JPH02258256A - Film containing copper ion and/or silver ion - Google Patents

Abstract

PURPOSE:To provide a film which displays anti-fungal properties stably for a long period of time and does not reduce its strength, by a method wherein a layer obtained by dispersing perticles comprised by compounding a compound capable of eluting a copper ion and/or a silver ion with a soluble glass is caused to exist on one and/or both sides. CONSTITUTION:By soluble glass is meant such which has a grain size passing 500mum mesh but not passing 350mum and 0.001-100mum/hr of a glass particle diameter reducing rate (mum/hr) in air bubble agitation at 40 deg.C when 1g of glass particles is charged in 500ml of distilled water. Gel sol method where a copper compound or a silver compound is dispersed in a soluble glass, or gel is prepared with a copper compound, a silver compound and glass ingredient, which is burnt in a range of 750-1200 deg.C, is available as a manufacturing method of the soluble glass containing a copper compound or a silver compound. It is preferable that the copper compound and silver compound contained in the soluble glass is respectively 10-50wt.% and 0.5-2.0wt.%. The quantity of a metallic ion contained in the film is 0.001-10wt.% and 0.0001-0.5wt.% respectively for the copper ion and silver ion from a view point of anti-fungal properties.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a film having antibacterial properties.

(Prior Art) Films have traditionally been used in a wide range of areas such as daily life-related materials, building materials, and packaging materials.
Bacteria and mold can grow under the influence of humidity, causing discomfort due to bad odors, corrosion of contents, and abnormalities.

Therefore, in recent years, various attempts have been made to provide films with antibacterial properties.

That is, it has been known that metals such as copper and silver have antibacterial effects, and this property has been utilized to develop films containing fine powder of water-insoluble copper compounds or silver compounds (Japanese Patent Laid-Open No. 61-138658). No. 2) has been proposed.

(Problems to be Solved by the Invention) However, with the above-mentioned method, antibacterial properties cannot be obtained unless a large amount of fine powder of a metal compound is added, and film strength is impaired. It was difficult to obtain a sex film.

In view of the above drawbacks, the present invention, as a result of extensive research, provides a film that stably exhibits antibacterial performance over a long period of time and does not impair film strength.

(Means for Solving the Problems) That is, the present invention provides i- in which particles made by blending a compound capable of eluting copper ions and/or silver ions into soluble glass are present on one and/or both sides. It is a film that does

In the present invention, the compound that can elute copper ions and/or silver ions may be any compound that becomes metal ions or metal ion-forming substances (substances that easily become metal ions) in or after elution from the glass. is Cu2O as a copper compound.

Cu, S, Cub, CuS, copper halide, Cu
Inorganic compounds such as (OH)z and Cu5Oa, and organic compounds such as copper acetate, copper aminoacetate, and copper formate can be used. In addition, as silver compounds, AgzO, AgtS
, HegNO, , Silver halide, A mouth SO4, AgzCO
Inorganic compounds such as s, and organic compounds such as silver acetate, silver oxalate, and silver salicylate can be used.

From the viewpoint of compatibility with soluble glass and metal content, Cu
O, Cu0g, or Ag, O is preferable.

The meltable glass of the present invention refers to the particle size of 500 μm bath 350
1 g of glass particles of μm remaining were put into 500 μm of distilled water,
Reduction rate of glass particle size during air bubble stirring at 40°C (
expressed in μm/hr), 0.001 to 100 B m
/hr, preferably 0.005 to 60 μm/hr. Satisfactory antibacterial performance cannot be obtained if the rate of decrease is less than 1 μm/hr.
If it exceeds hr, stable antibacterial performance cannot be obtained over a long period of time.

Specifically, the meltable glass of the present invention is 5i (h, BzOs
+P20. Network-forming oxides such as NazO, Kid
, Cab.

MgO, Bad, A1*Os+ ZnO+ Ti0g
The solubility can be adjusted by changing the composition ratio of these oxides.

A method for manufacturing meltable glass containing a copper compound or a silver compound is to disperse it in molten glass or to make a gel with a copper compound, a silver compound and a glass component.
There is a gel-sol method in which the material is fired in a temperature range of 1200''C.The melting method does not provide good dispersibility, so the gel-sol method is preferred.

A copper compound or a silver compound can be dispersed in soluble glass and made into fine particles by a conventional method. The particle size may be of a size that does not impair the mechanical properties of the film, and is 10 μm or less, preferably 3 μm or less.

The copper compound contained in the soluble glass is 10 to 50% by weight,
The silver compound content is preferably 0.5 to 20% by weight.

The amount of metal ions contained in the film is 0.001 to 10% by weight for copper ions and 0.001 to 10% by weight for silver ions in terms of antibacterial performance.
0001 to 0.5% by weight.

Resins that can be used in the film of the present invention include polyurethane resins, acrylic resins, silicone resins, polyvinyl alcohol resins, polystyrene resins, nylon resins, polyester resins, polycarbonate resins, fluorine resins, and polyethylene resins. , polypropylene resin, polyvinyl chloride resin, acrylonitrile-butadiene-styrene resin, and the like.

The film of the present invention is used as a single-layer or multi-layer film depending on its purpose, and protects the contents from bacteria and molds existing outside.

Alternatively, since the purpose is to prevent the growth of bacteria and mold within the contents, it is most effective to place the antibacterial film on one and/or both sides of the outermost layer.

This is because the metal compound blended into the film dissolves appropriately as the glass melts, providing stable antibacterial properties over a long period of time.

After blending and dispersing meltable glass containing a compound capable of eluting copper ions and/or silver ions into the film according to the present invention, coating method, inflation method, T-
It can be manufactured using the Gouy method, calendar method, casting method, etc.

Additionally, various additives commonly used in films may be included as necessary.

For example, heat stabilizers, antioxidants, light stabilizers, smoothing agents, water clarifying agents, hardening agents, plasticizers, thickeners, foaming agents, glossing agents,
Flame retardants, pigments, etc.

The film of the present invention can be used not only as a stand-alone film, but also as a laminate with fiber materials, papers, and metal foils, depending on the application. Lamination methods include polyurethane, acrylic,
There are a method of joining using a rubber-based adhesive or the like, a method of joining the film of the present invention by melt extrusion, and the like, but these are not particularly limited.

The antibacterial property of the film of the present invention shows a strong bactericidal effect against Staphylococcus aureus and Escherichia coli.

It also shows excellent resistance to molds other than bacteria.

Example 1 95 parts of low density polyethylene with a specific gravity of 0.92 and a nucleating agent (
0.5 part of bicarbonate of soda, 0.5 part of citric acid) and BxOs
29% by weight, 5iOz 51% by weight, Nato 1
0% by weight, Zn04% by weight, A11as 1% by weight, A
g, meltable glass consisting of 05% by weight (average particle size 3
After blending 4 parts of polyethylene (100 microns) and heating and melting, a foamed polyethylene film (thickness: 100 microns) was obtained using the T-die method. These are further processed by extrusion lamination of polyethylene (thickness 20 microns) and nylon film (thickness 1
5 micron) and laminated with nylon/polyethylene/
A laminated film composed of foamed polyethylene containing soluble glass was created.

Comparative Example 1 was a laminated film using foamed polyethylene that did not contain soluble glass.

Example 1 Using the film of Comparative Example 1, antibacterial properties were evaluated by the following method.

Test method (1) Bacteria count measurement medium for bacteria...normal bouillon agar medium) or M
-TOE agar medium (Difco) For fungi...Potato dextrose agar) (2) Preparation of bacterial liquid For bacteria...Normal bouillon liquid medium at 37°C - After culturing overnight, change the medium to M/15 It was diluted with phosphate buffer (PH=7).

For fungi... Potato dextrose agar slant medium 25
After culturing at °C for 17 hours, a portion of the medium was taken and suspended in a glucose-peptone liquid medium, and after culturing at 30°C overnight, a portion of the medium was diluted with M/15 phosphate buffer.

(3) Preparation of Test Piece Example 1 Comparative Example 1 was cut to a diameter of 4.7 cm to prepare a test piece.

(4) Operation of test pieces 1) Inoculate each test piece with a bacterial solution so that the number of bacteria becomes 10-104.

2) The test piece of Comparative Example 1 has a storage diameter, the test piece of Example and the test piece of Comparative Example have been cultured at 37°C for 24 hours for bacteria, and for 72 hours at 30°C for bacteria. Bacteria are in ordinary bouillon liquid medium and fungi are in glucose. Wash out the bacteria on the test piece using peptone liquid medium 1 (ld).

3) The number of viable bacteria was measured for this washing solution by the smearing method on the agar medium in (1), and the results are shown in Table 1.

Table 1 below: From the above, the antibacterial effect of the soluble glass-containing film is clear.

Example 2 97 parts of low density polyethylene with a specific gravity of 0.92 and a nucleating agent (
0.5 part of bicarbonate of soda, 0.5 part of citric acid) and BxOs
36% by weight, Sing 17% by weight, NazO5
After blending 2 parts of soluble glass (average particle size 2 microns) consisting of 42% by weight of Cu0 and heating and melting, T-
A foamed polyethylene film (thickness 100 microns) was obtained by the Gouy method.

This is then laminated on both sides of high-density polyethylene cross yarn (basis weight 32 g) by extrusion lamination of polyethylene (thickness 20 microns) to form soluble glass-containing foamed polyethylene/polyethylene/high-density polyethylene cross yarn/polyethylene/melting. A sheet having a structure of polyethylene foam containing polyethylene glass was obtained.

Comparative Example 2 was a laminated film using foamed polyethylene that did not contain soluble glass.

Table 2 (Table 2) From the above, it is clear that the antibacterial effect of the soluble glass-containing film is particularly effective as a packaging material when antibacterial films are present on both sides as in Example 2.

(Effect of the invention) The film of the invention has excellent antibacterial performance, and
Since copper ions and/or silver ions can be appropriately eluted, it exhibits stable antibacterial performance over a long period of time.

As a result, films with antibacterial properties can be used for household materials,
It can be widely used in construction materials, packaging materials, etc.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] A film that has a layer on one and/or both sides in which particles are dispersed and is made by blending a compound capable of eluting copper ions and/or silver ions into soluble glass.