JPH0720846B2 - Sterilization and removal of bacteria - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for sterilization and removal of bacteria.

(Prior Art) In our living space, various microorganisms such as bacteria, molds and bacteria are present. And in a hot and humid environment, their reproduction is particularly active, causing the phenomena such as fiber deterioration, discoloration, and deterioration, causing spoilage and fermentation, and generating an unpleasant odor. There is.

Also, despite the fact that modern surgical techniques and extremely complicated equipment are used for surgery, wound infections are still prevalent, and it is one of the items of great interest in hospitals.
Therefore, it prevents post-operative infection by pathogenic bacteria and is useful for wound healing, and when administering drugs etc. to the body, it is a material to prevent pathogenic microbial invasion from the route and medical treatment to make patients' illness life easier. The development of textile products for use was desired.

Conventionally, as an antibacterial and antifungal processing method, a method of applying or spraying a compound having an antibacterial activity to natural or synthetic fibers, for example, a quaternary ammonium salt, or impregnating the fiber with a compound solution is known.

However, in these methods, the effect is not sustainable, and the antibacterial agent is easily removed by subsequent washing or rubbing, which is a problem in terms of safety and hygiene and wastewater pollution. In addition, when the resin processing is performed using a resin to which an antibacterial agent is added, there is a drawback that the feel of the fiber is impaired.

(Problems to be Solved by the Invention) The present invention provides a method for selectively sterilizing and removing bacteria contained in air, water, an aqueous solution, and blood.

(Means for Solving Problems) The present invention has the following configurations.

A sterilization and removal method of a bacterium, which comprises contacting a bacterium or a medium containing the bacterium with a polymer having a functional group of the following general formula (1) as a substituent in a main chain or a side chain or a molded product thereof.

In the above formula, R ₁ represents an alkyl group having a methylene chain length of 3 or more and 18 or less in carbon number, and R ₂ and R ₃ represent a methyl group or an ethyl group. R ₄ and R ₅ represent a hydrogen atom or a lower alkyl group. X represents a usual anion represented by chlorine ion.

Hereinafter, the present invention will be described in detail.

Examples of the bacterium used in the present invention include gram-negative bacteria such as gram-negative cocci, gram-negative aerobic bacilli, and gram-negative anaerobic bacilli, and gram-positive bacteria represented by Staphylococcus aureus.

The polymer in the present invention means a polymer such as aromatic polyamide, polyester, polysulfone, polyphenylene sulfide, polystyrene, etc. Among them, polystyrene is particularly preferable because it is chemically stable. Further, if the polymer is reinforced with poly α-olefin represented by crystalline polypropylene, polyethylene, etc., it is more preferable because the mechanical properties are improved.

In the general formula (1), the alkyl group R _{1 has} a methylene chain length of 3
The number is preferably 18 or more and 18 or less, more preferably 5 or more and 11 or less. When it is 2 or less, hydrolysis resistance is poor, and
If the methylene chain length is 24 or more, it is difficult to obtain the raw material.
If the alkyl group of R ₂ and R ₃ has a large number of carbon atoms, the hydrophobicity of the polymer becomes too high and it becomes difficult to contact with the bacterium or the medium containing the bacterium, so the methyl group having the smallest number of carbon atoms is the best. . The alkyl group of R ₄ and R ₅ is most easily produced when it is a hydrogen atom.

The amount of the functional group represented by the general formula (1) in the polymer is not particularly limited, but if the amount is too small, the affinity of the polymer or its molded product with the bacterium or the medium containing the bacterium is poor. Therefore, the treatment capacity is lowered, so that it is preferable that the amount is 0.2 mmol or more, and more preferably 0.6 mmol or more per 1 g of the polymer. In addition, the polymer or its molded product is substantially inactive under the conditions of use and is substantially inactive. That is, unlike the case of imparting the sterilizing power by the chemical treatment or the surface treatment, it is safe because it itself retains the sterilizing power. For this reason, the effect continues even after long-term use, and its industrial utility value is extremely high.

The term "molded product" as used in the present invention means a fiber, a membrane, a hollow fiber, a granular material, and a highly processed product thereof. If it is a fiber, it can be used in a higher-order form such as woven fabric, knitted fabric, paper, felt, and filter. In particular, it is preferable that fibers and hollow fibers can be used in such a manner that a flow path can be secured. This property is important when the molded product is used as a treating agent for a highly viscous liquid such as blood. In this case, if the surface area of the molded product is too small, the treatment capacity for bacteria will be reduced, and if it is too large, the liquid permeability of the column packed with the molded product of the present invention will be poor. Surface area is 0.01 or more and 50 m ² / g or less,
More preferably, it is 0.05 or more and 10 m ² / g or less.

Specific examples of the method for preparing a molded article according to the present invention include polystyrene fiber reinforced with polypropylene having a multi-core sea-island structure and paraformaldehyde and N-methylol-α-chloroacetamide at room temperature in the presence of sulfuric acid and nitrobenzene. After insolubilization and amidomethylation by using, iodination is carried out by immersing in water-containing ethanol containing potassium iodide and heating. After that, this can be achieved by immersing the iodide in a solution of the amine represented by the general formula (2).

Illustrating a method of sterilizing and removing bacteria from a medium containing a bacterium or a bacterium using the molded article according to the present invention, the molded article is contacted with the bacterium or a medium containing a bacterium, and then the molded article is separated. do it. As a method of contact, a column filled with the molded product is prepared, and a medium containing a bacterium or a bacterium is passed through the column, or the molded product is made into a felt-like or filter-paper-like product, and a medium containing the bacterium or a bacterium. The method of filtering out is also preferably used. The molded product may be used alone or in combination with a product such as a porous membrane.

Examples of the use of the molded article according to the present invention include infusion fluid, dialysate or blood, physiological saline in a column filled with the molded article,
There are a method of circulating an aqueous solution, water, air and the like, and a method of coating the surface of a burned part or a scratched part with the molded product. In addition, as an example of a product obtained from the molded product, as a medical-related textile product, a blood contact material, an apron, a bed cover, a diaper, a surgical cover, a face mask, a feminine hygiene device, an incontinence pad, There are laboratory clothes, laundry bags, bandages, sheets, pillow cases, bed covers, surgical clothing, and sutures. In addition to medical items, clothes, wallpapers,
Examples include carpets, food storage containers, food packaging tools, and vacuum cleaner garbage bags.

Examples will be shown below.

(Example) (Preparation of material for sterilization and removal of bacteria) 50 parts of polypropylene (Mitsui "Nobren" J3HG) as an island component, 46 parts of polystyrene ("Stylon" 666), polypropylene (Sumitomo "Nobren" WF-727-F) ) Sea-island type composite fiber containing 4 parts of mixture as sea component (16 islands, single yarn fineness)
2.6 denier, tensile strength 2.9 g / d, elongation 50%, filament number 42) 50 g in a mixed solution consisting of 50 g of N-methylol-α-chloroacetamide, 400 g of nitrobenzene, 400 g of 98% sulfuric acid and 0.85 g of paraformaldehyde. Soak, 2
The reaction was carried out at 0 ° C for 1 hour. Remove the fiber from the reaction solution,
The reaction mixture was poured into ice water 51 at 0 ° C. to stop the reaction and then washed with water, and then nitrobenzene attached to the fiber was extracted and removed with methanol. This fiber was vacuum dried at 50 ° C. to obtain 71 g of chloracetamidomethylated fiber (fiber A).

10 g of fiber A obtained above containing 10 g of potassium iodide 10%
Soak in 200 ml of water-containing ethanol and heat at 55 ℃ for 4 hours.
Iodoacetamide methylated fiber (fiber B) was obtained.

10 g of the fiber B was immersed in a solution consisting of 30 g of N, N-dimethylhexylamine and 170 g of dimethyl sulfoxide and heated at 80 ° C. for 6 hours. Further, this fiber was packed in a chromatographic column and washed successively with 1 L of 1N-hydrochloric acid, 5 L of water, 1 L of 1N-NaOH, 5 L of water and 10 L of 1M-NaCl, which was the fiber of the present invention Example 1 N chloride. , N-Dimethyl-N-hexylammonium acetamide methylated fiber (neutral salt decomposition capacity 1.61meq / g, weak basic group amount 0.47meq / g, water content 1.91 / PH7.4, 2.06 / hydrochloric acid type) was obtained. .

Further, instead of the above N, N-dimethylhexylamine,
N, N-Dimethyl-N-octylammoniumacetamide-methylated chloride fiber, which is the fiber of Inventive Example 2 except that N, N-dimethyloctylamine is used, is treated in exactly the same manner as described above. meq / g, weak basic amount 0.86m
eq / g, water content 1.23 / PH7.4, 1.48 / hydrochloric acid type) were obtained.

(Method for measuring viable cell count) Escherichia coli (Escherichia coli ATCC 25922) was suspended in a sterilized phosphate buffer to prepare a concentration of about 10 ⁶ CFU / ml (cold forming unit). After shaking the fibers and bacterial liquid, bacteria solution 3 serial dilutions (10 ^0, 10 ^2, 10 ⁴ dilution), and each 0.1 ml DHL agar medium (Nissui Pharmaceutical Co., Nissui Plate DHL agar)
Was inoculated. After culturing at 37 ° C for 24 hours, the number of colonies was measured.

Example 1. The following sterilization and bacterium removal experiments were conducted on the fibers of Examples 1 and 2 of the present invention and the comparative fiber obtained in the examples. 0.25 g of the prepared fiber was cut into a length of 3 cm, put into a 10 ml glass test tube, 8 ml of distilled water was put therein, and then the tube was capped and autoclaved at 121 ° C. for 30 minutes. After this, remove the supernatant liquid
5 ml was added, and the mixture was shaken at room temperature and sampled at predetermined time intervals. As a control, a test tube into which only the bacterial solution was injected was prepared and shaken in the same manner. After shaking for a predetermined time, the viable cell count was measured and the results shown in Table 1 were obtained.

It can be seen from Table 1 that the number of bacteria is zero in a short time in the examples of the present invention, whereas the comparative example, which is a quaternary ammonium type having a similar chemical structure, has a small decrease in the number of bacteria and is ineffective.

The fiber of the comparative example was prepared as follows. Fiber B1
0 g was immersed in a solution consisting of 25 ml of N, N-dimethylethylamine and 180 ml of dimethyl sulfoxide and heated at 50 ° C. for 6 hours. This fiber was packed in a chromatographic column and 1 l of 1N-HC
l, 5 l water, 1 l 1N-NaOH water, 5 l water and 10 l 1M-Na
N, N-dimethylethylammonium acetamidomethylated chloride fiber as a comparative example fiber was sequentially washed with Cl (neutral salt decomposition capacity 0.67meq / g, weak basic group amount 1.44meq / g, water content 0.
92 / PH7.4, 1.32 / hydrochloric acid type) was obtained.

Example 2 Using the fiber of Example 1 of the present invention described in Example 1, sterilization and bacterium removal experiments were conducted by changing the bacterium species. As the bacterial species,
(1) Pseudomonas aeruginosa ATCC 27853
(2) Serratia marcescens ATCC 8100 (3)
Klebsiella pneumoniae ATCC 27736 (4)
Salmonella typhimurium ATCC 1331
1) was used. 0.25 g of the fiber of Example 1 of the present invention was cut into a length of 3 cm, placed in a 10 ml glass test tube, charged with 8 ml of distilled water, then plugged, and autoclaved at 121 ° C. for 30 minutes. After that, the supernatant was removed, 5 ml of the bacterial solution was added, and the mixture was shaken at room temperature and sampled at predetermined intervals. As a control, a test tube into which only the bacterial solution was injected was prepared and shaken in the same manner. After shaking for a predetermined time, the viable cell count was measured and the results shown in Table 2 were obtained.

It can be seen from Table 2 that the examples of the present invention have a strong bactericidal effect against Gram-negative bacteria other than E. coli.

Example 3 Using the fiber of Example 1 of the present invention described in Example 1, a sterilization test using Gram-positive bacteria and a bacteria removal experiment were conducted. Staphylococcus aureus ATCC 259
23) and Streptococcus faecalis ATC
C 29212) was used. 0.25 g of the fiber of Example 1 of the present invention was cut into a length of 3 cm, placed in a 10 ml glass test tube, charged with 8 ml of distilled water, then plugged, and autoclaved at 121 ° C. for 30 minutes. After that, the supernatant was removed, 5 ml of the bacterial solution was added, and the mixture was shaken at room temperature and sampled at predetermined intervals. As a control, a test tube into which only the bacterial solution was injected was prepared and shaken in the same manner. After shaking for a predetermined time, the viable cell count was measured and the results shown in Table 3 were obtained. The medium used was tryptosoya agar medium (Nissui plate manufactured by Nissui Pharmaceutical Co., Ltd.).

It can be seen from Table 3 that the examples of the present invention have a strong bactericidal effect even against Gram-positive bacteria.

EFFECTS OF THE INVENTION The present invention can reduce the level of bacterial contamination, control wound infection, and render the wound sterile. Moreover, since it does not elute from the material, it is non-toxic, non-sensitizing and non-irritating, and its antibacterial activity does not decrease during use, so it is safe and easy to handle.

Claims (1)

[Claims] 1. A sterilizer, which comprises contacting a bacterium or a medium containing the bacterium with a polymer having a functional group represented by the following general formula (1) as a substituent in its main chain or side chain, or a molded product thereof. How to remove bacteria. In the above formula, R ₁ represents an alkyl group having a methylene chain length of 3 or more and 18 or less in carbon number, and R ₂ and R ₃ represent a methyl group or an ethyl group. R ₄ and R ₅ represent a hydrogen atom or a lower alkyl group. X represents a usual anion represented by chlorine ion.