can adsorb acetic acid with a high adsorption capacity for the long term and can be molded easily.SOLUTION: An acetic acid adsorptive film comprises a binder comprising a resin selected from the group consisting of an ethylene-acetic acid vinyl copolymer, an ethylene-(meth)acrylic monomer copolymer, an ethylene-α-olefin copolymer, and a mixture of them, an acetic acid adsorbent dispersed in the binder, and a nonionic fatty acid ester surfactant.SELECTED DRAWING: None

Description

  The present invention relates to an acetic acid adsorption film. The present invention also relates to a packaging bag including the film and a medical device bag using the packaging bag. In particular, the present invention relates to an acetic acid adsorption film suitable for use in a place where acetic acid gas is generated, such as in the medical field.

  Conventionally, peracetic acid has been used as a disinfectant for medical instruments (for example, Patent Document 1). In this case, since peracetic acid is easily decomposed, the peracetic acid is accommodated in a container having a gas venting structure. Therefore, since acetic acid gas generated by decomposition leaks out of the container through the gas venting structure, acetic acid odor becomes a problem until it is used after production.

  For this reason, at present, a bottle container containing peracetic acid and a pack containing an acetic acid adsorbent are stored together in a bag with a chuck. Since acetic acid gas is continuously generated from the bottle container, the acetic acid adsorbent has been required to have an ability to adsorb acetic acid gas for a long period of time. Furthermore, in such a usage mode, there is a possibility that the pack containing the acetic acid adsorbent becomes a foreign substance in the medical field.

  It has also been found that there is a problem that acetic acid gas is generated in a trace amount from a wooden stand on which art works to be exhibited in the museum are corroded, and corrodes the art works.

  Similar problems exist in recording materials using acetate films, and Patent Documents 2 and 3 disclose molded products for removing acetic acid gas generated from these films. Here, a plate-shaped molded product is obtained by kneading a humidity control agent for avoiding deterioration due to moisture absorption of the film and a gas absorbing agent into a thermoplastic resin. In Patent Documents 2 and 3, by adopting such a configuration, the humidity control / gas absorption capability is sustained over a long period of time, and a delayed effect can be imparted.

JP 2002-350742 A Japanese Patent Laid-Open No. 08-217913 JP2013-104030A

  However, in the molded article for acetic acid adsorption described in Patent Documents 2 and 3, the acetic acid adsorption capacity may be insufficient. In addition, the molded article for adsorbing acetic acid described in these documents is not basically in the form of a film, so there are cases where the usage is limited. Accordingly, an object of the present invention is to provide an acetic acid adsorbing film that can adsorb acetic acid and can be easily molded with a long-term and high adsorption capacity.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means. That is, the present invention is as follows:
[1] A binder containing a resin selected from the group consisting of an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic monomer copolymer, an ethylene-α-olefin copolymer, and a mixture thereof, and the binder An acetic acid adsorbing film comprising an acetic acid adsorbing agent dispersed in a nonionic fatty acid ester surfactant.
[2] The film according to [1], wherein the acetic acid adsorbent is an inorganic adsorbent that chemically adsorbs acetic acid.
[3] The film according to [2], wherein the acetic acid adsorbent includes magnesium oxide.
[4] Of 100 parts by mass of the binder, 80 parts by mass or more are from ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic monomer copolymer, ethylene-α-olefin copolymer, and mixtures thereof. The film according to any one of [1] to [3], which is a resin selected from the group consisting of:
[5] Of 100 parts by mass of the binder, 50 parts by mass or more is an ethylene-vinyl acetate copolymer and / or ethylene- (meth) acrylic copolymer, and 10 parts by mass or more is another resin. , [1] to [3].
[6] Of 100 parts by mass of the binder, 50 parts by mass or more is an ethylene- (meth) acrylic monomer copolymer, and 10 parts by mass or more is an ethylene-α-olefin copolymer, low-density polyethylene, high The film according to any one of [1] to [3], which is a density polyethylene or a mixture thereof.
[7] Of 100 parts by mass of the binder, 10 parts by mass or more is an ethylene-α-olefin copolymer, and 50 parts by mass or more is polyethylene having a higher density than the ethylene-α-olefin copolymer. , [1] to [3].
[8] A film laminate in which a skin layer is laminated on the film according to any one of [1] to [7].
[9] The film laminate according to [8], wherein the skin layer is laminated on both sides of the acetic acid adsorption layer.
[10] Binder containing resin selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic monomer copolymer, ethylene-α-olefin copolymer, and mixtures thereof, acetic acid adsorption Kneading the agent and the nonionic aliphatic ester surfactant to produce a masterbatch;
Forming a master batch and forming an acetic acid adsorbing film.
[11] The method for producing an acetic acid adsorbing film according to [10], further comprising forming the acetic acid adsorbing film by forming a film after the master batch is in a pellet form and repelleting the master batch.

  According to the acetic acid adsorbing film of the present invention, acetic acid can be adsorbed over a long period of time and with a high adsorption capacity by improving the dispersibility of the acetic acid adsorbent. Moreover, this film can be easily formed from a resin composition and can be used in various applications. Furthermore, the peracetic acid bottle accommodation bag useful in a medical field can be provided by using the packaging bag containing this film.

FIG. 1 is a schematic view of the layer structure of the acetic acid adsorption film laminate of the present invention. FIG. 2 is a schematic view of a peracetic acid bottle storage bag. FIG. 3 is an optical microscope image showing the surface state of Example 1. FIG. 4 is an optical microscope image showing the surface state of Comparative Example 1. FIG. 5 is an optical microscope image showing the surface state of Comparative Example 2. FIG. 6 is an optical microscope image showing the surface state of Comparative Example 3. FIG. 7 is an optical microscope image showing the surface state of Comparative Example 4. FIG. 8 is an optical microscope image showing the surface state of Comparative Example 5. FIG. 9 is an optical microscope image showing the surface state of Comparative Example 6. FIG. 10 is an optical microscope image showing the surface state of Comparative Example 7. FIG. 11 is an optical microscope image showing the surface state of Example 3. FIG. 12 is an optical microscope image showing the surface state of Example 5.

<Acetic acid adsorption film>
The film of the present invention includes an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic monomer copolymer, an ethylene-α-olefin copolymer, and a binder and binder selected from the group consisting of these And an acetic acid adsorbent dispersed in the resin, as well as a nonionic aliphatic ester surfactant.

  Normally, when the adsorbent is dispersed in the resin, the adsorption performance of the adsorbent is greatly reduced due to the low gas permeability of the resin. However, the present inventors have discovered that the film having the constitution of the present invention can maintain its performance to some extent unexpectedly with respect to the adsorption capacity of acetic acid. The reason for this is not limited by theory, but for the ethylene-vinyl acetate copolymer and the ethylene- (meth) acrylic monomer copolymer, the presence of the carboxylic acid group or the ester moiety is the same as that of acetic acid. It is speculated that this is due to the high permeability of acetic acid to the binder due to the fact that the affinity of these is increased and / or their molecular structure has a relatively bulky steric structure. The Furthermore, with regard to the ethylene-α-olefin copolymer, acetic acid molecules easily enter spatially due to the large space in the polymer matrix resulting from the branching derived from the α-olefin, and the It is presumed to be due to the high permeability.

(binder)
The binder used for the film of the present invention includes one or more resins of ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic monomer copolymer, and ethylene-α-olefin copolymer. As described above, these resins are not only presumed to have high permeability to acetic acid, but are also preferred because they are relatively easy to process into a film.

(Binder: Ethylene-vinyl acetate copolymer)
The ethylene-vinyl acetate copolymer is a resin obtained by copolymerizing a monomer composition containing at least ethylene and vinyl acetate. The vinyl acetate content in the monomer composition is 2% by weight or more, 3% by weight or more, 5% by weight or more, or 10% by weight or more, 50% by weight or less, 40% by weight or less, or 30% by weight. It can be as follows. Generally, when the vinyl acetate content is high, the crystallinity of the resulting resin is low, and when the vinyl acetate content is low, the density of the resulting resin is low. Depending on the final application, an appropriate vinyl acetate content resin can be selected.

  As the thermal characteristics of the preferred ethylene-vinyl acetate copolymer, for example, when the melt mass flow rate is measured in accordance with JIS K6924-1 under the conditions of a temperature of 190 ° C. and a load of 21.18 N, Is 0.1 g / 10 min or more, 0.5 g / 10 min or more, 1.0 g or more, 3.0 g / 10 min or more, or 5.0 g / 10 min or more, 3000 g / 10 min or less, 100 g / 10 min or less, 50 g / 10 min. Or 30 g / 10 min or less.

(Binder: Ethylene- (meth) acrylic monomer copolymer)
The ethylene- (meth) acrylic monomer copolymer is a resin obtained by copolymerizing a monomer composition containing at least ethylene and a (meth) acrylic monomer. The content of the (meth) acrylic monomer in the monomer composition is 2% by weight or more, 3% by weight or more, 5% by weight or more, or 10% by weight or more, 50% by weight or less, 40% by weight or less. Or 30% by weight or less. Generally, when the content of the (meth) acrylic monomer is high, the softening temperature of the obtained resin is low, and when the content of the (meth) acrylic monomer is low, the density of the obtained resin is low. Depending on the final application, an appropriate (meth) acrylic monomer content resin can be selected.

  Here, suitable (meth) acrylic monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate, pentyl (meth) ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

  Specific examples of the ethylene- (meth) acrylic monomer copolymer include an ethylene-acrylic acid copolymer (EAA), an ethylene-methacrylic acid copolymer (EMAA), and an ethylene-ethyl acrylate copolymer (EEA). ), Ethylene-methyl acrylate copolymer (EMA), ethylene-methacrylate copolymer (EMMA), and the like.

  As a thermal characteristic of a preferable ethylene- (meth) acrylic monomer copolymer, for example, its melt mass flow rate was measured according to JIS K7210-1999 under conditions of a temperature of 190 ° C. and a load of 21.18 N. In this case, it is preferably 0.1 g / 10 min or more, 0.5 g / 10 min or more, 1.0 g or more, 3.0 g / 10 min or more, or 5.0 g / 10 min or more, 500 g / 10 min or less, 100 g / 10 min or less. , 50 g / 10 min or less, or 30 g / 10 min or less.

(Binder: Ethylene-α-olefin copolymer)
The ethylene-α-olefin copolymer has a short branched chain derived from the α-olefin, and the repeating unit of the methylene group including the branched chain is 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol. % Or more, 95 mol% or more, or 98 mol% or more of the resin. The ethylene-α-olefin copolymer is preferably an ultra-low density polyethylene having a density of less than 0.910 g / cm ³ .

  In particular, the ethylene-α-olefin copolymer is a linear low-density polyethylene that has substantially no long-chain branches, and the α-olefin is copolymerized at a specific ratio when producing polyethylene by the low-pressure method. To obtain. Therefore, in particular, the ethylene-α-olefin copolymer is a copolymer obtained by polymerizing a monomer composition containing ethylene and at least one α-olefin by a low pressure method using a metallocene catalyst, a Ziegler-Natta catalyst, or the like. It is a polymer. Examples of the α-olefin include α-olefins having 4 to 18, 4 to 10 or 4 to 8 carbon atoms, such as 1-butene, 1-hexene, 4-methylpentene-1, and 1-octene. be able to. Further, this copolymer may be copolymerized with propylene.

  Specific examples of the ethylene-α-olefin copolymer include an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-propylene-1-hexene copolymer. .

The ethylene -α- olefin copolymer, preferably 0.870 g / cm ³ or more, 0.875 g / cm ³ or more, or 0.880 g / cm ³ has a density greater than, 0.905 g / cm ³ or less Having a density of In addition, in this specification, a density means the value measured based on JISK7112-1999.

  As a preferred ethylene-α-olefin copolymer thermal characteristics, for example, when its melt mass flow rate is measured in accordance with JIS K7210-1999 under conditions of a temperature of 190 ° C. and a load of 21.18 N, Preferably they are 0.1g / 10min or more, 0.5g / 10min or more, 1.0g or more, 3.0g / 10min or more, or 5.0g / 10min or more, 100g / 10min or less, 50g / 10min or less, 30g / It is 10 min or less, or 20 g / 10 min or less.

(Binder: Composition)
The binder need not be composed only of the ethylene-vinyl acetate copolymer, the ethylene- (meth) acrylic monomer copolymer, and the ethylene-α-olefin copolymer. Particularly, among 100 parts by mass of the binder, the ethylene-vinyl acetate copolymer, the ethylene- (meth) acrylic monomer copolymer, the ethylene-α-olefin copolymer, or a mixture thereof is 10 parts by mass or more. It is preferably 20 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, or 95 parts by mass or more. Good.

  The present inventors have combined acetic acid adsorption performance and / or film by combining at least two kinds of resins among the above resins, or by combining at least one kind of resins and other resins. It has been found that the processability to can be improved.

  Specifically, the present inventors use the above-mentioned ethylene-vinyl acetate copolymer and / or ethylene- (meth) acrylic monomer copolymer in combination with other resins, thereby using them alone. It was unexpectedly found that the acetic acid adsorption performance of the composition of the present invention can be improved as compared with the case of using it. Although this is not bound by theory, it is considered that acetic acid permeability is increased due to the sea-island structure produced by the polymer blend.

  In this case, among 100 parts by mass of the binder, the ethylene-vinyl acetate copolymer, the ethylene- (meth) acrylic monomer copolymer, or a mixture thereof is 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more. 80 parts by mass or more, 90 parts by mass or more, or 95 parts by mass or more, and the remainder is other resin.

  In addition to the ethylene-vinyl acetate copolymer and the ethylene- (meth) acrylic monomer copolymer, other resins that can be used as a binder are not particularly limited, but the above-mentioned ethylene-α-olefins are particularly limited. A copolymer, a low density polyethylene, a high density polyethylene, etc. can be mentioned. Although not limited to theory, it is believed that a resin capable of at least partially forming a sea-island structure when blended with these resins is preferred.

In this specification, the low density polyethylene includes 80 mol% or more, 90 mol% or more, 95 mol% or more, or 98 mol% or more of repeating units of methylene groups including branched chains, or substantially all repeating units. Is a methylene group and has a density of 0.910 g / cm ³ or more and less than 0.930 g / cm ³ . In particular, this has a long-chain branched structure and can be obtained by radical polymerization of ethylene by a high-pressure method.

  As a preferable low density polyethylene thermal property, for example, the melt mass flow rate is preferably 0.1 g when measured in accordance with JIS K6922-1 under conditions of a temperature of 190 ° C. and a load of 21.18 N. / 10 min or more, 0.5 g / 10 min or more, 1.0 g or more, 3.0 g / 10 min or more, or 5.0 g / 10 min or more, 100 g / 10 min or less, 50 g / 10 min or less, 30 g / 10 min or less, or 20 g / 10 min or less.

In the present specification, high-density polyethylene includes 80 mol% or more, 90 mol% or more, 95 mol% or more, or 98 mol% or more of a repeating unit of a methylene group, including a difference in branching when having a branched chain, or substantially. And a polyethylene having a density of 0.930 g / cm ³ or more, wherein all repeating units are methylene groups. In particular, this has a density of 0.942 g / cm ³ or more, does not substantially have a long-chain branched structure, and can be obtained by radical polymerization of ethylene by a low pressure method.

  As a preferable high-density polyethylene, for example, when the melt mass flow rate is measured in accordance with JIS K6922-2 under the conditions of a temperature of 190 ° C. and a load of 21.18 N, preferably 0.1 g / 10 min or more, 0.5 g / 10 min or more, 1.0 g or more, 3.0 g / 10 min or more, or 5.0 g / 10 min or more, 100 g / 10 min or less, 50 g / 10 min or less, 30 g / 10 min or less, or 20 g / 10 min or less.

  Furthermore, the present inventors, in particular, when an ethylene-α-olefin copolymer is used as a binder, using a combination of resins having a higher density than that, while maintaining a certain degree of acetic acid adsorption performance, It has been found that processability comparable to that of the additionally used resin can be achieved in the film of the present invention.

  In this case, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 80 parts by mass or more, or 90 parts by mass or more among 100 parts by mass of the binder are ethylene-α. -It may be a resin having a higher density than the olefin copolymer.

  Here, examples of the resin having a higher density than the ethylene-α-olefin copolymer include low density polyethylene and high density polyethylene.

(Acetic acid adsorbent)
The acetic acid adsorbent used in the present invention is not particularly limited as long as it can adsorb acetic acid, and may be a chemical adsorbent or a physical adsorbent. The adsorbent used in the present invention may be an inorganic adsorbent, an organic adsorbent, or an organic-inorganic hybrid adsorbent. Preferably, the adsorbent used in the present invention is an inorganic adsorbent that chemically adsorbs acetic acid.

  Specific examples of the inorganic adsorbent used in the present invention include magnesium oxide, calcium oxide, calcium chloride, calcium sulfate, magnesium sulfate, sodium sulfate, aluminum oxide, quicklime, silica gel, and inorganic molecular sieves. Among these, in particular, magnesium oxide can be mentioned, and a substance containing this, for example, hydrotalcite is also useful. Examples of the organic adsorbent include the carboxylates described in Patent Document 3.

  The adsorbent used in the present invention is 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, or 10 parts by mass with respect to 100 parts by mass of the binder resin in consideration of kneadability and adsorption performance. It is preferably contained in an amount of not less than 500 parts by mass, not more than 300 parts by mass, not more than 100 parts by mass, not more than 50 parts by mass, not more than 40 parts by mass, or not more than 30 parts by mass.

(Nonionic fatty acid ester surfactant)
Nonionic fatty acid ester surfactants refer to nonionic ester surfactants derived from fatty acids. By containing this surfactant, the acetic acid adsorbent can be dispersed favorably, thereby improving the acetic acid adsorption amount.

  Examples of the fatty acid include fatty acids having 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more carbon atoms, and 100 or less, 50 or less, 30 or less, 22 or less, 20 or less, or 18 or less carbon atoms. preferable. Examples of such fatty acids include saturated fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and arachidic acid, and monounsaturated fatty acids such as oleic acid, ricinoleic acid, and erucic acid. And polyunsaturated fatty acids such as arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, linoleic acid, and α-linolenic acid. These fatty acids may be used alone, or a mixture of fatty acids may be used.

  Examples of the fatty acid mixture include vegetable oils such as rapeseed oil, olive oil, soybean fat, safflower oil, sesame oil, palm oil, sunflower oil, coconut oil, cacao butter and castor oil, and animal oils such as pork fat and beef fat. . Preferably, vegetable oils and fats, especially palm oil and palm oil are preferred.

  The content of the saturated fatty acid in the fatty acid is preferably 35% by mass or more, 40% by mass or more, or 42% by mass or more, and is preferably 95% or less, 90% or less, or 88% or less.

<Film laminate>
In the film laminate, a skin layer is laminated on an acetic acid adsorption film.

  As shown in FIG. 1 (a), the skin layer (4) may be laminated on one side of the acetic acid adsorption film (2), and as shown in FIG. 1 (b), the acetic acid adsorption film (2). It may be laminated on both sides.

  As shown in FIG. 1A, when the skin layer (4) is laminated on one side of the acetic acid adsorption film (2), another layer (6), for example, a barrier layer, may be laminated on the other side. it can.

  By further laminating a skin layer on the acetic acid adsorption film, it is possible to prevent the acetic acid adsorbent contained in the acetic acid adsorption film from falling off.

  The acetic acid adsorbing film laminate of the present invention is, in a specific embodiment, in the case where acetic acid adsorbed on the acetic acid adsorbing film binds with the acetic acid adsorbent to form an acetate salt. It is believed that the acetate can be damped inside the acetic acid adsorption film laminate before appearing on the body surface. As a result, the acetic acid adsorption film laminated body of this invention has the advantage that an acetate does not ooze on the surface.

(Skin layer)
The skin layer is a layer laminated on the acetic acid adsorbing film and adsorbs acetic acid on the acetic acid adsorbing film through the layer. This skin layer can prevent the acetic acid adsorbent contained in the acetic acid adsorbing film from falling off.

  The skin layer is preferably made of polyolefin, and is preferably made of polyethylene. Examples of the polyethylene include resins having a higher density than the ethylene-α-olefin copolymer, particularly low-density polyethylene and high-density polyethylene, which are mentioned with respect to the binder.

  The thickness of the skin layer can be selected so as to prevent acetic acid adsorbent from falling off while allowing permeation of acetic acid. For example, the thickness of the skin layer is 5% or more, 10% or more, or 15% of the thickness of the acetic acid adsorption film. It can also be 35% or less, 30% or less, or 25% or less.

(Other layers)
Examples of the other layer include a barrier layer. A barrier layer is a layer laminated | stacked on an acetic acid adsorption film, Comprising: Acetic acid is a layer which does not permeate | transmit substantially. As the barrier layer, for example, a metal foil such as an aluminum foil can be used.

<Method for producing acetic acid adsorption film>
The acetic acid adsorption film of the present invention can be produced by kneading the above binder, adsorbent, and surfactant to obtain a resin composition, which is then formed into a film. For kneading, for example, a batch kneader such as a kneader, a Banbury mixer, a mixing roll conical mixer, or a continuous kneader such as a biaxial kneader is used. In this case, kneading can be performed at a temperature of 100 ° C. or higher, 120 ° C. or higher, or 140 ° C. or higher, and 220 ° C. or lower, 200 ° C. or lower, or 180 ° C. or lower, depending on the material used.

  The acetic acid adsorption film of the present invention can be obtained by molding the kneaded resin composition into a film. For example, the kneaded resin composition can be formed into a film shape by extrusion molding such as press molding, inflation method, T-die method, coextrusion, or injection molding, or a laminate with other films. Can also be obtained as

  In particular, the method for producing an acetic acid adsorbing film of the present invention includes an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic monomer copolymer, an ethylene-α-olefin copolymer, and a mixture thereof. A binder containing the selected resin, an acetic acid adsorbent, and a nonionic aliphatic ester surfactant are kneaded to prepare a master batch, and the master batch is formed to form an acetic acid adsorbing film. Including. This master batch may have any shape, for example, a rod shape or a spherical shape.

  Preferably, from the viewpoint of better dispersing the acetic acid adsorbent, the method for producing an acetic acid adsorbing film of the present invention further includes forming the acetic acid adsorbing film by repelling the master batch and then forming the film.

<Method for producing acetic acid adsorption film laminate>
First, a resin composition is obtained by the method mentioned for the method for producing an acetic acid adsorbing film, and the resin composition and, for example, polyethylene are molded into an acetic acid adsorbing film and a skin layer, respectively, and laminated to form the acetic acid adsorbing of the present invention A film laminate can be obtained. For example, the resin composition can be formed into a film by extrusion molding such as press molding, inflation method, T-die method, or injection molding. Further, the molding and lamination can be performed together by a coextrusion method such as a coextrusion inflation method or a coextrusion T-die method.

<Packaging bag>
The acetic acid adsorbing film or acetic acid adsorbing film laminate can be formed into the packaging bag of the present invention by a conventional method (see: "Overview of Packaging Film Revised Edition", Revised 3rd Edition, Toyobo Packaging Co., Ltd.) Plan service). In this case, it is preferable to use an acetic acid adsorption film or an acetic acid adsorption film laminate as the innermost layer of the packaging bag.

<Peracetic acid bottle storage bag>
The present invention further relates to a peracetic acid bottle housing bag for disinfecting medical equipment, in which a bottle containing peracetic acid is housed in the packaging bag. As described above, peracetic acid is used to disinfect medical equipment such as an endoscope. In the medical field, peracetic acid is put in a bottle having a gas venting structure until it is used for disinfecting medical equipment. The bottle is put in a storage bag as shown in FIG. In the peracetic acid bottle containing bag (10) of the present invention, a bottle (30) containing peracetic acid is placed in the bag (10a) usually used, and the above acetic acid adsorbing film or acetic acid adsorbing film laminate (20) is placed. Or the bag itself is composed of the packaging bag described above. When the bag itself is composed of the packaging bag, the acetic acid adsorption film or the acetic acid adsorption film laminate (20) may not be accommodated in the peracetic acid bottle accommodation bag (10) of the present invention.

  EXAMPLES The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the examples.

≪Comparison of surface condition depending on type and presence of additive when ethylene-methyl methacrylate copolymer is used alone≫
<Production of acetic acid adsorption film>
An ethylene-methyl methacrylate copolymer, an acetic acid adsorbent (Kyoward 2200, Kyowa Chemical Co., Ltd.), and the additives shown in Table 1 below were blended at 89.9: 10: 0.1 and mixed in a twin-screw kneader. Then, a single-layer acetic acid gas adsorption film of 50 μm was obtained with a T-die film forming machine.

<Surface observation>
The obtained film was magnified 200 times with an optical microscope to observe the surface. The surface of the film of Example 1 is shown in FIG. 3, and the surface of the film of Comparative Examples 1-7 is shown in FIGS.

  3-10, the acetic acid adsorption film of Example 1 is disperse | distributing the solid content, ie, an acetic acid adsorption agent, more favorable compared with the acetic acid adsorption film of Comparative Examples 1-7. Therefore, it will be understood that it is effective to add a nonionic fatty acid ester surfactant as an additive.

≪Comparison with or without surfactant when ethylene-methyl methacrylate copolymer is mixed with other resin≫
<Production of acetic acid adsorption film>
(Example 2)
40 parts by mass of magnesium oxide as an acetic acid adsorbent, 59.2 parts by mass of an ethylene-methyl methacrylate copolymer, and 0.8 parts by mass of the nonionic fatty acid ester surfactant used in Example 1 Was kneaded with a 75 L Banbury mixer for 8 minutes to obtain a master batch. 25 parts by mass of this master batch, 59.96 parts by mass of an ethylene-methyl methacrylate copolymer, and 15.04 parts by mass of low-density polyethylene are dry blended and formed into a single layer by a small inflation film forming machine. The acetic acid adsorption film of Example 2 was obtained. The thickness of the acetic acid adsorption film was 50 μm.

(Comparative Example 8)
A single layer was formed in the same manner as in Example 2 except that an ethylene-methyl methacrylate copolymer was used in an amount of 60 parts by mass, and a master batch without using a nonionic fatty acid ester surfactant was used. The acetic acid adsorption film of Comparative Example 8 was obtained.

<Comparison of acetic acid adsorption amount>
The acetic acid adsorption films of Example 2 and Comparative Example 8 were trimmed to 20 mm × 20 mm, sealed in a 20 mL vial together with 30 μL of glacial acetic acid, and the weight was measured after one day to obtain the adsorption amount. The results are shown in Table 2.

  From Table 2, it will be understood that when Example 2 and Comparative Example 8 are compared, the amount of acetic acid adsorbed is improved by adding a surfactant. When this is combined with the results of surface observation, it will be understood that the dispersibility of the acetic acid adsorbent affects the amount of adsorbed acetic acid.

≪Comparison with and without repellet processing≫
<Production of acetic acid adsorption film>
In the following examples, the same master batch as the master batch prepared in Example 2 was used.

Example 3
First, the master batch was repellet processed with a twin screw extruder. 25 parts by mass of the re-pellet processed master batch, 59.96 parts by mass of an ethylene-methyl methacrylate copolymer, and 15.04 parts by mass of low density polyethylene were dry blended. This was made into the composition for acetic acid adsorption films used for Example 3.

  This composition for acetic acid adsorption film was formed into a single layer acetic acid adsorption film of Example 3 by using an inflation film forming machine. The thickness of the acetic acid adsorption film was 50 μm.

Example 4
A single-layer acetic acid adsorption film of Example 4 was obtained in the same manner as in Example 3 except that a master batch that was not re-pelletized was used instead of the re-pelleted master batch. The thickness of the acetic acid adsorption film was 50 μm.

(Example 5)
The acetic acid-adsorbing film composition produced in the same manner as in Example 3 was formed into a film by a two-layer / three-layer multilayer film forming machine together with the linear low-density polyethylene used for the skin layer. An adsorbent film laminate was obtained. The layer configuration was skin layer / acetic acid adsorption film / skin layer. The thickness of the skin layer was 10 μm, and the thickness of the acetic acid adsorption film was 50 μm.

(Example 6)
The acetic acid adsorption film laminated body of Example 6 was produced like Example 5 except having replaced the re-pellet processed master batch and using the master batch which has not been re-pellet processed. The thickness of the skin layer was 10 μm, and the thickness of the acetic acid adsorption film was 50 μm.

<Surface observation>
The acetic acid adsorption films (laminates) of Examples 3 and 5 were magnified 200 times with an optical microscope to observe the surface. Images of Examples 3 and 5 are shown in FIGS.

  Comparing FIGS. 3 and 11, for a single-layer acetic acid adsorption film, Example 3 (FIG. 11) in which repellet processing was performed was compared with Example 1 (FIG. 3) in which repellet processing was not performed. This confirms that the acetic acid adsorbent is more uniformly dispersed. Thus, it can be seen that Example 3 has a better dispersion of the acetic acid adsorbent than Example 1. In addition, it can be understood from FIG. 12 that in the case of a multilayer acetic acid adsorbing film, the acetic acid adsorbent is uniformly dispersed as in the case of a single layer.

<Comparison of acetic acid adsorption amount>
By trimming the acetic acid adsorbing films (laminates) of Examples 3-6 to 20 mm × 20 mm, encapsulating them in a 20 mL vial with 30 μL of glacial acetic acid, and measuring the weight after 1, 2 and 7 days The amount of adsorption was obtained. The results are shown in Table 3.

  From Table 3, it can be seen that Example 3 has a larger amount of adsorption at all times than Example 4, and Example 5 has a larger amount of adsorption at all times than Example 6. That is, it will be understood that the acetic acid adsorption amount is improved by repellet processing in both cases of a single layer film and a film laminate. When this is combined with the results of surface observation, it will be understood that the dispersibility of the acetic acid adsorbent affects the amount of adsorbed acetic acid.

  Further, in Example 3 and Example 4, the amount of adsorption decreased after 7 days, which is considered to be because the salt generated by the reaction between the adsorbent and acetic acid oozed from the surface. From this, it will be understood that it is more advantageous to use it as a film laminate when considering long-term acetic acid adsorption.

≪Reference example≫
Although the acetic acid adsorption film which does not contain surfactant is concretely demonstrated by a reference example and a reference comparative example, this film is not limited to a reference example. This reference example shows a resin suitable for an acetic acid adsorption film. Even when any of the resins used in this reference example is used, the dispersibility of the acetic acid adsorbent can be obtained by adding a surfactant and performing repellet processing in the same manner as in the above examples. Note that improves as well.

  Using the polymers described in Table 4, resin compositions having the compositions shown in Table 5 were prepared. Here, Kyoward 2200 (Kyowa Chemical Co., Ltd.) containing hydrotalcite was used as an adsorbent having acetic acid adsorption ability. In the composition of Table 5, each numerical value is part by mass.

  These resin compositions were kneaded with a conical mixer at a rotation speed of 100 rpm and a temperature of 140 ° C. for 5 minutes, and this kneaded body was pressed with a press machine at a temperature of 140 ° C. and a pressure of 20 MPa for 30 seconds to obtain a reference example 1 having a thickness of 50 μm. 11 and Reference Comparative Examples 1-2 were obtained.

  These films were trimmed to 20 mm × 20 mm and placed in a 20 mL vial, and 5 μL after 1 day and 8 μL glacial acetic acid after 8 days were injected into the vial. And the adsorption amount was obtained by measuring the amount of acetic acid gas in the vial after a fixed time by gas chromatography.

  These results are shown in Table 5.

  Comparing Reference Examples 1 to 5 with Reference Comparative Examples 1 and 2, it can be seen that the acetic acid adsorption film used in the present invention provides high acetic acid adsorption performance. In particular, it can be seen that there is a significant difference between Reference Examples 1 to 5 and Reference Comparative Examples 1 and 2 in the amount of adsorption after 8 days.

  Moreover, when the reference example 2 and the reference examples 6-8 are compared, this and polyethylene are mixed rather than the reference example 2 which used ethylene- (meth) acrylic-type monomer copolymer (EMMA) independently. It can be seen that the reference examples 6 to 8 used give higher acetic acid adsorption performance.

  Comparing Reference Example 4 and Reference Examples 9 to 13 shows that the acetic acid adsorption performance is maintained to a certain degree by blending an ethylene-α-olefin copolymer and low-density polyethylene and using it as a binder.

  By the way, when the film is formed, if the film has tackiness, the films stick to each other, and there is a problem in processing (workability) after film formation, such as film winding or lamination with other films. End up. Therefore, the processability of the film is determined by whether or not they can be peeled off (the presence or absence of tackiness) by using the same type of film and placing one film on the table and overlaying the other film. It was judged. Reference Examples 1 and 3 were excellent in workability because there was no sticking between films and there was no tackiness. When Reference Example 2 and Reference Examples 6-8 were compared, in Reference Example 2, sticking between the films was observed and the tackiness was slightly, but in Reference Examples 6-8, sticking between the films was seen. No tackiness was found, and it was found that the workability of Reference Examples 6 to 8 was improved. Moreover, when Reference Example 4 and Reference Examples 9-12 were compared, in Reference Example 4, although some sticking was seen to such an extent that films could be peeled apart easily, in Reference Examples 9-12, between films It was found that no sticking was observed, tackiness was suppressed, and workability as a film was improved. Further, it was confirmed that Reference Examples 5 and 13 had tackiness substantially the same as Reference Example 4 and had workability.

Claims (11)

  A binder containing a resin selected from the group consisting of an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic monomer copolymer, an ethylene-α-olefin copolymer, and a mixture thereof; An acetic acid adsorbing film, and a nonionic fatty acid ester surfactant.   The film according to claim 1, wherein the acetic acid adsorbent is an inorganic adsorbent that chemically adsorbs acetic acid.   The film according to claim 2, wherein the acetic acid adsorbent comprises magnesium oxide.   Of 100 parts by mass of the binder, 80 parts by mass or more are from the group consisting of ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic monomer copolymer, ethylene-α-olefin copolymer, and mixtures thereof. The film as described in any one of Claims 1-3 which is resin selected.   50 parts by mass or more of 100 parts by mass of the binder is an ethylene-vinyl acetate copolymer and / or an ethylene- (meth) acrylic copolymer, and 10 parts by mass or more is another resin. The film as described in any one of 1-3.   Of 100 parts by mass of the binder, 50 parts by mass or more is an ethylene- (meth) acrylic monomer copolymer, and 10 parts by mass or more is an ethylene-α-olefin copolymer, low density polyethylene, high density polyethylene or The film according to any one of claims 1 to 3, which is a mixture thereof.   10 parts by mass or more of 100 parts by mass of the binder is an ethylene-α-olefin copolymer, and 50 parts by mass or more is polyethylene having a higher density than the ethylene-α-olefin copolymer. The film as described in any one of 1-3.   The film laminated body by which the polyethylene skin layer is laminated | stacked on the acetic acid adsorption film as described in any one of Claims 1-7.   The film laminate according to claim 8, wherein the polyethylene skin layer is laminated on both sides of the acetic acid adsorption layer. Binder containing a resin selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic monomer copolymer, ethylene-α-olefin copolymer, and mixtures thereof, acetic acid adsorption Kneading the agent and the plant surfactant to produce a masterbatch;
Forming a master batch and forming an acetic acid adsorbing film.   The method for producing an acetic acid adsorbing film according to claim 10, further comprising forming the acetic acid adsorbing film by repellet processing the master batch.