WO2016051444A1

WO2016051444A1 - Antibacterial resin film and antibacterial article

Info

Publication number: WO2016051444A1
Application number: PCT/JP2014/075790
Authority: WO
Inventors: 尚久千東
Original assignee: 積水フィルム株式会社
Priority date: 2014-09-29
Filing date: 2014-09-29
Publication date: 2016-04-07
Also published as: JPWO2016051444A1

Abstract

The present invention provides an antibacterial resin film and antibacterial article having excellent antibacterial activity and excellent long-term persistence of antibacterial capability. The present invention is the antibacterial resin film formed from a single layer or multiple layers, and characterized in that at least one layer contains a polyvinyl alcohol polymer having amino groups in the side chains.

Description

Antibacterial resin film and antibacterial article

The present invention relates to an antibacterial resin film and an antibacterial article.

Conventionally, in order to impart antibacterial properties to resin products, it has been studied to add an antibacterial agent to the resin, and in particular, such a study is required in the medical field.

In the medical field, antibacterial articles exhibiting high antibacterial properties are required. For example, in the medical field, medical instruments and linens contaminated with blood, body fluid, excrement, etc. are washed, sterilized and reused. In the process of collecting, transporting, cleaning, sterilizing, etc., these medical instruments and linens, the workers engaged in the process must come into direct or indirect contact with the contaminated medical instruments and pollutants attached to the linens. Secondary infection by is a problem. For this reason, when collecting contaminated medical devices and linens, antibacterial articles such as laundry bags are formed with resin products containing antibacterial agents so that workers do not come into contact with the pollutants. It is necessary to enclose.

As a resin product containing an antibacterial agent that can be used for such an antibacterial article, for example, in a polyvinyl alcohol (hereinafter also referred to as PVA) synthetic fiber, a polymer polyamine or polymer polycarboxylic acid, and An antibacterial fiber containing an antibacterial substance (see Patent Document 1), a PVA film comprising a cyclodextrin inclusion compound in which a compound having antibacterial properties and the like is included in the molecular structure of cyclodextrin (see Patent Document 2) ) Has been proposed.

However, since the above-mentioned resin products use polymer antibacterial substances, etc., there is a problem that the antibacterial substances are difficult to uniformly disperse and have a portion that cannot exhibit antibacterial properties, resulting in inferior antibacterial properties. .

In addition, as a resin product containing an antibacterial agent, for example, a cleaning bag (see Patent Document 3) using an imidazole or pyrethroid agent as an antibacterial agent, antibacterial zeolite particles and 30 ° C. water at the time of immersion An antibacterial film (see Patent Document 4) made of a vinyl alcohol polymer having a weight swelling degree of 2.0 or less has been proposed.

However, since the above-mentioned resin products use organic compounds or inorganic compounds as antibacterial agents, there is a problem that the antibacterial agents bleed out over time and the antibacterial performance is inferior in long-term sustainability.

Therefore, it is desired to develop a resin product having excellent antibacterial properties and excellent long-term sustainability of antibacterial performance.

Japanese Patent Laid-Open No. 11-124723 Japanese Patent Laid-Open No. 11-116756 JP-A-5-170267 Japanese Patent Laid-Open No. 4-7335

The present invention has been made in view of the above problems, and an object thereof is to provide an antibacterial resin film and an antibacterial article excellent in antibacterial properties and excellent in long-term sustainability of antibacterial performance.

As a result of intensive studies to achieve the above object, the present inventors have a single layer or a plurality of layers, and at least one layer includes an antibacterial resin film containing a polyvinyl alcohol polymer having an amino group in a side chain. And, according to the antibacterial article using the antibacterial resin film, the inventors have found that the above object can be achieved, and have completed the present invention.

That is, the present invention relates to the following antibacterial resin film and antibacterial article.
1. An antibacterial resin film consisting of a single layer or multiple layers,
At least one layer contains a polyvinyl alcohol polymer having an amino group in the side chain.
An antibacterial resin film characterized by that.
2. The antibacterial resin film includes a plurality of layers, and includes a layer containing a polyvinyl alcohol polymer having an amino group in the side chain and a layer containing a polyvinyl alcohol polymer having no amino group in the side chain. Item 2. The antibacterial resin film according to Item 1.
3. Item 1 or 2 wherein the layer containing the polyvinyl alcohol polymer having an amino group in the side chain is formed by applying a resin composition containing a polyvinyl alcohol polymer having an amino group in the side chain. The antibacterial resin film described in 1.
4). An antibacterial article using an antibacterial resin film,
The antibacterial resin film contains a polyvinyl alcohol polymer having an amino group in a side chain in at least one layer.
Antibacterial article characterized by that.

Hereinafter, the antibacterial resin film and the antibacterial article of the present invention will be described in detail.

The antibacterial resin film of the present invention comprises a single layer or a plurality of layers, and at least one layer contains a polyvinyl alcohol polymer having an amino group in the side chain. The antibacterial resin film exhibits antibacterial properties when at least one of the layers constituting the antibacterial resin film contains a polyvinyl alcohol polymer having an amino group in the side chain. Since the uneven distribution of the antibacterial agent in the resin film, which occurs when imparting the properties, is suppressed and the antibacterial property can be exhibited over the entire resin film, the antibacterial property is excellent.

In addition, since the antibacterial resin film of the present invention exhibits antibacterial properties by containing a polyvinyl alcohol polymer having an amino group in the side chain in at least one layer, an antibacterial agent is added to the resin to impart antibacterial properties. As the antibacterial agent bleed-out, which occurs when the antibacterial agent is performed, the antibacterial performance is excellent in long-term sustainability.

That is, according to the present invention, an antibacterial resin film having excellent antibacterial properties and antibacterial performance for a long period of time can be obtained. It is possible to provide an antibacterial article excellent in antibacterial performance and long-term sustainability.

Also, for example, in the medical field, in order to prevent secondary infection, it must be possible to clean without taking out medical equipment or linen enclosed in a laundry bag. For this reason, the antibacterial resin film used for manufacturing a laundry bag as an antibacterial article needs to be dissolved by immersing it in a chemical solution in a state where a medical instrument or the like is enclosed, and water solubility is required. Is done. In addition, when the antibacterial article is a laundry bag for medical use, medical instruments, linen, etc. enclosed in the laundry bag may be washed with warm water of 80 ° C. or more for the purpose of sterilization. When used, the antibacterial resin film is not necessarily soluble in cold water, but may be soluble in hot water.

Since the antibacterial resin film of the present invention contains a layer containing a polyvinyl alcohol polymer having an amino group in the side chain in at least one layer, the layer exhibits water solubility, and other layers described later are also water soluble. By using an adhesive resin, the antibacterial resin film exhibits water solubility. Thus, for example, when a laundry bag is manufactured using the antibacterial resin film of the present invention, the laundry bag dissolves and disappears by immersing it in a chemical solution in a state in which medical instruments, linen, etc. are enclosed in the laundry bag. Therefore, it is not necessary for the worker to take out the contaminated medical device, and secondary infection can be suppressed.

1. Antibacterial Resin Film The antibacterial resin film of the present invention comprises a single layer or a plurality of layers, and at least one layer contains a polyvinyl alcohol polymer having an amino group in the side chain.

The polyvinyl alcohol polymer having an amino group in the side chain is not particularly limited as long as it has an amino group in the side chain and has a vinyl alcohol structural unit. The thing containing the structural unit which has an amino group shown by Formula (1) is mentioned.

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, or a formyl group.

In the above formula (1), R ₁ is preferably a hydrogen atom. R ₂ is preferably a hydrogen atom or a formyl group, and more preferably a hydrogen atom.

The polyvinyl alcohol polymer preferably contains 0.1 to 30 mol% of structural units having an amino group represented by the above formula (1) with respect to 100 mol% of all structural units of the polyvinyl alcohol polymer. . When there are too few structural units which have the said amino group, there exists a possibility that a resin film cannot fully exhibit antibacterial property. If the amount is too large, the number of structural units having a hydroxyl group in the side chain is relatively small, and the antibacterial resin film may be inferior in water solubility.For this reason, a laundry bag or the like is formed using the antibacterial resin film, When used after being dissolved in water, the processability may be inferior.

As the polyvinyl alcohol polymer having an amino group in the side chain, as shown in the general formula (1), a carbon atom constituting the main chain of the polyvinyl alcohol polymer and a nitrogen atom constituting the amino group And are not limited to those containing structural units directly linked to each other. For example, what contains the structural unit which has a hydrocarbon group etc. between the carbon atom which comprises the principal chain of a polyvinyl alcohol-type polymer, and the nitrogen atom which comprises an amino group can be used.

The polyvinyl alcohol polymer further contains a vinyl alcohol structural unit represented by the following general formula (2).

By including such a vinyl alcohol structural unit, water-solubility can be imparted to the antibacterial resin film, and laundry bags and the like formed using the antibacterial resin film are immersed in water together with the contents after use. By doing so, it becomes possible to dissolve and process laundry bags and the like.

The polyvinyl alcohol polymer preferably contains 49 to 99.4 mol% of vinyl alcohol structural units represented by the above formula (2) with respect to 100 mol% of all structural units of the polyvinyl alcohol polymer. More preferably, it is contained in an amount of ˜99 mol%. When there are too few vinyl alcohol structural units, there exists a possibility that the water solubility of a resin film may be inferior, and when there are too many, the hydrogen bond between hydroxyl groups may become strong and there exists a possibility that water solubility may fall.

The polyvinyl alcohol polymer may further contain a vinyl alkyl ester structural unit represented by the following general formula (3).

In the formula, R ₃ represents a hydrogen atom or an alkyl group.

In the above formula (3), R ₃ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably a methyl group.

The polyvinyl alcohol polymer is composed of a vinyl alcohol structural unit represented by the above formula (2) and a vinyl alkyl ester structural unit represented by the above formula (3), and the total of these polyvinyl alcohol polymers. The content is preferably 70 to 99.9 mol%, more preferably 70 to 99.5 mol%, based on 100 mol% of the structural unit.

As the polyvinyl alcohol polymer having an amino group in the side chain, a polyvinyl alcohol polymer represented by the following general formula (4) can be preferably used.

In the formula, m and n are numbers such that m + n is 70 to 99.9, and x and y are numbers such that x + y is 0.1 to 30.

By using the polyvinyl alcohol polymer represented by the general formula (4) as the polyvinyl alcohol polymer having an amino group in the side chain, the resin film exhibits particularly excellent antibacterial properties and has an appropriate water solubility. Can show.

The polyvinyl alcohol polymer having an amino group in the side chain may be a copolymer obtained by further copolymerizing other monomers as long as the object of the present invention is not impaired. Examples of such other monomers include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid and the like. Unsaturated acids or salts thereof, mono- or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid, or Its salts, alkyl vinyl ethers, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinyl chloride , Polyoxyalkylene (meth) allyl ethers such as polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether, polyoxyalkylenes such as polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate ( Polyoxyalkylene (meth) acrylamides such as (meth) acrylate, polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, poly Oxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene Or the like can be mentioned vinyl amine.

The polyvinyl alcohol polymer having an amino group in the side chain preferably has a saponification degree of 70 to 99.5 mol%. If the degree of saponification is too low, the antibacterial resin film may be inferior in water solubility, and when the antibacterial resin film is used to form a laundry bag or the like and dissolved in water after use, the processability May be inferior. If it is too high, the hydrogen bond between the hydroxyl groups becomes strong, and the water solubility may decrease.

The degree of saponification refers to the vinyl alcohol polymer having an amino group, the vinyl alcohol structural unit represented by the general formula (2), and the vinyl alkyl ester structural unit represented by the general formula (3). The ratio of the vinyl alcohol structural unit represented by the general formula (2) with respect to the total is expressed in mol%. For example, in the polyvinyl alcohol polymer represented by the general formula (4), {n ÷ (N + m)} × 100.

The weight average molecular weight of the polyvinyl alcohol polymer having an amino group is preferably 5,000 to 2,000,000 g / mol. More preferably, it is 10,000 to 1,500,000 g / mol, still more preferably 15,000 to 1,000,000 g / mol, and particularly preferably 20,000 to 500,000 g / mol.

The method for producing the above-mentioned polyvinyl alcohol polymer having an amino group is not particularly limited, and can be produced by a conventionally known method. As such a production method, vinyl formamide and vinyl alkyl esters are copolymerized, the formyl group of the obtained copolymer is hydrolyzed to form an amino group, and the alkyl ester group is hydrolyzed to hydroxyl group. The manufacturing method which forms group is mentioned.

Examples of the method for producing the polyvinyl alcohol polymer having an amino group include (a) 99 to 1 mol% of N-vinylformamide and (b) 1 to 99 mol% of one or more kinds of vinyl C1-C10. Alkyl esters are copolymerized and then 30 to 100 mol% of the formyl groups from the copolymerized units (a) are hydrolyzed to form amino groups, resulting in C1-C10 alkyls from the copolymerized units (b). The manufacturing method which hydrolyzes 30 to 100 mol% of ester groups and forms a hydroxyl group is mentioned.

Specifically, the manufacturing method is a manufacturing method including the following steps.
a) Charge the first portion of the total amount of N-vinylformamide into the reactor;
b) loading the first part of the total amount of at least one vinyl C1-C10 alkyl ester into the reactor;
c) continuously feeding a first portion of the total amount of free radical polymerization catalyst into the reactor at a first catalyst flow rate;
d) contacting a first portion of N-vinylformamide, a first portion of at least one vinyl C1-C10 alkyl ester in the presence of a free radical polymerization catalyst under polymerization conditions for a first period;
e) After the first period, under the polymerization conditions until the total amount of N-vinylformamide, the total amount of vinyl C1-C10 alkyl ester, and the total amount of free radical polymerization catalyst are fed into the reactor, the second period During which time a second portion of N-vinylformamide is continuously fed into the reactor in at least 4 hours, while at the same time a second portion of at least one vinyl C1-C10 alkyl ester is introduced into the reactor. -Feeding simultaneously with vinylformamide and simultaneously feeding the second part of the free radical polymerization catalyst into the reactor to produce an intermediate copolymer containing polyvinylformamide and one or more polyvinyl C1-C10 alkyl esters Here, in the third period, the solid content of the intermediate copolymer in the reactor is about 20 wt% or more and about 70 wt% or less. Sometimes it ends; Next, after the step of removing the polymerizable monomer unreacted give Intermediate copolymer.
f) The copolymer is saponified under either acidic or basic conditions to produce an intermediate polyvinylamide-polyvinyl alcohol copolymer;
g) The intermediate polyvinylamide-polyvinyl alcohol copolymer is hydrolyzed under either acidic or basic conditions to produce a water soluble copolymer.
h) This is washed in the presence of methanol and subjected to a dehydration drying step to obtain a water-soluble copolymer.

The antibacterial resin film of the present invention only needs to contain at least one layer containing a polyvinyl alcohol polymer having an amino group in the side chain.

The layer containing the polyvinyl alcohol polymer having an amino group in the side chain in at least one layer contains an antibacterial agent as long as the antibacterial property and antibacterial performance of the antibacterial resin film of the present invention are not hindered. You may do it. The antibacterial agent is not particularly limited, and conventionally known antibacterial agents can be used. Examples of the antibacterial agent include commercially available organic and inorganic antibacterial agents. Specifically, magnesium, calcium and copper or zinc composite metal hydroxide, or oxide, silver, copper, zinc, titanium, etc. Oxides of silver, copper, zinc, calcium, magnesium, etc., ionic substances in an antibacterial metal alone or in a mixed state, silver, copper, zinc in water-insoluble composites supported on silica glass, zeolite, zirconium phosphate, etc. Organic antibacterial agent alone or organic antibacterial agent and inorganic carrier mixture or composite, or organic antibacterial agent and inorganic antibacterial agent mixture or composite.

When the above antibacterial agent is used, bleeding out occurs and the antibacterial performance of the antibacterial resin film changes with time. Therefore, the antibacterial resin film of the present invention preferably contains no antibacterial agent. *

The antibacterial resin film of the present invention may be formed of a single layer containing a polyvinyl alcohol polymer having an amino group in the side chain, or at least one layer of polyvinyl alcohol having an amino group in the side chain. As long as it has a layer containing an alcohol polymer, it may be formed of a plurality of layers.

When the antibacterial resin film is formed of a plurality of layers, the layer structure is not particularly limited as long as at least one layer includes a layer containing a polyvinyl alcohol polymer having an amino group in the side chain. That is, you may provide other layers other than the layer containing the polyvinyl alcohol-type polymer which has an amino group in the said side chain.

The resin forming the other layer is not particularly limited as long as it does not hinder the long-term durability of the antibacterial and antibacterial performance of the antibacterial resin film. For example, polyethylene terephthalate resin (PET), polyamide resin, polypropylene resin (PP), polyethylene resin (PE), cellophane, triacetyl cellulose resin (TAC), vinyl chloride resin and the like.

Examples of the other layer include a layer containing a polyvinyl alcohol polymer having no amino group in the side chain. By adopting such a layer as the other layer, the other layer has a configuration similar to the configuration of the structural unit of the layer containing the polyvinyl alcohol polymer having an amino group in the side chain. The antibacterial resin film having excellent interlayer adhesion can be obtained. In addition, when an antibacterial article to be described later is formed using an antibacterial resin film employing such a layer as the other layer, all the layers constituting the antibacterial article contain a polyvinyl alcohol polymer. The antibacterial article is water-soluble. Thereby, for example, when a laundry bag is manufactured as an antibacterial article, if the laundry bag is immersed in a chemical solution or the like with the contaminant in the laundry bag, the laundry bag dissolves and disappears. Contaminants can be easily cleaned.

FIG. 1 shows an example of a layer structure when the antibacterial resin film is formed of a plurality of layers. In FIG. 1, an antibacterial resin film 1 of the present invention includes a layer 2 containing a polyvinyl alcohol polymer having an amino group in the side chain, a polyvinyl alcohol polymer having no amino group in a high molecular weight side chain, and the like. And a layer 3 containing a water-soluble polymer having a high tear strength. By making such a layer structure, for example, when manufacturing a laundry bag which is an antibacterial article using an antibacterial resin film, the layer 2 containing a polyvinyl alcohol polymer having an amino group in the side chain is formed. If the layer 3 containing a water-soluble polymer having a high tear strength, such as a polyvinyl alcohol polymer having no amino group in the high molecular weight side chain, is used as the outside, the inner layer 2 can be used in the laundry bag. Bacteria growth can be suppressed, and the inner layer 2 can be protected by the outer layer 3.

FIG. 2 shows another example of the layer structure when the antibacterial resin film of the present invention is formed in a plurality of layers. As shown in FIG. 2, the antibacterial resin film 1 of the present invention comprises a layer 2 containing a polyvinyl alcohol polymer having an amino group in the side chain, and a polyvinyl alcohol heavy polymer having no amino group in the high molecular weight side chain. It is good also as a structure clamped from the both sides by the layer 3 containing the water-soluble polymer with high tear strengths, such as coalescence.

The antibacterial resin film of the present invention may be insolubilized depending on the intended use. For example, as will be described later, when an antibacterial article that is a coating material such as a wall covering or a flooring is produced using the antibacterial resin film of the present invention, Durability can be improved. The insolubilization treatment can be performed by irradiating the antibacterial resin film of the present invention with an electron beam.

The electron beam irradiation method is not particularly limited, and for example, irradiation can be performed using an electron beam irradiation apparatus such as a dynamitron electron accelerator. The dose of the electron beam is preferably 40-80 KGy.

The thickness of the antibacterial resin film is not particularly limited, and may be a thickness suitable for a desired product.

The method for producing the antibacterial resin film of the present invention is not particularly limited.For example, on one side or both sides of the film used as the other layer, a polyvinyl alcohol polymer having an amino group in the side chain is water-soluble, Examples thereof include a method of applying a resin composition adjusted to an optimum viscosity for each coating method by adding an antifoaming agent, a slip agent, etc., forming a coating film, and heating and drying. As a coating method of the coating liquid, a conventionally known method can be used, and examples thereof include a coating method by a wet process such as gravure coating, micro gravure coating, and bar coater coating. In the antibacterial resin film of the present invention, the layer containing a polyvinyl alcohol polymer having an amino group in the side chain is preferably a layer formed by applying the resin composition. The antibacterial resin film of the present invention can be easily produced by forming a layer containing a polyvinyl alcohol polymer having an amino group in the side chain by applying the resin composition.

The thickness of the coating film is preferably 0.1 to 5.0 μm, more preferably 0.5 to 2.0 μm.

Examples of the method for producing the antibacterial resin film of the present invention include film formation methods such as an inflation film formation method and a T-die method film formation method.

2. Antibacterial article The present invention is also an antibacterial article using the antibacterial resin film. Although it does not specifically limit as said antibacterial article, For example, a packaging material, a coating material, etc. are mentioned.

Examples of packaging materials include packaging materials for packaging medical items such as laundry bags. The laundry bag should just be manufactured using the said antibacterial resin film, and the magnitude | size and shape should just be suitably set according to the medical instrument, linens, etc. which collect | recover and convey.

The molding method and the joining method when manufacturing a laundry bag using the antibacterial resin film are not particularly limited, and include conventionally known methods such as joining by heat sealing.

As coating materials, wall coverings used to coat walls, floors, and ceilings of factories and other buildings in fields that require suppression of contamination of food and cosmetics, and operating rooms in the medical field. And interior materials such as wood and flooring. Moreover, the sheet | seat used for the surface of the foot-wiping mat used at the time of entering the factory adjusted to bioclean environment is also mentioned. Further, in the agricultural field, an antifogging layer or the like laminated on the inner surface of a stretch film for agricultural house used in a vinyl house that requires antifogging and antibacterial properties is also included.

Since the antibacterial article of the present invention uses the above-mentioned antibacterial resin film, it is excellent in antibacterial properties and long-term sustainability of antibacterial performance.

Since the antibacterial resin film of the present invention exhibits antibacterial properties by containing a polyvinyl alcohol polymer having an amino group in the side chain in at least one layer, the antibacterial property is imparted by adding an antibacterial agent to the resin. Since the uneven distribution of the antibacterial agent in the resin film is suppressed and the antibacterial property can be exhibited over the entire resin film, the antibacterial property is excellent.

In addition, since the antibacterial resin film of the present invention exhibits antibacterial properties by containing a polyvinyl alcohol polymer having an amino group in the side chain in at least one layer, an antibacterial agent is added to the resin to impart antibacterial properties. Since the occurrence of bleed-out of the antibacterial agent that occurs when the antibacterial agent is performed is suppressed, the antibacterial performance is excellent in long-term sustainability.

For this reason, the antibacterial resin film of the present invention is excellent in antibacterial properties and has excellent long-term sustainability of antibacterial performance, and is excellent in antibacterial properties by making an antibacterial article using the antibacterial resin film. In addition, an antibacterial article excellent in antibacterial performance for a long time can be provided.

It is sectional drawing which shows an example of a layer structure in the case of forming the antibacterial resin film of this invention by multiple layers. It is sectional drawing which shows an example of a layer structure in the case of forming the antibacterial resin film of this invention by multiple layers.

(Example)
Examples of the present invention will be described below. The present invention is not limited to the following examples.

Example 1
A vinyl acetate monomer and an N-vinylformamide monomer were copolymerized to obtain a copolymer of these monomers. A film containing a polyvinyl alcohol polymer having an amino group in the side chain by hydrolyzing a formyl group of this copolymer to form an amino group and hydrolyzing an alkyl ester to form a hydroxyl group Was prepared.

In the obtained film, the polyvinyl alcohol polymer having an amino group in the side chain is composed of 8 mol% of the structural unit having an amino group and the vinyl alcohol structure with respect to 100 mol% of the total structural unit of the polyvinyl alcohol polymer. It contained 90 mol% units and 2 mol% vinyl acetate structural units.

Using the obtained film, the film was stored for 1 hour at a temperature of 50 ° C., and then subjected to 20 accelerated tests with 1 cycle stored at a temperature of 0 ° C. for 1 hour, and the surface of the film after the accelerated test. Was wiped off with linen.

Comparative Example 1
Selvol (registered trademark) 205 (manufactured by Seki Swiss Specialty Chemical Co., Ltd.) was prepared as a polyvinyl alcohol polymer having no amino group in the side chain (polyvinyl alcohol resin not modified with amine). 5 parts by mass of diglycerin as a plasticizer is added to 100 parts by mass of the polyvinyl alcohol resin, and further, as an antioxidant, a phosphorus-based antioxidant (Irgaphos 168 manufactured by BASF) and a hindered phenolic acid inhibitor (BASF A resin composition was prepared by adding 0.5 parts by mass of a mixture of Irganox 3114) manufactured by the company. After pelletizing the obtained resin composition, extrusion molding was performed by a T-die method to prepare a 50 μm film. Using the obtained film, the same acceleration test as the acceleration test performed in Example 1 was performed.

Comparative Example 2
Selvol (registered trademark) 205 (manufactured by Sekisui Specialty Chemicals America, Inc.) was prepared as a polyvinyl alcohol polymer having no amino group in the side chain (polyvinyl alcohol resin not modified with amine). To this resin, 2- (4-thiazolyl) -benzimidazole was added as an antibacterial agent so as to have a content of 1.5 wt% and mixed to prepare a resin composition. After pelletizing the obtained resin composition, extrusion molding was performed by a T-die method to prepare a 50 μm film. Using the obtained film, the same acceleration test as the acceleration test performed in Example 1 was performed.

The films after the acceleration test obtained in Example 1 and Comparative Examples 1 and 2 were sampled so as to be 5% by weight with respect to 100% by weight of purified water or physiological saline, respectively, and purified water or physiological saline. To prepare a solution. The prepared lysate was used for the antibacterial test of Escherichia coli and the antibacterial test of Staphylococcus aureus under the following conditions. Moreover, in the following antibacterial test, for comparison, purified water in which the film was not dissolved and physiological saline in which the film was not dissolved were prepared.

(Antimicrobial test of E. coli)
After culturing E. coli (gram-negative bacteria) on an agar medium at 35 ° C. for 18 to 24 hours, suspended in purified water so that the number of bacteria becomes 10 ⁷ to 10 ⁸ / ml. A liquid was prepared. 10 ml of the lysate prepared in Example 1, Comparative Examples 1 and 2 and the purified water as Comparative Example 3 prepared using purified water were collected and inoculated with 0.1 ml of the test bacterial solution. A test solution was prepared. The number of viable bacteria in the test liquid immediately after inoculation with the test bacterial liquid was 9.0 × 10 ⁵ / ml.

The obtained test solution was allowed to stand at room temperature, and after 15 minutes, 1 hour, and 24 hours, each was diluted 1000 times with SCDLP medium, and the number of viable bacteria during the test was measured. The measurement was performed by culturing at 35 ° C. for 2 days by using a pour plate culture method using an SCDLP medium.

Antibacterial activity was evaluated according to the following criteria based on the measured viable count.
A: Number of viable bacteria less than 10 ³ ○: Viable cell count of 10 ³ or more and less than 10 ⁴ Δ: Viable cell count of 10 ⁴ or more and less than 10 ⁵ ×: Viable cell count of 10 ⁵ or more

(Antimicrobial test for Staphylococcus aureus)
Staphylococcus aureus (gram-positive bacteria) is cultured on an agar medium at 35 ° C. for 18 to 24 hours, and then suspended in physiological saline so that the number of bacteria becomes 10 ⁷ to 10 ⁸ / ml. A test bacterial solution was prepared. 10 ml of the lysate obtained in Example 1, Comparative Examples 1 and 2 and the physiological saline as Comparative Example 3 prepared using physiological saline were collected, and 0.1 ml of the test bacterial solution was added to each. A test solution was prepared by inoculation. The number of viable bacteria in the test solution immediately after inoculation with the test bacterial solution was 7.3 × 10 ⁵ / ml.

Antibacterial activity was evaluated according to the following criteria based on the measured viable count.
◎: viable cell number less than 10 ³ ○: viable cell number 10 ³ 10 less than ⁴ △: viable cell number 10 ⁴ 10 less than ⁵ ×: Table 2 shows the viable cell number 10 ⁵ or more results.

Example 2
As a polyvinyl alcohol polymer having an amino group in the side chain, amine-modified PVA (12 mol% modified product manufactured by Seki Swiss Specialty Chemical Co., Ltd.) was prepared. The polyvinyl alcohol polymer having an amino group in the side chain was dissolved in water at 40 ° C. to prepare a 5% by mass aqueous solution of the polyvinyl alcohol polymer having an amino group in the side chain. The viscosity of the aqueous solution was 30 to 120 cps. Ethyl alcohol and isopropyl alcohol were added to this aqueous solution to prepare a polyvinyl alcohol polymer solution having an amino group in the side chain. The content of ethyl alcohol was 10% by mass, and the content of isopropyl alcohol was 5% by mass, assuming that the solution was 100% by mass. Resin composition containing polyvinyl alcohol polymer having amino group in side chain, 0.2 parts by mass of silicone-based antifoaming agent and 2 parts by mass of wax are added to 100% by mass of the solution. Was prepared. The obtained resin composition exhibited an appropriate viscosity and drying rate, and was given water-soluble gravure paint suitability.

The obtained resin composition was applied to one side of cellophane paper PT # 300 (manufactured by Rengo Co., Ltd.) with a coating amount of 6 g / m ² using a 175 line gravure cylinder, and a drying temperature of 80 ° C. Then, coating was carried out at a processing speed of 50 m / min to form a layer containing a polyvinyl alcohol polymer having an amino group in the side chain having a solid content of 0.3 g / m ² . This prepared the antibacterial resin film provided with the layer containing the polyvinyl alcohol-type polymer which has an amino group in a side chain on cellophane paper.

Examples 3-8
Instead of cellophane paper, an antibacterial resin film was prepared in the same manner as in Example 2 except that the following film was used.
Example 3: PET film (Toyobo Co., Ltd. E5102 thickness 12 μm Corona-treated surface coating)
Example 4: Polyamide film (manufactured by Toyobo Co., Ltd., N1102 thickness 15 μm, corona-treated surface application)
Example 5: OPP film (manufactured by Toyobo Co., Ltd., P2161, thickness 20 μm, corona-treated surface application)
Example 6: L-LDPE film (Ramilon MF, 50 μm thick, corona-treated surface coating manufactured by Sekisui Film Co., Ltd.)
Example 7: TAC film (manufactured by Konica Minolta, Inc. TAC thickness 50 μm)
Example 8: Hard vinyl chloride resin film (F100 thickness 100 μm, manufactured by Sekisui Molding Industry Co., Ltd.)
Comparative Examples 4-10
In Examples 2 to 8, a resin composition containing a polyvinyl alcohol polymer having an amino group in the side chain was not applied, and a layer containing a polyvinyl alcohol polymer having an amino group in the side chain was not formed. It was. That is, cellophane paper, PET film, polyamide film, OPP film, L-LDPE film, TAC film, and hard vinyl chloride resin film were used as Comparative Examples 4 to 10, respectively.

Examples 2 to 8 and Comparative Examples 4 to 10 were subjected to the antibacterial test for E. coli and the antibacterial test for Staphylococcus aureus. The results are shown in Table 3.

Example 9
5 parts by mass of a polyvinyl alcohol polymer having an amino group in the side chain (12 mol% modified product made by Seki Swiss Specialty Chemical Co., Ltd.) per 100 parts by mass of Selvol (registered trademark) 205 (Sekisui Specialty Chemicals America Co., Ltd.) Part was added. 5 parts by mass of diglycerin was added as a plasticizer, and a mixture of a phosphorus antioxidant (Irgaphos 168 manufactured by BASF) and a hindered phenol antioxidant (Irganox 3114 manufactured by BASF) was added as an antioxidant. .5 parts by mass was added and kneaded to prepare a resin composition containing a polyvinyl alcohol polymer having an amino group in the side chain. For the kneading, a general twin-screw extruder for melt extrusion used for producing pigment pellets was used.

In Example 9, the resin composition is a polyvinyl alcohol polymer having an amino group in the side chain (12 mol% manufactured by Seki Swiss Specialty Chemical Co., Ltd.) with respect to 100 parts by mass of Selvol (registered trademark) 205 (Seki Swiss Specialty Chemical Co., Ltd.). Since the modified product was prepared by adding 5 parts by mass, it had melt extrusion suitability.

After pelletizing the obtained resin composition, extrusion molding was performed by a T-die method to prepare a 50 μm antibacterial resin film. Extrusion molding by the T-die method is performed under temperature conditions that do not raise the decomposition start temperature (180 ° C.) or higher of the polyvinyl alcohol polymer having an amino group in the side chain, die diameter 50 mm, L / D: 30, compression ratio: It carried out using the extruder of a full flight screw by the conditions of 2.8.

Example 10
Co-extrusion molding was performed by a three-layer T-die method to prepare an antibacterial resin film having a three-layer structure of surface layer / intermediate layer / back surface layer. As the composition used for forming the surface layer, the resin composition containing a polyvinyl alcohol polymer having an amino group in the side chain prepared in Example 8 was used. Moreover, as a composition used for formation of an intermediate | middle layer and a back surface layer, the resin composition containing the polyvinyl alcohol polymer which does not have an amino group in the side chain prepared in the comparative example 1 was used.

After pelletizing the resin composition, coextrusion molding is performed by the T-die method, and the antibacterial resin film has a thickness ratio of 1/2/1 to the surface layer / intermediate layer / back surface layer and a total thickness of 50 μm. Was prepared. In the co-extrusion molding by the T-die method, the same extruder as that used in Example 8 is disposed in the center, and other extruders include a die diameter of 40 mm, L / D: 30, and a compression ratio of 2.8. And two full flight screw extruders were used.

Example 11
Using the resin composition containing a polyvinyl alcohol polymer having an amino group in the side chain prepared in Example 9, extrusion molding was performed by an inflation method to prepare an antibacterial resin film having a thickness of 50 μm. Extrusion molding by the inflation method was performed using an inflation mold having a diameter of 300 mm under a blow ratio of 1.0.

Examples 9 to 11 and Comparative Example 1 were subjected to the antibacterial test for E. coli and the antibacterial test for Staphylococcus aureus. The results are shown in Table 4.

Example 12
The antibacterial resin film prepared in Example 3 is irradiated with an electron beam from the layer side containing a polyvinyl alcohol polymer having an amino group in the side chain, and the polyvinyl alcohol polymer having an amino group in the side chain. Was insolubilized to prepare an antibacterial resin film of Example 12. The electron beam irradiation conditions were performed by irradiating a dose of 40 KGy using a dynamitron type electron accelerator.

Example 13
An antibacterial resin film of Example 13 was prepared in the same manner as in Example 12 except that the antibacterial resin film prepared in Example 10 was used.

Comparative Example 11
A resin composition was prepared by adding an inorganic antibacterial agent (silver / zeolite antibacterial agent manufactured by Sinanen Co., Ltd.) to LLDPE resin (2045G manufactured by Dow Chemical Company), and extrusion molding was performed by an inflation method. The content of the inorganic antibacterial agent was 0.5% with respect to 100% by mass of the resin composition. Otherwise, a film was prepared in the same manner as in Example 12.

Examples 12 and 13 and Comparative Example 11 were subjected to the above antibacterial test for Escherichia coli and the antibacterial test for Staphylococcus aureus. In addition, about Example 12 and 13, the said test was done using the layer side which performed insolubilization. The results are shown in Table 5.

From the results of Table 5, it was found that the antibacterial resin film can sufficiently exhibit antibacterial properties even when the polyvinyl alcohol polymer having an amino group in the side chain is insolubilized.

(Measurement test of the minimum growth inhibitory concentration of anaerobic bacteria)
The resin composition prepared in Example 9 and Comparative Example 1 was added to water and gradually dissolved with stirring at 60 ° C. to adjust the concentration, thereby preparing a test solution. Using the test solution, the minimum inhibitory concentration (MIC) of anaerobic bacteria (Clostridium difficile) was measured. The measurement is carried out by an agar plate dilution method with an inoculum amount of 10exp5cfu / Spot, and the test medium inoculated with the test strain in an anaerobic chamber (nitrogen 82% carbon dioxide 10% hydrogen gas 8%) in an environment of 35 ° C. This was carried out by standing for 48 hours, measuring the number of distributed strains after culture, and evaluating according to the following criteria.
○: Less than 15 distributed strains ×: 15 or more distributed strains The results are shown in Table 6.

From the results of Table 6, in Example 9 using a resin composition containing a polyvinyl alcohol polymer having an amino group in the side chain, the growth of anaerobic bacteria was suppressed even at a concentration of 6.4 Mg / ml or less. It was found that it exhibits antibacterial properties against anaerobic bacteria. On the other hand, in Comparative Example 1 using a resin composition containing a polyvinyl alcohol polymer having no amino group in the side chain, the number of distributed strains is large at a concentration of 6.4 Mg / ml or less, and X judgment was made. It was. Moreover, in the comparative example 1, it became x determination also in the density | concentration exceeding 6.4 Mg / ml, and it turned out that the antibacterial property to anaerobic bacteria is inferior.

DESCRIPTION OF SYMBOLS 1 ... Antibacterial resin film, 2 ... The layer containing the polyvinyl alcohol-type polymer which has an amino group in a side chain, 3 ... The layer containing the polyvinyl alcohol-type polymer which does not have an amino group in a side chain

Claims

An antibacterial resin film consisting of a single layer or multiple layers,
At least one layer contains a polyvinyl alcohol polymer having an amino group in the side chain.
An antibacterial resin film characterized by that.
The antibacterial resin film includes a plurality of layers, and includes a layer containing a polyvinyl alcohol polymer having an amino group in the side chain and a layer containing a polyvinyl alcohol polymer having no amino group in the side chain. The antibacterial resin film according to claim 1.
The layer containing a polyvinyl alcohol polymer having an amino group in the side chain is formed by applying a resin composition containing a polyvinyl alcohol polymer having an amino group in the side chain. 2. The antibacterial resin film according to 2. *
An antibacterial article using an antibacterial resin film,
The antibacterial resin film contains a polyvinyl alcohol polymer having an amino group in a side chain in at least one layer.
Antibacterial article characterized by that.