JPH0768656A - Antibacterial acrylic film - Google Patents

Abstract

PURPOSE:To improve weather discoloring resistance, chemical resistance, contamination resistance, etc., by forming of an acrylic resin having specific weight and an antibacterial agent containing a phosphate in which a quaternary ammonium salt compound is adsorbed and fixed as a main ingredient. CONSTITUTION:The antibacterial acrylic film is formed of 100 pts.wt. of an acrylic resin and 0.1-40 pts.wt. of an antibacterial agent containing a phosphate in which a quaternary ammonium salt compound is adsorbed and fixed as a main ingredient. As a material of the film, methyl methacrylate, ethyl methacrylate, propylmethacrylate, etc., are included. The agent contains the phosphate in which the quaternary ammonium salt compound is adsorbed and fixed as a main ingredient, and as the phosphate, zirconium phosphate, titanium phosphate, aluminum tripolyphosphate, etc., are included. This film is used by thermal laminating, in-mold forming or laminating it to various base materials via an adhesive.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic film having antibacterial properties and a wallpaper made thereof.

[0002]

2. Description of the Related Art An acrylic film obtained from an acrylic resin is adhered or laminated to suppress deterioration of weather resistance of a base material, impart design characteristics, and prevent dirt from adhering. It can be prevented and its demand is increasing in recent years.

Plastic materials such as vinyl chloride resin and ABS resin are used outdoors, in kitchens, bathrooms, toilets or washbasins,
Alternatively, when used around water such as home appliances, it is widely practiced to add various antibacterial agents to the resin in order to suppress the growth of bacteria. The acrylic film is used by adhering or laminating it to the plastic product as described above, but if this is done, the antibacterial property imparted to the substrate will be impaired.

[0004] On the other hand, wallpaper has been known to be laminated on a wall or ceiling in a room to improve its appearance. Vinyl wallpaper, inorganic wallpaper and the like are known, but they are liable to be discolored by weathering, easily soiled, and hard to remove stains. Has the problem of. As a countermeasure against this, in some wallpapers, an acrylic, polyester, polyethylene, or other film is attached to the compound layer mainly composed of polyvinyl chloride resin, or acrylic resin, urethane resin, urethane acrylic resin is used. Processing such as coating with paint is performed. Among them, the wallpaper on which the acrylic resin film is laminated is excellent in weathering discoloration, chemical resistance, stain resistance and the like.

Further, the wallpaper used around the water in the kitchen, bathroom, toilet or washbasin in the room is apt to be moldy. Therefore, it is known to add an antifungal agent to an acrylic resin film. However, antifungal agents cannot suppress the growth of bacteria.

Further, nosocomial infections have become a problem in hospitals and the like, and antibacterial properties are required not only in floor materials and curtains but also in wallpaper. In addition, antibacterial wallpaper is required even in places where there are many people with weak resistance, such as nursing homes, nursery schools, and kindergartens.

In order to solve these problems, various antibacterial agents may be added to the acrylic film, but the processing temperature of the acrylic resin is usually about 250 ° C., and the acrylic resin composition containing the antibacterial agent is added. However, there is a problem that it is thermally deteriorated during processing, resulting in poor appearance and discoloration. Further, there is a problem that even an inorganic antibacterial agent which is considered to have excellent heat resistance is discolored during processing or a weather resistance test.

[0008]

SUMMARY OF THE INVENTION The gist of the present invention is to provide an antibacterial agent mainly composed of a phosphate having 100 parts by weight of an acrylic resin and a quaternary ammonium salt compound adsorbed and immobilized therein in an amount of 0.1 to 40 parts by weight. And an antibacterial acrylic film comprising a part and an antibacterial wallpaper formed by laminating the film on a wallpaper support.

The material of the acrylic resin film used in the present invention is not particularly limited, but methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate are used as main raw materials, and if necessary, have 1 to 10 carbon atoms. A homopolymer or a copolymer obtained by using an acrylic ester having an alkyl group of 8, vinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylonitrile or the like as a copolymerization component is used. Furthermore, Japanese Examined Patent Publication No. 62-19309,
JP-A-63-20459 and JP-A-63-7796.
An acrylic resin copolymerized in multiple stages as described in Japanese Patent Publication No. 3 can be used.

The antibacterial agent used in the present invention mainly contains a phosphate having an adsorbed and immobilized quaternary ammonium salt. Examples of the phosphate include zirconium phosphate, titanium phosphate, aluminum tripolyphosphate and the like. Specific examples of the quaternary ammonium salt include aliphatic ammonium halides, benzalkonium halides, cetylpyridinium halides and the like.
These salts are used alone or as a mixture, and are used after being exchange-adsorbed and fixed to phosphate. The adsorption and immobilization can be performed by the ion exchange method, but can also be performed by other conventional methods. The ion exchange method is preferable from the viewpoint of holding power.

The content of the antibacterial agent is 0.1 parts by weight or more based on 100 parts by weight of the acrylic resin from the viewpoint of antibacterial property, and 40 parts by weight or less from the viewpoints of film-forming property, appearance and economy. Is desirable. It is preferably 0.3 part by weight or more and 10 parts by weight or less.

The average particle size of the antibacterial agent used in the present invention is preferably 5 μm or less from the viewpoint of dispersibility.
If the particle size is large, the dispersibility will be poor, and sufficient antibacterial performance will not be obtained, or seeds will be generated during processing, causing poor appearance.

As the method for producing the antibacterial acrylic film of the present invention, a melt casting method of an acrylic resin containing a phosphate having a predetermined amount of a quaternary ammonium salt compound adsorbed and immobilized, a T-die inflation method, etc. Although any method such as the melt extrusion method and the calendar method may be used, the T-die method is preferable from the viewpoint of economy.

In the antibacterial acrylic film of the present invention, if necessary, general compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact resistance aids, foaming agents, fillers, colorants, and ultraviolet rays are used. An absorbent or the like can be included.

The antibacterial acrylic film of the present invention can be used by laminating it to various substrates by means such as heat lamination, in-mold molding, or adhesion with an adhesive. Lamination is a very useful method because it can efficiently disperse expensive antibacterial agents on the surface, and is widely applied to wallpaper, bathrooms, toilet seats, household products such as public phones and washing machines, etc. It is a technology that can be done.

A wallpaper obtained by laminating the antibacterial acrylic film of the present invention on a wallpaper support such as a vinyl chloride resin is excellent in weathering discoloration, chemical resistance and stain resistance.

[0017]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In the description, "part" means "part by weight".

As an acrylic resin, Mitsubishi Rayon Co., Ltd.
The product "Hi-Pet (trade name) HBS-001" was used.
For 100 parts of this resin, as an antibacterial agent, cetylpyridinium chloride was immobilized on calcium phosphate, "RASAP (trade name) QC2500S" (average particle diameter of more than 5 μm) manufactured by RASA INDUSTRY CO., LTD. Particle size 1 μm) in the proportions shown in Table 1,
The pellets were shaped from a 30 mmφ twin-screw extruder at 240 ° C. and a discharge rate of 8 kg / hour. For comparison, "Bioside (trade name) 905A" and "Bioside 871" manufactured by Taisho Technos Co., Ltd., which use organic nitrogen compounds as antibacterial agents,
The company's "Bioside 843" which uses an organic sulfur halogen compound as an antibacterial agent, "BACTEKILLER" (trade name) manufactured by Kanebo Co., Ltd. in which antibacterial silver is immobilized on zeolite, and "HBS-001" containing no antibacterial agent The same was applied to the simple substance.

[0019]

[Table 1]

With respect to the obtained pellets, anoxic state,
Heat for 1 hour under the condition of 240 ℃, observe the appearance change,
The heat resistance was evaluated. The results are shown in Table 2. From Table 2, it can be seen that the blending amounts of Examples 1 to 5 are excellent in thermal stability.

[0021]

[Table 2]

Next, the obtained acrylic resin composition (pellets) was extruded under the following conditions to obtain 16 kinds of films. 40 mmφ (screw diameter) extruder with 300 mm T die Resin temperature 245 ° C. Discharge rate 15 kg / hour (for thickness 20 μm) Medium of the obtained film Comparative Example 8 has a lot of lumps, Comparative Example 2, Comparative Example 9 and Comparative Example 10 Because of its perforation, none of them could be used as an acrylic film in terms of appearance. Although a few spots were found in Examples 1 and 2, it was not a problem for use as an acrylic film. All of the other films had good appearances.

The antibacterial acrylic film thus obtained was evaluated as follows. Echerichia coli IFO as antibacterial test (contact method) cells
Using 12734 strain, each of these strains was inoculated into trypto soya broth medium, shake-cultured at 30 ° C. for 18 hours, then centrifuged, washed three times with sterile physiological saline, and then washed.
It was diluted 0 times to obtain a bacterial suspension. Sterilize by adding 10 ml of phosphate buffer solution (pH 7.2) to a Meyer flask,
0.1 ml of the above-mentioned bacterial suspension was inoculated to obtain a culture solution.

The acrylic film obtained as described above was cut into a bag having an inner surface area of 5 cm × 10 cm. The cultured Escherichia coli suspension was diluted and 0.1 ml was dispensed into the prepared bag so that the bacterial suspension could spread in the bag. This was put in a sterilized polyethylene bag and cultured at 30 ° C. for 24 to 48 hours, and the viable cell count was measured by the pour method. The results are shown in Table 3. It is clear from Table 3 that Examples 1 to 4 and Comparative Examples 5 and 6 have excellent antibacterial properties.

[0025]

[Table 3]

Halo test Staphylococcus aureu as bacterial cells
Staphylococcus au prepared by culturing using s ATTC 11522 strain in the same manner as in the contact method.
0.1 ml of reus suspension is added to 100 ml of agar medium, and an acrylic film is adhered on it, and the temperature is 30 ° C.
After culturing for 24 hours in the same manner, the size of the area (halo) around the film where the growth of the bacterial cells was inhibited was measured. The results are shown in Table 4. From Table 4, it was found that halos were found in Examples 1 to 4 and the antibacterial properties were excellent.

[0027]

[Table 4]

Examples 1-5, Comparative Examples 1, 3-7 and 11
In the same manner as above, for the wallpaper in which the acrylic film obtained in step 1 was pasted on a vinyl chloride resin wallpaper using a heating roll, the antibacterial test against Escherichia coli and the Staphylococcus aur were conducted.
A halo test with eus was performed. The results are shown in Table 5. The results of the halo test were the same as those in Table 4.

[0029]

[Table 5]

Claims (2)

[Claims] 1. An antibacterial acrylic film comprising 100 parts by weight of an acrylic resin and 0.1 to 40 parts by weight of an antibacterial agent mainly composed of a phosphate having a quaternary ammonium salt compound adsorbed and immobilized thereon. 2. An antibacterial wallpaper obtained by laminating the antibacterial acrylic film of claim 1 on a wallpaper support.