JPH08188513A - Antimicrobial agent for wall paper, furniture and miscellaneous goods - Google Patents

Abstract

PURPOSE: To obtain an antimicrobial agent high in antimicrobial effect and safety, free from discoloration and offensive odor, by making antimicrobial metal(s) such as silver, copper and/or zinc adsorb to a kind of various proteins, esp. scleroprotein or vegetable protein. CONSTITUTION: Fine powder of a protein such as originated from eggshell membrane (esp. scleroprotein) is first mixed with a solution of at least one kind of various metals such as silver, copper and zinc to effect adsorption of the metal(s) to the protein. Secondly, the resultant fine powder is recovered by filtration or precipitation with a solvent, and then washed with water or an alcohol to obtain the objective antimicrobial agent. As the other proteins, vegetable proteins such as of soybean, corn or wheat, decomposed product thereof, or purified product thereof (esp. zein) are preferable. This antimicrobial agent can be produced very easily.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antibacterial agent for wallpaper, furniture and sundries.

[0002]

2. Description of the Related Art Wallpapers for indoor walls, bran, ceiling, etc., various furnitures and miscellaneous goods are molded from pulp, vinyl chloride resin, acrylic resin, polyester resin, polyethylene resin and the like. In recent years, the use of aluminum sashes for buildings has improved the airtightness, the spread of air conditioning and heating, the use of humidifiers, etc.
It is a problem because it breeds in miscellaneous goods and causes stains.
Further, these microorganisms are directly in contact with or inhaled to the human body, and they are a food for mites, causing diseases such as MRSA and allergies, which is an important problem for hygiene. Conventionally, in order to prevent microbial contamination and generation of wallpaper, furniture, sundries, etc., synthetic antibacterial agents, antibacterial metals and inorganic substances containing them have been added to the materials of wallpaper, furniture, sundries or adhesives. However, these techniques are disclosed. For example, Japanese Patent Laid-Open No. 01-272
In 898, an antibacterial wallpaper mixed with a thiazole-based and / or thiazoline-based synthetic antifungal agent is disclosed. In JP-A-3-898, a paper containing an N-long chain amyl amino acid salt of an antibacterial metal is disclosed, and in JP-A-5-31840. A mildew-proof / antibacterial decorative sheet formed by foaming vinyl chloride paste sol mixed with a silver ion-containing soluble glass is disclosed. But,
When the above-mentioned synthetic antibacterial agent or an inorganic substance containing an antibacterial metal is added or applied to wallpaper, furniture, sundries, the synthetic antibacterial agent has a problem in terms of safety to humans and bad odor. In the case of contained inorganic substances, they themselves discolor due to light, air, moisture, detergent, etc., resulting in wallpaper, furniture,
Discoloration and coloring of miscellaneous goods cannot be avoided.

[0003]

Accordingly, there is a strong demand for an antibacterial agent for wallpaper, furniture and miscellaneous goods which has a strong antibacterial effect, is highly safe, and has no coloring or odor.

[0004]

[Means for Solving the Problems] As a result of intensive research to solve the above problems, various proteins, particularly hard proteins and vegetable proteins, are strongly adsorbed with antibacterial metals such as silver, copper and zinc. The present invention was first found to exhibit antibacterial properties, and the present invention was completed. That is, the present invention provides an antibacterial agent for wallpaper, furniture and miscellaneous goods in which an antibacterial metal is adsorbed on a protein.

The present invention will be described in detail below. The protein of the present invention is not particularly limited, for example, eggshell membrane,
Feather, wool, silk and collagen isolated from them,
Hard proteins such as silk fibroin and elastin can be used, but eggshell membranes or proteins derived from eggshell membranes are preferable. These hard proteins are fibrous proteins that are insoluble in water, salt solutions and other solvents, and are very stable proteins. As the protein of the present invention, vegetable protein such as soybean, corn, wheat, etc., its degradation product, or purified product can be used, and zein is preferred. Among these proteins, the eggshell membrane, which has a high metal adsorption capacity, is preferable. The particle size of these proteins can be appropriately changed depending on the wallpaper used, furniture, materials of miscellaneous goods, and addition method. The form of these proteins may be any of a crushed product, a fine powder, a solution or dispersion in water or a solvent, and a solubilized product, but a fine powder is preferred from the viewpoint of operability.

As the antibacterial metal of the present invention, silver, copper or zinc can be used, and silver is preferable from the viewpoint of antibacterial property. The method for producing the antibacterial protein of the present invention is as follows. That is,
The protein is mixed with the above-mentioned various metal solutions of silver, copper and zinc to adsorb metal ions, and then collected by filtration or solvent precipitation. After that, non-adsorbed metal ions are washed off with water or a solvent such as alcohols or acetone, and dried to obtain the product of the present invention. The metal solution used is silver nitrate, silver sulfate, silver perchlorate, silver oxide, silver chloride,
Examples thereof include aqueous solutions of diammine silver nitrate, diammine silver sulfate, copper nitrate, copper sulfate, copper chloride, zinc nitrate, zinc chloride, and the type and concentration thereof can be appropriately selected depending on the solubility and the amount adsorbed to proteins. Further, the solvent to be used can be appropriately selected from ethanol, methanol, isopropyl alcohol, acetone and the like depending on the kind of the metal compound. The concentration of the solution can be used in the range of 0.001% to 10%. The content of the metal to be adsorbed to various proteins is not particularly limited, but 0.005 to the protein weight from the viewpoint of antibacterial property.
It is preferably set to 10%. The thus obtained antibacterial agent for wallpaper, furniture and miscellaneous goods does not impair the properties such as safety of protein and the antibacterial property of metal, and the chemical,
Since it is physically and biologically very stable, the antibacterial agent for wallpaper, furniture and miscellaneous goods of the present invention is added to various materials such as pulp, vinyl chloride resin, acrylic resin, polyester resin and polyethylene resin. Alternatively, it can be used in various methods such as coating. Hereinafter, the present invention will be described with reference to Examples and Test Examples, but the present invention is not limited thereto.

[0007]

【Example】

Example 1 100 g of eggshell membrane powder (average particle size 10 μm) obtained from chicken eggs was added to 500 ml of 0.2% silver nitrate aqueous solution, stirred for 10 minutes, filtered, and washed with water until non-adsorbed silver was removed,
Finally, it was dehydrated and dried with acetone to obtain 101 g of the antibacterial agent for wallpaper, furniture and sundries of the present invention. Silver content per egg shell membrane was 0.4% as measured by atomic absorption spectrometry
Met. Example 2 100 g of collagen powder (average particle size: 10 μm) purified from cowhide was added to 500 ml of a 0.2% silver nitrate aqueous solution to give 5
After stirring for a minute, the mixture was filtered, washed with water until the non-adsorbed silver disappeared, and finally dehydrated and dried with acetone to obtain 95 g of the antibacterial agent for wallpaper, furniture and sundries of the present invention. The silver content per collagen weight was 0.11% as measured by atomic absorption spectrometry.

Example 3 To 500 ml of 0.2% silver nitrate aqueous solution was added 100 g of zein powder separated from corn, and the mixture was stirred for 10 minutes.
It was filtered, washed with water until the non-adsorbed silver disappeared, and finally dehydrated and dried with acetone to obtain 105 g of the antibacterial agent for wallpaper, furniture and sundries of the present invention. The silver content per egg shell membrane weight was 0.18% as measured by atomic absorption spectrometry. Example 4 100 g of eggshell membrane powder (average particle size 10 μm) obtained from chicken eggs was added to 500 ml of 0.5% copper sulfate solution, stirred for 10 minutes, filtered and washed with water until non-adsorbed copper disappeared,
Finally, it was dehydrated and dried with acetone to obtain 100 g of the antibacterial agent for wallpaper, furniture and sundries of the present invention. The copper content per weight of the eggshell membrane was measured by an atomic absorption method to be 2.3.
%Met.

Example 5 100 g of egg shell membrane powder (average particle size 10 μm) obtained from chicken eggs was added to 500 ml of 0.5% zinc nitrate solution, stirred for 10 minutes, filtered, and washed with water until the non-adsorbed zinc was eliminated. Dehydrated and dried with acetone for wallpaper of the present invention,
100 g of an antibacterial agent for furniture and miscellaneous goods was obtained. The zinc content per egg shell membrane weight was 0.5% as measured by atomic absorption spectrometry. Test Example 1 (Antibacterial property test) The antibacterial property test of the antibacterial agents for wallpaper, furniture and miscellaneous goods obtained in Examples 1 to 5 was conducted by the following method. Molds as test strains; Asperigillas niga
r ATCC3275), Aureobasidium pullulans (Aureo
basidium pullulans IFO6353), Penicillium citrinum IFO7784, Tricophyton mentagrophytes IF
O5809), yeast; Saccharomyces cerevisiae (Sacchar
omyces cerevisiae IFO0203), Candida albicans IFO1061), bacteria; Bacillus subtilis IFO3007, Staphylococcus aureus IFO12732)
Pseudomonas aerugin
osa IFO3080), Eschericia coli I
FO3545), Streptococcus mutans (Strepto
coccus mutans MT8148), Bacteroides gingivalis ATCC33277, Propionibacterium

Acnes (Propionibacterium acnes GAI54
19) was used to determine the minimum growth inhibitory concentration (%) by the agar dilution method. The medium used is mold, YM agar medium (made by Difco) for yeast, standard agar medium (made by Eiken Chemical Co., Ltd.) or GAM for bacteria.
It is an agar medium (manufactured by Eiken Chemical Co., Ltd.). An agar medium containing samples of various concentrations was prepared, and one platinum loop of the bacterial solution of each strain previously cultured in the enrichment medium was inoculated on the agar and cultured under each condition. After the culture, the minimum growth inhibitory concentration was measured from the growth state of the bacteria. The results are shown in Table 1.

[0011]

[Table 1]

Test Example 2 (Stability Test) The antibacterial agents for wallpaper, furniture and miscellaneous goods obtained in Examples 1 to 5 were stored for a long period of time and tested for antibacterial properties, degree of coloring and degree of malodor. As a result of storing this antibacterial agent at room temperature for half a year for one year, the antibacterial property was maintained and neither coloring nor spoiled odor was observed. Test Example 3 The antibacterial agent for wallpaper, furniture and miscellaneous goods obtained in Example 1 was added to 200 ml of a 30% pulp concentration solution in an amount of 1% based on the weight of pulp, and starch was used as a sizing agent by a conventional method. A handmade wallpaper (pulp 60 g / m ² ) was prepared. This wallpaper was placed on a potato dextrose agar medium coated with Aspergillus niger, Penicillium citrulinum, Trichophyton mentaglophytes and Candida albicans, and cultured at 25 ° C. for 4 days. As a result, no growth of bacteria was observed on the wallpaper.

Test Example 4 An artificial leather made of an existing polyester resin was coated with 10 g / m ^{2 of} a polyurethane solution containing 20% by weight of the product of the present invention obtained in Example 1. To this artificial leather, apply Staphylococcus aureus, Pseudomonas aeruginosa, Essericia collie, Proteus, Klebziella, respectively, at 25 ° C,
After leaving it for 24 hours under the condition of relative humidity of 80%, it was placed on nutrient broth agar medium and cultured at 37 ° C. for 24 hours. In addition, an artificial leather coated with a polyurethane solution containing no product of the present invention was prepared, and a bacterial solution was similarly coated as a control and tested. As a result, 100 pieces / cm for the control
^{Although two} or more bacteria were detected, no growth of bacteria was observed in the treated product of the product of the present invention. From the above results, it was shown that the antibacterial agent for wallpaper, furniture and miscellaneous goods of the present invention in which antibacterial metal is adsorbed to various proteins has excellent antibacterial property and excellent long-term stability.

The embodiments of the present invention and the desired products are as follows. (1) An antibacterial agent for wallpaper, furniture and miscellaneous goods in which an antibacterial metal is adsorbed on protein. (2) The antibacterial agent for wallpaper, furniture and sundries according to (1) above, wherein the protein is a hard protein. (3) The antibacterial agent for wallpaper, furniture and miscellaneous goods as described in (2) above, wherein the hard protein is an eggshell membrane. (4) The antibacterial agent for wallpaper, furniture and miscellaneous goods according to (2), wherein the hard protein is collagen. (5) The antibacterial agent for wallpaper, furniture and miscellaneous goods according to (2) above, wherein the hard protein is silk fibroin. (6) The antibacterial agent for wallpaper, furniture and sundries according to (2) above, wherein the hard protein is elastin. (7) The antibacterial agent for wallpaper, furniture and miscellaneous goods according to (1) above, wherein the protein is a vegetable protein. (8) The antibacterial agent for wallpaper, furniture and miscellaneous goods according to (7) above, wherein the vegetable protein is zein. (9) The above (1) to which the antibacterial metal is silver, copper or zinc.
(8) An antibacterial agent for wallpaper, furniture and sundries.

[0015]

The various proteins used in the present invention are extremely safe since they are materials used in large quantities in the food field and the like. Therefore, an antibacterial agent for wallpaper in which an antibacterial metal is adsorbed on these proteins is also highly safe and has excellent antibacterial properties and stability. Furthermore, since the manufacturing method is extremely simple, it can be applied to wallpaper, furniture, sundries, and the like.

Claims (5)

[Claims] 1. An antibacterial agent for wallpaper, furniture and miscellaneous goods in which an antibacterial metal is adsorbed on a protein. 2. The antibacterial agent for wallpaper, furniture and sundries according to claim 1, wherein the protein is a hard protein. 3. The antibacterial agent for wallpaper, furniture and sundries according to claim 2, wherein the hard protein is obtained from an eggshell membrane. 4. The antibacterial agent for wallpaper, furniture and sundries according to claim 1, wherein the protein is a vegetable protein. 5. The antibacterial agent for wallpaper, furniture and sundries according to claim 1, wherein the antibacterial metal is silver, copper or zinc.