JPS5920644B2 - Sterilizing polymer material and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides films, sheets, etc. for packaging or storage containers containing hypochlorites such as calcium, magnesium, and lithium, and exhibiting properties such as sterilization, preservative, mold prevention, and deodorization. Relates to sterilizing polymeric materials such as plates and their manufacturing methods.

Conventionally, cleaning films, sheets, etc. made of polyethylene resin, polypropylene resin, polyvinyl chloride resin, etc. have been used for preservation packaging of various items such as clothing, food, precision equipment, and garbage. When the above items are sealed and stored using packaging materials such as clean films and sheets, mold and bacteria often develop and multiply in the contents, especially when the environment is warm for a long period of time. Strict quality checks were required to preserve and manage the contents, as this led to deterioration and decay.

In addition, bleaching powder, chlorinated incyanuric acid, chloramine B1 chloramine T1 chlorinated hydantoin, etc. are known as disinfectants, but these are easily decomposed at high temperatures, so
These disinfectants cannot be incorporated into polymeric materials by methods requiring high temperatures such as dissolving and kneading, and polymeric materials for packaging containing these disinfectants have not been known at all.

While researching polyethylene film packaging materials containing quicklime, the present inventors discovered that polyethylene film absorbs chlorine gas extremely easily in a chlorine gas atmosphere at room temperature. When the polyethylene film is handled in the air, it absorbs moisture from the air and some of the quicklime in the polyethylene film turns into slaked lime, so chlorine absorption easily occurs when it comes into contact with chlorine gas. It was discovered that calcium chlorite was formed, and the food did not develop mold or rot even after it was sealed and stored in a warm environment for a long time using polyethylene film containing calcium hypochlorite. They discovered that this does not occur and completed the present invention.

The object of the present invention is to provide a thermoplastic polymer material in the form of a film, sheet, or plate that does not change the quality of the contents when the product is packaged and stored under sealed conditions, and exhibits properties such as sterilization, antifungal, antiseptic, and deodorizing properties. The object of the present invention is to provide a manufacturing method thereof.

The first invention of the present application is a germicidal polymeric material containing as main components 100 parts by weight of a thermoplastic organic polymer and 0.001 to 300 parts by weight of hypochlorite of calcium, magnesium, or lithium, or a mixture thereof. The second invention is a polymer material containing as main components 100 parts by weight of a thermoplastic organic polymer and 0.5 to 300 parts by weight of an oxide of calcium, magnesium or lithium, or a mixture thereof in the presence of water. A third invention is a method for producing a bactericidal polymeric material characterized by reacting it with chlorine, and the third invention is
100 parts by weight of a thermoplastic organic polymer, 0.5 to 300 parts by weight of an oxide of calcium, magnesium or lithium, or a mixture thereof, and 0.5 parts by weight of a hydroxide of the metal.
This is a method for producing a bactericidal polymeric material, which is characterized by reacting a polymeric material containing chlorine as a main component with chlorine.

In a preferred embodiment of the third invention, 100 parts by weight of a thermoplastic organic polymer and 0.5 to 300 parts of an oxide of calcium, magnesium or lithium, or a mixture thereof.
After melting and mixing, parts by weight are formed into a film, sheet, or plate-like material, and the resulting molded product is reacted with water to convert the metal oxide in the molded product into a hydroxide of the metal with a ratio of 0.1 to 100. A method for producing a bactericidal polymeric material, which is characterized in that the sterilizing polymer material is chlorinated after being converted to mixture 0.5
~300 parts by weight and 0.5 to 300 parts by weight of the metal hydroxide
This is a method for producing a sterilizing polymeric material, which is characterized by melt-kneading parts by weight, molding into a film, sheet, or plate-like product, and reacting the resulting molded product with chlorine.

The thermoplastic organic polymer used in the present invention is a thermoplastic resin commonly used as a packaging material,
For example, polyethylene, ethyl, lene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, polypropylene, propylene-butene copolymer, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Examples include vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-vinylidene chloride copolymer, and the like.

Calcium contained in the bactericidal polymeric material of the present invention,
The hypochlorite of magnesium or lithium has the chemical formula % formula %, respectively, but may be in the form of a hydrated salt thereof, a double salt such as bleached powder, a composition, or the like.

The hypochlorite contained in the germicidal polymeric material of the present invention gradually decomposes when the germicidal polymeric material of the present invention is handled in the air, releasing chlorine with germicidal activity, This has the effect of killing fungi in the package contents or killing fungi that have penetrated the packaging film within the film.

In addition to the thermoplastic organic polymer and the hypochlorite, the bactericidal polymeric material of the present invention may contain any other components, such as molding processing aids, as long as the object of the present invention is achieved. No problem.

Usually, the sterilizing polymeric material of the present invention has a thickness of 5μ to 10m.
It is a film-like, sheet-like, or plate-like object of about 100 m in diameter, but its shape may be arbitrary.

For example, the shape of a bottle or equivalent container is also preferable depending on the purpose of use.

Furthermore, a laminated structure in which a film, sheet, etc. of the thermoplastic organic polymer is laminated on the front, back, or both surfaces of these film, sheet, or plate materials may also be used.

The oxides of calcium, lithium magnesila, etc. used in the present invention each have the chemical formula Cab.

MgO, L 120 may contain other optional components as long as the purpose of the present invention is achieved, quicklime,
Industrial products such as magnesia are sufficient.

In addition, calcium, magnesium,
Hydroxides such as lithium also have the chemical formula Ca(OH).
It is represented by 2tMg(OH)2tLiOH, and may contain any other components as long as the purpose of the present invention is achieved, and for example, industrial products such as slaked lime are sufficient.

The bactericidal polymeric material of the present invention contains the thermoplastic organic polymer and hypochlorite as main components, and the ratio thereof is 0.001 to 300 parts by weight of hypochlorite per 100 parts by weight of the organic polymer.
Parts by weight are preferably 0.01 to 30 parts by weight.

If it is less than 0.001 part by weight, the bactericidal properties will be poor, and
If it exceeds 300 parts by weight, the amount of active chlorine generated will be too large, which will easily change the quality of the contents of the package, and may also cause insufficient strength as a packaging material and deterioration of the surface properties of the package, which is not practical. Often not.

Since the sterilizing polymeric material of the present invention exhibits heat-adhesive properties, it can be used to package an article and then heat-seal it to easily package the article in a hermetically sealed manner.

The first method for producing the bactericidal polymeric material of the present invention is as follows:
A film, sheet, or plate containing as main components 100 parts by weight of the thermoplastic organic polymer and 0.5 to 300 parts by weight, preferably 5 to 150 parts by weight of the oxide of calcium, magnesium, or lithium, or a mixture thereof. This method involves reacting polymeric materials such as chlorine with chlorine in the presence of water.

Examples of reaction methods include a method in which a small amount of a mixed gas of water vapor and chlorine gas is brought into contact with the film, sheet, plate-shaped object, etc., a method in which chlorine is dissolved in chlorine water, or a method in which chlorine is added to water while supplying chlorine gas. Examples include a method of bringing water into contact with the film, sheet, plate-like object, etc. described above.

The reaction proceeds satisfactorily at room temperature, and usually requires contact for several minutes to several tens of hours.

Polymer materials such as films, sheets, and plate-like materials containing oxides such as calcium, magnesium, and lithium can be produced by mixing the thermoplastic organic polymer and the powder of the metal oxide using a conventional melt-kneading machine, such as a single screw extrusion machine. After melt-kneading in a machine, the product can be easily formed into a film, sheet, or plate using a conventional molding method, such as an inflation film molding machine, a T-die molding machine, an injection molding machine, or a blow molding machine. It will be done.

The thickness is usually preferably about 5 μm to 1Q mm.

In addition, if the amount of the metal oxide to be contained is 0.5 parts by weight or less per 100 parts by weight of the organic polymer, even if it is reacted with chlorine in the presence of water, the metal oxide will remain in the film, sheet or plate-like material. A polymer material with a low hypochlorite content and sufficient bactericidal properties cannot be obtained.

Moreover, if it is more than 300 parts by weight, the film, sheet or plate-like product obtained by reacting with chlorine in the presence of water will have poor surface properties and strength, which is not preferable.

The second method for producing the bactericidal polymeric material of the present invention is to prepare 100 parts by weight of the thermoplastic organic polymer and 0.0 parts by weight of an oxide of calcium, magnesium, or lithium, or a mixture thereof.
5 to 300 parts by weight, and 0.5 to 30 parts by weight of the metal hydroxide.
Films, sheets containing 0 parts by weight as a main component,
This method involves reacting a polymeric material such as a plate with chlorine gas.

The content of metal oxide in the polymer material in this second manufacturing method is determined for the same reason as in the first manufacturing method.

Furthermore, when the content of metal hydroxide in the polymeric material is 0.5 parts or less, hypochlorite is not easily generated in the polymeric material during the subsequent reaction with chlorine gas. On the contrary, 30
When the amount is 0 parts or more, the amount of heat generated during the subsequent reaction with chlorine gas becomes excessive, making it difficult to obtain a preferable packaging material.

The reaction with chlorine gas in this second production method may be the same as in the first production method.

In a preferred embodiment of the second production method for the bactericidal polymeric material of the present invention, the film, sheet, or plate-like material containing an oxide of calcium, magnesium, lithium, etc. in the first production method is reacted with water in advance. After that, a method of reacting with chlorine gas can be mentioned.

The water used in the reaction may be liquid water, steam, or air, but humidified air is particularly preferred.

The reaction with water and the reaction with chlorine gas are sufficient at room temperature, but when reacting with water, 0.1 to 10
It is necessary to convert 0%, preferably about 0.5 to 30%, into metal hydroxide.

If it is less than 0.1%, hypochlorite will not be easily formed in films, sheets, or plates even if it is subsequently reacted with chlorine gas, and if it is more than 30%, it will be converted to metal hydroxide. During the subsequent reaction with chlorine gas, by-product water is eluted and rapid heat generation occurs, making it impossible to obtain a desirable packaging material.

Another unfavorable aspect of the second manufacturing method of the bactericidal polymeric material of the present invention is that 100 parts by weight of the thermoplastic organic polymer and 0.5 to 300 parts by weight of the oxide of calcium, magnesium, lithium, etc. and hydroxides of the above metals 0.5-3
A method may be mentioned in which 00 parts by weight are melted and mixed in the same manner as above, formed into a film, sheet, or plate-like object, and then the obtained formed object is reacted with chlorine gas.

The reaction with chlorine gas may be the same as in the second production method.

Furthermore, the content of the metal oxides and metal hydroxides must be avoided in addition to the same reasons as above, since dehydration and foaming will occur during melting and mixing, so that large amounts of the metal oxides and metal hydroxides should be avoided.

By the production method of the present invention described above, a sterilizing thermoplastic polymer material containing hypochlorite of the metal can be obtained, but the obtained sterilizing polymer film, sheet, or plate-like material contains raw materials. Even if metal oxides based on the above remain, it has sufficient practicality.

In some cases, residual metal oxides may be desirable, imparting a moisture-proofing effect to the packaging material.

The bactericidal film, sheet, or plate-like material of the present invention is stable and suitable as a material for long-term packaging storage, and exhibits the ability to gradually release active chlorine even after one year, for example.

The thermoplastic polymer material containing hypochlorite of the present invention has a low hypochlorite content, for example, one with an active chlorine concentration of 50 p1 Mll or less, and can be used as a sterile packaging material and a high These materials can be used as sterilizing packaging materials.

For example, depending on the type of hypochlorite contained, the thickness of the film, the type of resin material, and the presence or absence of lamination,
It can be used for various purposes of deodorization.

For example, if the bag made of the sterilizing polyethylene film according to the present invention is filled with clothing and stored hermetically, there is no need to enclose insect repellent such as yeast brain, and when the wet towel is packaged and stored, the number of attached bacteria can be reduced. can be extremely reduced.

Foods such as mochi, bread, and meat can be packaged and stored for a long time without deterioration.

Furthermore, it is also possible to store precision instruments such as cameras and lenses in anti-fungal packaging.

It is also possible to provide odor-proof packaging for foods such as dried fish and other raw garbage.

Furthermore, for deodorizing purposes, it can also be used as an underlay for shoe soles.

Examples will be described below, but the technical scope of the present invention is not limited thereto.

Example 1 Calcium oxide powder containing 0.5% calcium hydroxide and magnesium oxide containing 0.6% magnesium hydroxide were added and mixed in the proportions listed in Table 1 to 100 parts by weight of high-density polyethylene. After melting and mixing at 220° C., a tubular film with a thickness of 80 μm and a diameter of 300 mm was formed by the inflation method, and then the film was kept in a cabin at room temperature filled with chlorine gas to react with chlorine.

The film of the present invention thus produced could be cut and heat-sealed in the same way as polyethylene film produced by the usual inflation method, and could be made into bags of any desired shape.

When the active chlorine content in the above film was analyzed, the content was as shown in Table 1.

A bag with a depth of 300 m was made from the above film of the present invention.

Example 2 A mixture of 100 parts by weight of high-density polyethylene and 100 parts by weight of the same calcium oxide powder as used in Example 1 and the above-mentioned high-density polyethylene were melt-kneaded at about 220°C by a three-layer coextrusion method, followed by an inflation method. The film was formed into a tubular film with a diameter of 3001111K (7).

When the cross section of this tubular film was examined, the thickness of the polyethylene layers in the inner and outer layers was about 20 μm, and the thickness of the polyethylene layer containing calcium oxide in the middle layer was about 40 μm.

Next, this tubular film was placed in a cabin filled with chlorine gas at room temperature for 1 hour.
It was brought into contact with chlorine gas by staying there for a certain period of time.

The tubular film thus obtained could be cut and heat-sealed in the same way as ordinary polymeric materials, and bags of any shape could be made.

When the active chlorine content in this tubular film was analyzed, it was found to be in the 2 weight range.

A bag with a depth of 300+78 was made from this tubular film.

Example 3 A mixture of 100 parts by weight of high-density polyethylene and 100 parts by weight of the same calcium oxide powder as used in Example 1 and the above polyethylene were melt-kneaded at about 220°C and formed by a three-layer coextrusion blow molding method. A polyethylene bag bottle with a three-layer structure was molded.

The thickness of the inner and outer polyethylene layers is 100μ each, and the thickness of the middle layer of polyethylene containing calcium oxide is 200μ.
Met.

This bottle has a body diameter of 1201n1rL1, a height of 150cm, and a diameter of 5Qim.

Next, the above-mentioned bottle was allowed to remain in a cabin filled with chlorine gas at room temperature for about 5 hours to be brought into contact with chlorine gas, thereby obtaining a sterilizing polyethylene bottle of the present invention.

Example 4 The films of the present invention obtained in Examples 1 and 2 were cut to prepare square films each having a vertical and horizontal length of 300 mm.

Furthermore, as a comparison, a square high-density polyethylene film having a thickness of 80 μm and a vertical and horizontal length of 3007 nm was prepared.

Next, place the above three types of films on the table in the culture room during the daytime.
After extending the time, they were extracted with physiological saline and cultured for general bacteria and mold, and the results shown in Table 2 regarding the bactericidal efficacy of the film against airborne bacteria were obtained.

The results in the above table show that the film of the present invention has excellent bactericidal effect.

Example 5 A wet towel (length and width: 260 mm x 28 Qim) having a general bacteria count of approximately 10 x 103 cells/sheet was prepared in Example 2.
Each sample was sealed in the bag of the present invention obtained in .

Separately, as a comparison, the thickness is 80μ, and the length and width are 30μ each.
07XiX The wet towels were sealed in the same way in a 300 mm polyethylene bag, and stored in a constant temperature and humidity chamber at 40°C and relative humidity of 100 ot for 48 hours, then taken out and the number of general bacteria attached to each towel. When measured, the results shown in Table 3 below were obtained.

The results in the above table show that the bags of the present invention have significantly superior bactericidal effects.

Example 6 10g of raw beef meat was placed in the bag of Example 1 and the bag of Example 2 and heat-sealed, and the bottle of Example 3 was also placed in a 10μ bottle and sealed tightly.

Separately, as a comparison, a regular polyethylene bag (thickness 8
0μ, 30 (I17AX300?W71L) also 109
Add raw meat and heat seal.

When these were left in a constant temperature bath at 40°C for 48 hours and then opened, a strong putrid odor was felt from the comparison bag, but no putrid odor was felt from the bags and bottles of the present invention. .

Example 7 Freshly made bread that does not use preservatives is prepared in advance for 22 hours.
After leaving it in a room at ~25°C for 3 hours, each piece was placed in the same packaging material used in Example 4, sealed, and placed in a constant temperature and humidity chamber at 20~25°C and relative humidity of 80%. After storing the bread for two weeks, we opened the bag and observed the growth of mold, and found that there was no mold at all on the bread made using the bag of the present invention, whereas the bread that was stored in the regular polyethylene bag for comparison was There was blue mold all over the bread.

Claims (1)

[Claims] 1. 100 parts by weight of a thermoplastic organic polymer, calcium,
A sterilizing polymer material containing 0.001 to 300 parts by weight of magnesium or lithium hypochlorite or a mixture thereof as a main component. 2 100 parts by weight of thermoplastic organic polymer, calcium,
A method for producing a bactericidal polymeric material, which comprises reacting a polymeric material containing 0.5 to 300 parts by weight of a magnesium or lithium oxide or a mixture thereof as a main component with chlorine in the presence of water. 3 100 parts by weight of thermoplastic organic polymer, calcium,
0.5 to 300 parts by weight of an oxide of magnesium or lithium or a mixture thereof and 0.5 parts by weight of a hydroxide of the above metal.
A method for producing a germicidal polymeric material, which comprises reacting a polymeric material containing 300 parts by weight as a main component with chlorine gas. 4. The polymer material is prepared by melt-kneading 100 parts by weight of a thermoplastic organic polymer and 0.5 to 300 parts by weight of an oxide of calcium, magnesium or lithium, or a mixture thereof, and then forming the material into a film, sheet or plate. Claim 3, wherein the metal oxide in the molded product is converted from 0.1 to 100% into the metal hydroxide by reacting the obtained molded product with water. A method for producing a bactericidal polymeric material. 5 The polymeric material is 100 parts by weight of a thermoplastic organic polymer, 0.5 to 300 parts by weight of an oxide of calcium, magnesium or lithium, or a mixture thereof, and 0.05 to 5 parts by weight of the hydroxide of the metal. 4. The method for producing a sterilizing polymeric material according to claim 3, wherein the sterilizing polymeric material is formed into a film, sheet, or plate after melting and cross-mixing.