JPH10264297A - Antibacterial laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial laminate suitably used for a wall material of a water section of a kitchen or a bathroom needing low water permeability by providing excellent sterilization of fungus and bacteria and breeding suppressing effect. SOLUTION: This antibacterial laminate comprises a metal plate 1, a thermosetting adhesive 3 coating a surface of the plate 1 and being heated, and a resin film 2 containing 0.05 to 30 pts.wt. of antibacterial agent of powder mixed with 100 pts.wt. of the film and adhered onto the adhesive 3 in the state that its high temperature is maintained. The agent has a mean particle size of 1 μm or less, and contains 30 to 80 pts.wt. of silicon carbide or silicon oxide, 10 to 40 pts.wt. of aluminum oxide, 9 to 30 pts.wt. of titanium oxide and 1 pt.wt. or less of silver or copper, and is baked.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate in which a resin film such as a vinyl chloride resin film, a polyolefin resin film, and a fluororesin film is adhered to a metal plate.

[0002]

2. Description of the Related Art A laminated plate in which a resin film is adhered to a metal plate has a lower water permeability than a coated metal plate in which a resin paint is applied to a metal plate, so that a wall material around water, such as a bath wall or a ceiling, is used. Often used for toilet booths, kitchen equipment, etc.
On these laminated plates, a thermosetting adhesive is applied to a metal plate and heated, and a resin film is bonded while the high temperature is maintained. There is a method in which a resin film is heated to a temperature at which the resin film is melted, and a resin film is bonded to the metal plate under the heated state by heat fusion. Bonding the resin film at high temperature is advantageous in terms of manufacturing efficiency and quality control because the bonding is completed instantly, and those with poor adhesion such as polyolefin resin film and fluororesin film are treated at high temperature. The reason for this is that the adhesive strength cannot be obtained unless they are bonded in a heat-sealed state.

[0003]

However, when the above-mentioned laminate is used around water in a bath, kitchen, toilet, etc., molds and other bacteria tend to propagate. 2. Description of the Related Art Conventionally, as a means for suppressing sterilization and propagation of bacteria, an antibacterial agent is added to a resin paint applied to a metal plate. As the antibacterial agent, an organic eluting antibacterial agent such as a thiazole type or an imidazole type, or a zeolite to which a bactericidal metal ion such as silver ion or zinc ion is adsorbed is known. However, an organic antibacterial agent is not suitable for bonding a resin film at a high temperature, such as the above-mentioned laminate, since the active ingredient is easily decomposed by heat when exposed to a high temperature. In the latter zeolite,
Since it is sterilized by direct contact with bacteria, if water adheres, the antibacterial effect is reduced by half, and since metal is present in the form of metal ions, dust is easily charged. Also, the antibacterial effect is reduced by half.

SUMMARY OF THE INVENTION The present invention has been made to solve such a problem, and it has been proposed to disinfect fungi and bacteria in a low water-permeable laminate in which a resin film is bonded to a metal plate with an adhesive or heat fusion. And increase the effect of suppressing reproduction,
Moreover, an object of the present invention is to provide an antibacterial laminate having an excellent sterilizing effect even when water or dust adheres.

[0005]

The antibacterial laminate of the present invention is obtained by applying a thermosetting adhesive to a surface of a metal plate and heating the same. 0.05-30 powder antibacterial agent per 100 parts by weight of resin film
The resin film blended by weight is bonded, the antibacterial agent has an average particle size of 1 μm or less, 30 to 80 parts by weight of silicon carbide or silicon oxide, and aluminum oxide 10
-40 parts by weight, titanium oxide 9-30 parts by weight, silver or copper 1
It is fired at a ratio of not more than parts by weight. Instead of bonding the resin film to the surface of the metal plate with a thermosetting adhesive, the resin film can be bonded by heat fusion.

[0006]

[Action] An antibacterial agent comprising the above composition blended in a resin film radiates electromagnetic waves in the infrared region, and resonates water molecules in bacteria that form general bacteria and water molecules of environmental moisture necessary for their propagation. In addition, it excites and inhibits the physiological function of the cells and suppresses the growth of the cells. In addition, since the antibacterial agent emits electromagnetic waves like that, it has an antibacterial effect even in the state of non-contact with bacteria,
Even if water and dust adhere, the antibacterial effect does not decrease.

If the amount of the powdered antibacterial agent is less than 0.05 part by weight per 100 parts by weight of the resin film, a sufficient antibacterial effect cannot be obtained. If the amount exceeds 30 parts by weight, it is difficult to uniformly disperse the resin film. In addition, the moldability of the resin film is reduced. By reducing the average particle size of the antibacterial agent to 1 μm or less, the surface area ratio becomes much larger than that of a conventionally used antibacterial agent of 10 μm or more, and the radiation efficiency of electromagnetic waves in the infrared region from the antibacterial agent component is increased. be able to.

[0008] Silicon carbide and silicon oxide radiate electromagnetic waves in the entire infrared region from the near infrared region to the far infrared region, and further in the range from the ultraviolet region to the water in bacteria and water contained in the breeding environment of bacteria. The molecules resonate and excite, inhibiting the physiology of bacteria. This silicon carbide or silicon oxide is effective if the mixing ratio is 30 to 80 parts by weight.

Aluminum oxide emits electromagnetic waves in the far-infrared region to assist the resonance excitation of the silicon compound. However, the effect of aluminum oxide is weak when it is less than 10 parts by weight, and the effect is saturated when it exceeds 40 parts by weight. Titanium oxide is resonantly excited by external light energy, particularly electromagnetic waves in the ultraviolet region, creates free active oxygen, exerts a bactericidal action, and simultaneously oxidizes and decomposes odor components. However, if the amount is less than 9 parts by weight, the bactericidal property is significantly reduced, and
A remarkable bactericidal effect cannot be obtained even if the amount exceeds 0 parts by weight.

[0010] Silver and copper are antibacterial due to an oligodynamic effect, and also act on silicon carbide, silicon oxide and aluminum oxide and act as a catalyst to enhance the emission of electromagnetic waves. However, silver or copper is preferably used in an amount of 0.1 part by weight or more in order to exert its effect effectively. However, when it exceeds 1 part by weight, there is a possibility that the organic compound is deteriorated.

Since the antibacterial agent is made by baking these inorganic components at a high temperature, even if the resin film is bonded to the metal plate at a high temperature, the antibacterial agent does not thermally decompose.

[0012]

FIG. 1 is a sectional view of an antibacterial laminate according to the present invention. Reference numeral 1 denotes a metal plate, such as a steel plate, a galvanized steel plate, a zinc-aluminum alloy-plated steel plate, a stainless steel plate, or an aluminum plate. The metal plate 1 is previously subjected to a surface treatment such as a surface cleaning treatment or a chemical conversion treatment. 2 is
A resin film bonded with a thermosetting adhesive 3 to the surface of a metal plate 1 which has been surface-treated in advance, such as a vinyl chloride resin film, a polyolefin resin film, or a fluorine resin film.

The vinyl chloride resin film (colored)
It is inexpensive, has excellent adhesiveness and printability, and has good moldability when formed into a laminate. The thickness of the vinyl chloride resin film is 40 to 300 μm, preferably 100 to 300 μm.
150 μm. As the adhesive 3 used for bonding the vinyl chloride resin film, polyester resin,
It is an acrylic resin or a urethane resin, and the coating amount is ^{2 to} 10 g / m ² , preferably 4 to 7 g / m ² .
Heating plate temperature is 150-260 ° C, preferably 190-2 ° C
00 ° C.

Polyolefin resin film (colored)
Is difficult to bond and print, but has no adverse effect on the environment because it does not contain chlorine, and is excellent in chemical resistance as compared with a vinyl chloride resin film. The polyolefin-based resin film includes a polypropylene-based resin film, a polyethylene-based resin film, or a blend thereof. The thickness of this polyolefin resin film is 50 to
It is 300 μm, preferably 100 to 200 μm. The adhesive 3 used for bonding the polyolefin-based resin film is a solvent-dispersed modified polyolefin-based resin, and has a coating amount of ² to 10 g / m ² , preferably 3 to 5 g.
/ M ² . The heating plate temperature is 160 to 260 ° C, preferably 210 to 230 ° C.

The fluororesin film (colored) has poor adhesion, but is excellent in stain resistance and non-adhesion. Examples of the fluorine resin film include a vinylidene fluoride resin film, an ethylene / tetrafluoroethylene copolymer resin film, an ethylene tetrafluoride / perfluoroalkoxyethylene copolymer resin film, and a tetrafluoroethylene resin film. Among them, those with tetrafluoride are particularly excellent in stain resistance and non-adhesion. The thickness of the fluororesin film is 12 ~
100 μm. The adhesive 3 used in the adhesion of the fluororesin film, an epoxy resin or a polyester resin, the coating amount of 2 to 10 g / m ^2, preferably 4-6 g / m ^2. Heating plate temperature is 180 ~ 32
0 ° C.

The fluorine-based resin film (colored) can be heat-sealed. The heating plate temperature at this time is 250 to 350
° C. The thickness of this fluororesin film is 20 to
100 μm.

FIG. 2 shows a schematic diagram of the production line.
The metal plate (coil) 1 is subjected to a surface treatment such as a surface cleaning treatment or a chemical conversion treatment by a surface treatment device 4, and then an adhesive coating device 5
Then, the thermosetting adhesive 3 is applied to the surface of the metal plate 1 and subsequently heated by passing through a heating device 6, the resin film 2 is pressed and bonded by a laminating roll 7 and simultaneously water-cooled from above and below the strip. Take up.

In the above-mentioned ethylene / tetrafluoroethylene copolymer resin film, ethylene tetrafluoride / perfluoroalkoxyethylene copolymer resin film, and tetrafluoroethylene resin film, the coloring pigment is difficult to disperse in the resin. In this case, a colored undercoat layer is formed on the metal plate 1,
What is necessary is just to adhere | attach these resin films on this coloring undercoat layer. When corrosion resistance is required, a rust preventive pigment is incorporated in the undercoat layer. However, the resin film 2 may be uncolored and transparent.

The antibacterial agent blended in the resin film 2 is fired at 700 to 900 ° C. to produce an average particle size of 1 μm or less. The average particle size of each composition of the antibacterial agent is 0.01 to
It is about 0.3 μm. The antibacterial agent is formed by using silicon carbide or silicon oxide, aluminum oxide and titanium oxide as main components, and further adding silver or copper. For more information,
After the above components are atomized and mixed so that the average particle size becomes 0.01 to 0.03 μm, the mixture is fired at a temperature of 700 to 900 ° C., and the fired body is atomized to obtain the average particle size. Was adjusted to 1 μm or less. The mixing ratio of each component is 30 to 80 parts by weight of silicon carbide or silicon oxide, 10 to 40 parts by weight of aluminum oxide, and 9 to 40 parts by weight of titanium oxide.
30 parts by weight, and silver or copper is 1 part by weight or less. The compounding ratio of the antibacterial agent is 0.05 to 30 parts by weight based on 100 parts by weight of the resin film. More preferably, 0.
1 to 5 parts by weight is blended.

[0020]

EXAMPLES Examples 1 to 8 and Comparative Examples 1 and 2 given below.
In common, the composition of the antibacterial agent to be added to each resin film was 50 parts by weight of silicon carbide, 30 parts by weight of aluminum oxide, 29.99 parts by weight of titanium oxide, and 0.01 parts by weight of silver. In Examples 1 to 6, a hot-dip galvanized steel sheet was manufactured by successively performing the steps of chromate treatment, adhesive application, heating, and lamination. Examples 7 and 8 were manufactured in the same manner except that a heat fusion step was performed instead of the adhesive application and heating steps.

Examples 1 and 2 An antibacterial agent having the above composition was blended with 100 parts by weight of a vinyl chloride resin film in Example 1 in an amount of 0.3 parts by weight and in Example 2 in an amount of 5.0 parts by weight. The adhesive used was a polyester resin “SC-611” (manufactured by Sony Chemical). The heating plate temperature was 199 ° C. The thickness of the vinyl chloride resin film is 150 μm.

Examples 3 and 4 The antimicrobial agent having the above composition was added to 100 parts by weight of the polypropylene resin film, 0.3 parts by weight in Example 3 and Example 4
In this case, 5.0 parts by weight were blended. The adhesive used was a modified propylene resin “96A025302pp” (manufactured by Sony Chemical). The heating plate temperature was 216 ° C. The thickness of the polypropylene resin film is 150 μm.

Examples 5 and 6 An antibacterial agent having the above composition was blended with 100 parts by weight of the vinylidene fluoride resin film in Example 5 by 0.3 parts by weight and in Example 6 by 5.0 parts by weight. The adhesive used was an acrylic resin "SC-457" (manufactured by Sony Chemical). The heating plate temperature was 160 ° C. The thickness of the vinylidene fluoride resin film is 40 μm.

Examples 7 and 8 Ethylene / tetrafluoroethylene resin film 100
The antibacterial agent having the above composition is used in an amount of 0.1 part by weight in Example 7 with respect to parts by weight.
3 parts by weight, and 5.0 parts by weight in Example 8 were blended. The heat fusing heating plate temperature was 310 ° C. The resin film thickness is 25 μm.

Comparative Example 1 The same as in Example 1 except that no antibacterial agent was added. Comparative Example 2 Same as Example 3 except that no antibacterial agent was blended.

An antibacterial test was carried out on the antibacterial laminates of the respective examples and comparative examples prepared as described above in the following manner. Antibacterial test An antibacterial test was performed on Staphylococcus aureus, a bacterium. This test method was performed at 35 ° C., 24 ° C. on a standard agar medium.
Using test bacteria cultured for a period of time, the number of test bacteria is 1-3 × 10 ⁷
A test bacterial solution was prepared by adjusting the number of cells to be used per ml. Next, a contact method in which 0.5 ml of the bacterial solution is directly dropped on each test piece and the filter paper is allowed to stand thereon, and a piece of aluminum having a thickness of 1 mm is placed on the test piece and 0.5 ml of the bacterial solution is dropped thereon. And a non-contact method in which a filter paper was allowed to stand thereon. Every 24 hours, 48 hours, 72 hours, and 168 hours from the start of the test, the filter paper was taken out, put in 9.5 ml of sterilized water, 0.1 ml was taken out from the filter paper, smeared and cultured, and the number of viable cells after culture (Pcs / ml) were examined.

The chart in FIG. 3 shows the results of the above antibacterial test. In the chart, the number of viable bacteria is 10 ³ to 10 ⁴ cells / ml.
A sign, the 10 ⁴ to 10 ⁵ cells / ml in ○ mark, ¹⁰⁵ to
⁶ cells / ml is △ mark, 10 ⁶ cells / ml or more are represented by × mark. As is clear from this chart, test pieces 1 to
In Example 8 (Examples 1 to 8), the antibacterial action was clearly observed, and it was found that the longer the elapsed time, the more reliably the propagation of the test bacteria could be suppressed. Especially test pieces 2,4
In Examples 6 and 8 (Examples 2, 4, 6, and 8), 24
At the point when time has passed, it shows sufficient antibacterial action,
From this, it was found that if the compounding amount of the antibacterial agent was as much as 5 parts by weight, a sufficient antibacterial action could be obtained at an early stage. Approximately the same antibacterial results were obtained in both the contact and non-contact methods. In other words, it was confirmed that a sufficient antibacterial action can be exerted even in a portion that is not in direct contact with the test piece, and it was confirmed that the antibacterial action can be exerted even in a portion where water or dust is attached.

[0028]

According to the present invention, the antibacterial agent contained in the resin film adhered to the metal plate radiates electromagnetic waves in the infrared region, and is necessary for water in bacterial cells forming general bacteria and its propagation. Since the water molecules of the environmental moisture are resonated and excited, the physiological function of the cells can be inhibited, and the growth of the cells can be suppressed. Further, since the average particle size of the antibacterial agent is set to 1 μm or less to increase the surface area ratio, the radiation efficiency of electromagnetic waves in the infrared region can be increased accordingly, and the propagation of bacteria can be more effectively suppressed. A laminated board made by bonding a resin film containing an antimicrobial agent to a metal plate has lower water permeability than a coated metal plate coated with a resin paint on a metal plate, and has an antibacterial effect even when water or dust adheres. Because it can be demonstrated, especially in kitchens and baths,
It can be suitably used for antibacterial wall materials around water such as toilets.

[Brief description of the drawings]

FIG. 1 is a sectional view of an antibacterial laminate showing one embodiment of the present invention.

FIG. 2 is a schematic view of a production line for the antibacterial laminate shown in FIG.

FIG. 3 is a table showing the results of antibacterial tests of Examples and Comparative Examples.

[Explanation of symbols]

 Reference Signs List 1 metal plate 2 resin film 3 thermosetting adhesive

Claims (2)

[Claims] 1. A thermosetting adhesive is applied to the surface of a metal plate and heated, and under the condition, on the thermosetting adhesive,
Powder antibacterial agent is 0.0 to 100 parts by weight of resin film
5 to 30 parts by weight of the resin film is mixed, the antimicrobial agent has an average particle size of 1 μm or less, silicon carbide or silicon oxide 30 to 80 parts by weight, aluminum oxide 10 to 40 parts by weight, An antibacterial laminate which is fired at a ratio of 9 to 30 parts by weight of titanium oxide and 1 part by weight of silver or copper. 2. The antibacterial laminate according to claim 1, wherein the resin film is bonded to the surface of the metal plate by heat fusion instead of being bonded by a thermosetting adhesive.