JPH09263508A - Antimicrobial treated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject flexible treated material large in adhesivity to thin oxide films, excellent in the antimicrobial property, enabling to select the materials of substrates in a wide range, and useful for plastic bags, etc. SOLUTION: This antimicrobial treated material 10 is obtained by forming a thin oxide film 12 having a thickness of 20-500nm and containing Ag and one or more kinds of elements selected from the group consisting of Mg, Al and Si on the surface of a substrate 11 comprising a plastic film or paper. Therein, the content of the Ag, the content of one or more kinds of the Mg, the Al and the Si, and the content of oxygen in the thin oxide film are preferably 19-80at.%, 0.4-40at.% and 19-60at.%, respectively. A material for the substrate includes various kinds of plastics such as polyvinyl chloride and polyvinylidene chloride, Japanese or Western papers such as roughened paper and fine quality paper, and glass substrates.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a disposable substrate whose surface is subjected to antibacterial treatment. More specifically, the present invention relates to a plastic film for packaging foods, cleaning products and the like, a plastic bag, a garbage bag, a toilet seat paper sheet and the like, the surface of which has been subjected to antibacterial treatment.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an antibacterial treated product of this kind, silver is vapor-deposited on the surface of a substrate such as a synthetic resin film or paper, and then this silver is selected from the group consisting of chlorine, bromine and iodine. There has been proposed a method for producing a bactericide for water treatment, which comprises reacting with a halogen component to convert it into silver halide (JP-A-49-48824). According to this method, a porous thin layer of silver halide can be obtained, and the elution of silver ions can be controlled by the surface structure of the thin layer. For this reason the product is convenient as a bactericide for water treatment. In addition, since the thin layer has a porous structure, its true surface area is large, so when it is placed in water, it has high solubility and can be installed as a flat plate piece in a water purifier. There is no danger of Further, as an antibacterial treated product, an antibacterial film sheet is disclosed in which a first film made of silver or copper is further formed on a resin film substrate, and a second film of a phosphazene-based curable resin is further formed thereon. (JP-A-4-352964). This antibacterial treated product has a high surface hardness (pencil hardness 9H) and is a detergent,
The surface has a second film made of phosphazene curable resin that is resistant to cosmetics and various oils, so the surface is hard and is not easily scratched, and dirt is not easily attached. . Further, the volatilization of the solvent in the second film facilitates the formation of pinholes in the second film, and the pinholes formed at this time slowly dissolve the silver or copper metal ions of the first film. And has an antibacterial effect.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
In the method disclosed in Japanese Patent No. 824, since chlorine is released under reduced pressure when polyvinyl chloride or the like is used for the substrate,
The substrate has a problem that it is limited to substances that do not react with silver halide. Further, in the antibacterial film sheet disclosed in the above-mentioned JP-A-4-352964, when the second antibacterial film sheet has a high surface hardness, the application of the antibacterial film sheet is a bag or sheet requiring flexibility. In addition, the adhesion of the first and second coatings to the substrate was not necessarily strong, and the first and second coatings were easy to peel off during use. Also, two films, a first film and a second film, had to be formed, which made manufacturing complicated and pushed up the product cost.

An object of the present invention is to provide an antibacterial treated product having a relatively strong adhesion of an oxide thin film and a high antibacterial property. Another object of the present invention is to select a wide range of materials for the substrate from plastic films or papers, to apply it to bags and sheets that require flexibility, and to have an antibacterial structure that is simple and easy to manufacture. To provide processed products.

[0005]

As shown in FIG. 1, the invention according to claim 1 is selected from the group consisting of Ag, Mg, Al and Si on the surface of a substrate 11 made of a plastic film or paper. An oxide thin film 12 containing one or more elements is formed, the content of Ag in the oxide thin film 12 is 19 to 80 at%, and one or two of Mg, Al and Si are included. Antibacterial treatment product 1 having a seed content of 0.4 to 40 at% and an O content of 19 to 60 at%
0. When only Ag is deposited, the adhesion to the substrate is not sufficient, and as an oxide together with elements such as Mg, Al and Si, for example, an oxide thin film containing Ag and Mg or an oxide containing Ag and Al. By forming a thin film, the adhesive force is increased. The invention according to claim 2 is the invention according to claim 1, wherein the oxide thin film 12 has a thickness of 20 to
The antibacterial processed product 10 has a thickness of 500 nm. Oxide thin film 1
By setting the thickness of 2 in the range of 20 to 500 nm, the oxide thin film adheres relatively strongly.

The invention according to claim 3 is the antibacterial treatment product 10, characterized in that a SiO ₂ thin film interspersed with Ag particles is formed on the surface of a substrate 11 made of a plastic film or paper. The invention according to claim 4 is the invention according to claim 3, wherein the oxide thin film 12 containing Ag and Si is formed on the surface of the substrate 11 made of a plastic film or paper.
And the content of Ag in the oxide thin film 12 is 19 to 2
0 at% and Si is 27 to 28 at%,
The antibacterial treatment product 10 has an O content of 53 to 54 at%. With the above composition, it is possible to form a SiO ₂ thin film in which Ag particles are scattered on the surface of the substrate.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. As the substrate material of the present invention, various plastic films such as polyvinyl chloride, polyvinylidene chloride, polyethylene, polyester, polycarbonate, polyimide, and polyamide, or Japanese-Western paper such as rough surface paper and high-quality paper, or a glass substrate is used. be able to. An oxide thin film containing Ag is formed on one side or both sides of this substrate. This thin film is formed by sputtering as follows depending on the material of the substrate, the use of the antibacterial material, and the like. The first method uses an Ag target as the Ag source, or
_{Using 2} O target, M as Mg, Al, Si source
g, Al, Si target, or MgO,
An oxide thin film is formed by multi-source sputtering using a SiO ₂ or Al ₂ O ₃ target. As a second method, an Ag ₂ O target and MgO, SiO ₂ , Al ₂
An oxide thin film is formed by sputtering using a mixture target of one kind or two kinds of O ₃ . A
The proportion of g and one or two of Mg, Al, and Si and O is at% and is selected from the following range.

Ag: (one or two of Mg, Al and Si): O = 19 to 80: 0.4 to 40:19 to 60 Here, Ag is at least 19 at in order to obtain antibacterial properties.
% Must be included. One or two of Mg, Al and Si is at least 0.4a for good adhesion.
It is necessary to include t%. O must be contained at least 19 at% for good adhesion. In particular, MgO has an ethylene absorbing action to maintain the freshness of plants. The atmosphere during sputtering has an Ar partial pressure of 5 × 10 ^−4.
Up to 5 × 10 ^-3 torr and O ₂ partial pressure of 1 × 10 ^-4 torr
A mixed gas atmosphere of r or more is preferable.

[0009]

Next, examples of the present invention will be described together with comparative examples. (a) Confirmation of antibacterial film composition dependence <Examples 1 to 8> In order to confirm the antibacterial film composition dependence, eight kinds of oxide thin films (hereinafter , AgMgO film) Corning 7059
It was formed on the surface of a glass substrate made of F glass. In order to measure these compositions, eight kinds of AgMgO films were formed under the same conditions on the surface of the Ta substrate which was inactive against Ag, Mg, and O. All film thicknesses were about 0.1 μm. All these film formations were performed by reactive high frequency sputtering of co-sputtering. An Ag plate and a Mg plate were used as sputtering targets, the distance between the Ag target and the Mg target was set to about 20 cm, and the distance between the line connecting both targets and the substrate was set to about 20 cm. Argon partial pressure is 1 × 10 ^{−3 in} the atmosphere during sputtering.
A mixed gas atmosphere having an O ₂ partial pressure of 5 × 10 ⁻⁴ torr was set at torr. In order to change the contents of Ag, Mg and O, the high frequency power on the Ag side was set to two types, 100 W and 400 W, while the high frequency power on the Mg side was kept at 400 W. In addition, while changing this power, the glass substrate is changed to the above 2
Ag from the Mg target side while maintaining a distance of 0 cm
It was shifted to the target side in four steps.

<Examples 9 to 12> In order to confirm the dependence of the antibacterial property on the film composition, the contents of Ag, Al and O were changed to 4
Similar types of oxide thin films (hereinafter referred to as AgAlO films) were formed on the surface of a glass substrate made of Corning 7059F glass in the same manner as in Example 1. The atmosphere during sputtering was the same as in Example 1. The specific method of changing the contents of Ag, Al and O was the same as in Examples 1 to 8. However, the high frequency power on the Ag side was 100 W, while the high frequency power on the Al side was 400 W.

<Examples 13 to 16> In order to confirm the dependency of antibacterial property on the film composition, four kinds of oxide thin films (hereinafter, referred to as AgSiO films) having different contents of Ag, Si and O were used in Example 1. It was formed on the surface of a glass substrate made of Corning 7059F glass in the same manner as in. The atmosphere during sputtering was the same as in Example 1. The specific method of changing the contents of Ag, Si and O was the same as in Examples 1 to 8.
Even if the SiO ₂ target is used as the Si source, no substantial difference is caused in the film characteristics.
A SiO ₂ target was used as the i source. The high frequency power on the Ag side is kept at 100 W, while the high frequency power on the Si side and S
The high frequency power on the iO ₂ side was 400 W, respectively.

Example 17 In order to confirm the dependency of antibacterial property on the film composition, an oxide thin film (hereinafter referred to as AgMgAlSiO film) having different contents of Ag, Mg, Al, Si and O was used as Example 1. Similarly, it was formed on the surface of a glass substrate made of Corning 7059F glass. The atmosphere during sputtering was the same as in Example 1. Ag, Mg and A
The specific method of changing the contents of l, Si, and O was the same as that in Example 1 except that the Al chip and the Si chip were mounted on the Mg target. Comparative Example 1 Example 1 in which no oxide thin film is formed
A glass substrate made of the same Corning 7059F glass was used as Comparative Example 1.

<Antibacterial Confirmation Test> An antibacterial confirmation test was conducted by a method based on the bacterial count method. That is, Examples 1 to
AgMgO film, AgAlO film on each of the 17 glass substrates,
0.1 ml of 10 ⁶ cells / ml of Staphylococcus aureus solution was dropped on each surface of the AgSiO film, the AgMgAlSiO film and the glass substrate of Comparative Example 1, cultivated at 30 ° C., and after 24 hours, the bacteria were recovered with distilled water. The number of bacteria was measured. On the other hand, T
a AgMgO film formed on the surface of the substrate, AgAlO
The composition of the film, AgSiO film and AgMgAlSiO film is E
It was measured by PMA (electron probe microanalysis). The number of bacteria measured, the AgMgO film, the AgAlO film,
Table 1 shows the compositions of the AgSiO film and the AgMgAlSiO film.

[0014]

[Table 1]

As is clear from Table 1, Example 13A
Antibacterial properties were observed in all the treated products from the oxide thin film having a g content of about 20% to the oxide thin film of Example 8 having an Ag content of about 80%. On the other hand, bacteria were detected on the glass substrate of Comparative Example 1.

(B) Confirmation of Film Composition Dependence of Film Adhesion Force on Substrate <Examples 18 to 22> It was investigated whether the adhesion force of the oxide thin film to the substrate changes depending on the film composition. A commercially available wrap for food packaging (polyvinylidene chloride) is used as a base, the wrap is cut into a size of JIS A row No. 4, and the surface of the base is sputtered under the conditions shown in Table 2 to obtain an AgMgO film, AgAlO. A film, an AgSiO film and an AgMgAlSiO film were formed. The film thickness of one substrate was not uniform, and was about 0.02 μm at the thinnest portion and about 0.14 μm at the thickest portion. The other sputtering conditions of Example 18 were the same as those of Examples 1 to 4, and the other sputtering conditions of Example 19 were those of Examples 1 to 4.
8 and other sputtering conditions of Example 20 were the same as those of Examples 9 to 12. The other sputtering conditions of Example 21 were the same as those of Examples 13 to 16, and the other sputtering conditions of Example 22 were the same as those of Example 17. <Comparative Example 2> Ar partial pressure of 1 × 10 ^{−3 for} only Ag target
Sputtering was performed under the conditions of torr, target power of 100 W, and a distance between the target and the substrate of 20 cm.
The Ag film was formed on the substrate of the same commercial food packaging wrap as 8.

<Adhesiveness Confirmation Test> The wraps having the oxide thin film formed in Examples 18 to 22 were spread, and the wraps having no other oxide thin film formed on the films on the surfaces of these wraps were similarly spread. They were rubbed so that they would be pressed by hand from above the lever, and they were in close contact. Then, the adhered wrap was slowly peeled off, and it was examined whether the thin film on the surface of the laps of Examples 18 to 22 was peeled off at this time. Table 2 shows the results.
The Ag film of Comparative Example 2 became fine powder immediately after the film was formed on the surface of the wrap, and the Ag film spontaneously peeled off from the wrap without adhering another wrap.

[0018]

[Table 2]

As is clear from Table 2, Examples 18-2
All of the thin films of No. 2 did not peel off even if another wrap was adhered and peeled off. These thin films contained 19 at% or more of O and showed sufficient film adhesion.

(C) Confirmation of Freshness Retention of Fresh Flower <Example 23> In order to confirm the freshness retention of fresh flower, the same wrap as in Example 18 was used as a substrate, which was 15c in length.
After being cut into m and 10 cm in width, sputtering was performed under the same conditions as in Example 18 to form an AgMgO film. The film thickness is not uniform for one substrate, and is about 0.
It was about 0.14 μm at the thickest part of 02 μm.

<Example 24> In order to confirm the freshness of fresh flowers, a Kent paper having a size of row A of JIS No. 4 was used as a substrate, and an AgMgO film was formed by sputtering under the same conditions as in Example 18. The film thickness of one substrate was not uniform, and was about 0.15 μm at the thinnest portion and about 0.4 μm at the thickest portion. <Comparative Example 4> The same Kent paper as in the above example was used as Comparative Example 4 except that the AgMgO film was not formed.

<Freshness preservation confirmation test of fresh flowers> As fresh flowers,
Four branches of commercially available cut flowers (product name: Denfare) were prepared. Each branch had many petals as shown in FIGS. The water passed through the household water purifier was put in four containers, placed indoors, and four branches were soaked in water in each container for 8 days. During storage, room temperature was maintained at 20-21 ° C and relative humidity at 35-40%. The wrap with the AgMgO film of Example 23 was dipped in the water of the first container before dipping the branches. Nothing other than the branches was immersed in the water in the second container. This method is referred to as Comparative Example 3. The water in the first and second containers was not changed for 8 days. The branch entirely covered with Kent paper with the AgMgO film of Example 24 was immersed in water in the third container. The branches covered with Kent paper of Comparative Example 4 were immersed in water in the fourth container. The water in the third and fourth containers was changed once a day.

After 8 days, the degree of change in the flower axis, petals and buds was observed. Further, regarding the water in the first and second containers, the number of viable bacteria and the number of molds in the water were measured after 14 days had passed. Table 3 shows the results.
FIG. 2 shows a photograph of the morphology of branches, petals and buds immersed in water in which the wrap with the AgMgO film of Example 23 was immersed for 8 days. Fig. 3 shows a photograph of the buds and petals that had fallen off from the branches after 8 days. FIG. 4 shows a photograph of the morphology of the branches and petals of Comparative Example 3 immersed in water in which nothing was dipped except the branches for 8 days. FIG. 5 shows a photograph of the morphology of the petals that had fallen off from the branch after 8 days. FIG. 6 shows a photograph of the morphology of branches, petals and buds covered with Kent paper with an AgMgO film of Example 24 and soaked in water for 8 days. FIG. 7A of Comparative Example 4
3 shows photographs taken of the morphology of branches, petals and buds covered with Kent paper without gMgO film and soaked in water for 8 days. FIG. 8 shows a photograph of the morphology of the petals that have fallen off from the branches after 8 days.

[0024]

[Table 3]

As is clear from FIGS. 2 to 8 and Table 3,
Freshness of fresh flowers after 8 days was AgM of Example 24.
A cut flower covered with Kent paper with a gO film and changed every day,
A cut flower of Comparative Example 4 covered with Kent paper without AgMgO film and subjected to water change every day, a cut flower of Example 23 immersed in water with wrap with AgMgO film and non-wrapped water of Comparative Example 3 immersed. The order was cut flowers without water change. Due to the antibacterial property of Ag, it is possible to obtain a freshness-retaining effect by covering the plant with an AgMgO film. If the wrap with the AgMgO film is soaked in water, the freshness is about the same as daily replacement without water exchange. It was found that a retaining effect was obtained.

(D) Confirmation of Freshness Retention of Food <Example 25> In order to confirm the freshness retention of food, the same wrap as in Example 18 was used as a substrate, and this was used in JIS A row 4 size. After cutting, sputtering was performed under the same conditions as in Example 18, and AgMgO was formed on the surface of this lap.
A film was formed. The film thickness of one substrate was not uniform, and was about 0.02 μm at the thinnest portion and about 0.14 μm at the thickest portion. <Comparative Example 5> A lap in which an AgMgO film was not formed on the surface of Example 25 was used as Comparative Example 5.

<Freshness preservation confirmation test of food> Thickness 2 cm,
Four pieces of bread having a length of 4 cm and a width of 4 cm were prepared, and two bread pieces each were wrapped with the wrap with the AgMgO film of Example 25 and the wrap without the film of Comparative Example 5 and stored for 8 days. During storage, room temperature was maintained at 20-21 ° C and relative humidity at 35-40%. After 8 days, the occurrence of mold on bread was observed. The results are shown in Table 4.

[0028]

[Table 4]

<Confirmation of Ag Ag Fine Particles> Example 1
C with support film for transmission electron microscope (TEM) under the condition of 3
When a film was formed on the u grid and observed by TEM, it was confirmed that black speckled Ag particles were scattered on the SiO ₂ thin film as shown in FIG.

[0030]

As described above, according to the present invention, it is possible to obtain an antibacterial treated product having a relatively strong adhesion of the oxide thin film and a high antibacterial property. In addition, the material of the substrate can be selected from a wide range of plastic films or papers, can be applied to bags and sheets that require flexibility, and has an excellent effect that the structure is simple and the manufacturing is easy.

[Brief description of drawings]

FIG. 1 is a partially enlarged cross-sectional view of an antibacterial treatment product of the present invention.

FIG. 2 is a photograph showing the morphology of branches, petals, and buds immersed in water in which the wrap with an AgMgO film of Example 23 was immersed for 8 days.

FIG. 3 is a photograph showing the morphology of buds and petals that have fallen off the branches after 8 days.

FIG. 4 is a photograph showing the morphology of the branches and petals of Comparative Example 3 immersed in water in which nothing was dipped except the branches for 8 days.

FIG. 5 is a photograph showing the morphology of petals that have fallen off from the branches after 8 days.

FIG. 6 is a photograph showing the morphology of branches, petals and buds covered with Kent paper with an AgMgO film of Example 24 and soaked in water for 8 days.

7 is a photograph showing the morphology of branches, petals and buds covered with Kent paper without an AgMgO film and dipped in water for 8 days in Comparative Example 4. FIG.

FIG. 8 is a photograph showing the morphology of petals that have fallen off from the branches after 8 days.

9 is an AgSiO film formed under the conditions of Example 13. FIG.
The TEM photograph figure of a membrane.

[Explanation of symbols]

 10 Antibacterial treated material 11 Base material 12 Oxide thin film

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─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A01N 59/06 A01N 59/06 Z A61L 2/16 A61L 2/16 A B65D 81/28 B65D 81 / 28 C C01G 1/02 C01G 1/02

Claims (4)

[Claims] 1. An oxide thin film (12) containing Ag and one or more elements selected from the group consisting of Mg, Al and Si on the surface of a substrate (11) made of a plastic film or paper. And the Ag content of the oxide thin film (12) is 19 to 80 at%.
And the content of one or two of Mg, Al, and Si is 0.4 to 40 at%, and the content of O is 19 to
An antibacterial treated product characterized by being 60 at%. 2. The oxide thin film (12) has a thickness of 20 to 500 n.
The antibacterial treated product according to claim 1, which is m. 3. An antibacterial treated product, characterized in that a SiO ₂ thin film interspersed with Ag particles is formed on the surface of a substrate (11) made of a plastic film or paper. 4. An oxide thin film (12) containing Ag and Si is formed on the surface of a substrate (11) made of a plastic film or paper, and the content of Ag in the oxide thin film (12) is 19-2.
0 at% and Si is 27 to 28 at%,
The antibacterial treated product, wherein the O content is 53 to 54 at%.