JPH0411945A - Microbe adsorbent for gas phase - Google Patents

Abstract

PURPOSE:To obtain an adsorbent having excellent microbe adsorptivity even in a gas phase by depositing vinyl copolymers of specified structure and a moisture keeping agent on the surface of a carrier. CONSTITUTION:Vinyl copolymers expressed by formula I (wherein R1 is benzyl group or alkyl group of 4-16 carbon number, R2 is hydrogen atom or alkyl group or 1-3 carbon number, X is halogen atom, Y is hydrogen or alkyl group of 1-3 carbon number) and a moisture keeping agent such as calcium chloride, polyvinylalcohol, etc., are used and made to deposite on a base material comprising a porous body such as nonwoven fabric or a structural material such as a honeycomb body. By this method, microbe absorptivity can be maintained even in gas phase by water adsorbed on the moisture keeping agent, and thereby, microbe in air can be efficiently collected.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a microbial adsorbent for gas phase that adsorbs microorganisms present in gas.

[Prior art] Conventionally, masks, air filters, etc. have been loaded with adsorbents such as activated carbon and zeolite to capture microorganisms such as viruses and bacteria as well as other harmful substances and dust contained in the gas. (Unexamined Japanese Patent Publication No. 53-5689)
No. 4). However, with this method, it was not possible to preferentially or selectively collect microorganisms, and the ability to collect microorganisms was not sufficient.

On the other hand, in fields such as water treatment, attempts have been made to collect microorganisms using resins that adsorb microorganisms.
JP-A-41641 reports an insoluble polymer compound made of cross-linked polyvinylpyridinium halide as a resin having a very high ability to adsorb microorganisms. However, since this resin has a three-dimensional crosslinked structure, it is difficult to form into a solution, difficult to process, and can only be used in specific shapes such as beads.

For this reason, the present inventors developed a solvent-soluble vinylpyridinium halide copolymer in order to preserve the microbial adsorption ability of the above resin and improve processability. The material was proposed in Japanese Patent Application No. 1-181576. This microbial adsorbent is soluble in solvents and can be easily processed into substrates, so if it is attached to the surface of a substrate with a high surface area such as a porous substrate, a high microbial adsorption ability can be obtained. Because it is insoluble in water, it is an excellent microbial adsorbent in aqueous systems. However, the presence of water is essential for the above-mentioned resin to adsorb microorganisms, and even microbial adsorbents that are very effective in aqueous systems cannot be used in gaseous phases because their ability to adsorb microorganisms decreases.

[Problems to be Solved by the Invention] The present invention has been made in order to eliminate the drawbacks of the above-mentioned prior art. The purpose of the present invention is to provide a gas-phase microbial adsorbent that exhibits excellent performance.

[Means for Solving the Problems] The present invention has a general formula, R a vinyl copolymer represented by an alkyl group, X is a halogen atom, Y is a hydrogen atom, an alkyl group of 01 to C3, a benzyl group, an ether group, a carboxyl group, a carboxylic acid ester group, or an aryl group) and a moisturizing agent. The present invention relates to a microbial adsorbent for gas phase, characterized in that it is attached to the surface of a base material.

[Function] That is, in the gas-phase microbial adsorbent of the present invention, since the above-mentioned vinyl copolymer and humectant are attached to the base material, a predetermined amount of moisture 7 is absorbed into the base material by the action of the humectant. This moisture keeps the functional groups of the vinyl copolymer that adsorb microorganisms on the surface in an active state, and exhibits a high ability to adsorb microorganisms even in the gas phase.

In addition, although the vinyl copolymer is insoluble or poorly soluble in water, it is soluble in organic solvents and can be made into a solution, so it can be used for impregnation or coating on desired base materials. can be easily processed. Therefore, by choosing a substrate with a large surface area such as a porous substrate,
It becomes possible to adsorb a large amount of microorganisms with a small amount of the vinyl copolymer.

In the present invention, a vinyl copolymer represented by the following general formula is used, which is obtained by copolymerizing 4-vinylpyridine and a monovinyl monomer and then reacting with a halide.

I However, in the formula, R1 is a benzyl group, an alkyl group of 04 to C16 or a pentafluorophenylmethyl group, R2 is a hydrogen atom or an alkyl group of 01 to C, X is a halogen atom, Y is a hydrogen atom, and They are an alkyl group, a benzyl group, an ether group, a carboxyl group, a carboxylic acid ester group, or an aryl group. Further, this vinyl copolymer is a random copolymer or a block copolymer.

Monovinyl monomers used for copolymerization include monoolefins such as ethylene, propylene, and butene, styrene, vinyl acetate, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, aliphatic vinyl esters, acrylonitrile, and derivatives thereof. However, various types can be used alone or in combination.

The ratio of this 4-vinylpyridine to monovinyl monomer, that is, the ratio n:m, varies depending on the type of monovinyl monomer used and the degree of polymerization, but is approximately 10
:90 to 90:10 is desirable. If the proportion of 4-vinyl and lysine is less than this range, sufficient microbial adsorption will not be obtained, and if the proportion is greater than this, the resulting copolymer will be highly water-soluble, for example, water on the surface of the adsorbent may If the amount is large, the vinyl copolymer may be dissolved in this water and may be moved.

Further, the degree of polymerization of the vinyl copolymer is at least 30
It is desirable that the degree of polymerization is 0 or more, and if the degree of polymerization is lower than this, the resulting copolymer will have high water solubility.

The copolymer of the monovinyl monomer and 4-vinylpyridine is obtained by quaternizing pyridine by reacting it with a halide such as alkyl halide, benzyl halide, or pentafluorophenylmethyl halide, and is expressed by the following formula. Forms a functional group.

Formula: is positively charged, and the cell surface of microorganisms is generally negatively charged, so it is presumed that electrostatic interaction is one important factor.

The vinyl copolymer thus obtained is dissolved in an organic solvent to form a solution, which can be coated, sprayed, etc.
It is attached to a base material by means such as impregnation. Organic solvents include alcohols, esters, phenols,
Although ethers can be used, it is preferable to use alcohols from the viewpoint of ease of handling.

The amount of the vinyl copolymer adhered to the base material is not particularly limited, but the adhesive thickness of the vinyl copolymer is 0.001
Since it is desirable that the thickness be in the range of ~1 μm, it is preferable that the adhesion range be approximately 0.001 to 100% by weight relative to the base material. If it is less than 0.001% by weight, a sufficient adsorption effect for microorganisms will be obtained, but if it is more than 100% by weight, the adsorption effect will not increase even though the amount of vinyl copolymer used increases, and it will become uneconomical.

On the other hand, the humectant used in the present invention may be one that has the property of absorbing moisture in gas, such as alkaline earth metal salts such as calcium chloride and magnesium chloride, lithium chloride, potassium metasilicate, sulfuric acid, etc. Suitable materials include deliquescent substances such as titanium, water-soluble polymers such as polyvinyl alcohol, polyacrylates, vinyl pyrrolidone, and carboxymethyl cellulose, silica gel, zeolite, collagen, ethylene glycol, diphosphorous pentoxide, magnesium oxide, and calcium oxide. .

The moisturizing agent may be attached to the substrate before or after the vinyl copolymer is attached to the substrate, or at the same time. In particular, when applying a moisturizer at the same time as the vinyl copolymer,
It is sufficient to coexist a humectant in the above-mentioned solvent solution of the vinyl copolymer. Used by dispersing it in a polymer solution.

The amount of the humectant attached varies depending on the type of humectant and its water adsorption ability, but it is approximately 5 to 50% of the amount of the vinyl copolymer mentioned above.
It is desirable that the amount of the humectant be in the range of 500% by weight; if the amount of the humectant is less than this, it will not be possible to supply the moisture necessary to maintain the activity of the microbial adsorption site of the vinyl copolymer. Even if the amount increases, the moisture adsorption effect will not improve.

The base material to which the above-mentioned vinyl copolymer and humectant are attached may be porous materials such as nonwoven fabrics, woven fabrics, knitted fabrics, paper, foams, ceramic sintered bodies, organic or inorganic particulate materials, and honeycombs. , structures such as multi-tiered plates are used. Among these, porous materials are suitable as microbial adsorbents because of their large surface area, and nonwoven fabrics having a three-dimensional structure are particularly desirable because they have excellent functions as gas filters.

The microorganisms to be adsorbed by the gas-phase microorganism adsorbent of the present invention include bacteria, fungi, algae, viruses, and the like.

The gas-phase microbial adsorbent of the present invention adsorbs microorganisms with specific functions present in the gas in a live or highly active state, and then activates the enzymes contained in these microorganisms to generate reaction products. It can be used in bioreactors, biosensors, etc. for obtaining and sorting substances.

Further, the gas-phase microbial adsorbent of the present invention can be used as a mask or an air filter, but in this case, there are two methods: using the adsorbent as it is, and using a disinfectant in combination. To use a sterilizing agent in combination, the sterilizing agent may be attached to the surface of the base material, or sterilizing fibers containing a sterilizing agent or sterilizing fibers into which a functional group having a sterilizing action has been introduced may be used as a constituent material of the base material.

If a disinfectant is used in combination, the microorganisms adsorbed on the adsorbent will no longer be able to proliferate, eliminating the fear of clogging due to microbial growth and extending the service life of masks and air filters. As a disinfectant,
For example, antibiotic polymyxins, positive surfactants such as quaternary ammonium salts, amphoteric surfactants such as alkylaminoethylglycine, biguanides such as chlorhexidine, polyhexamethylene biguanidine, higher fatty acids such as undecylenic acid, metals and Ions, phenols, etc. can be used. Among these, in particular, powders such as gold, silver, and copper, antibacterial zeolite in which zeolite is substituted with metal ions having bactericidal properties, and biguanides or quaternary ammonium salts fixed to polymer chains such as polyvinyl, polyacrylate, polyester, and polyamide. Preferred are water-insoluble or sparingly soluble fungicides, such as polymer-type immobilized fungicides, such as 3-(trimethoxysilyl)-brobyltrimethyloctadecyl ammonium chloride, and silicone-based immobilized fungicides.

In addition, in the gas-phase microbial adsorbent of the present invention, the higher the humidity of the gas to be treated, the greater the amount of moisture that can be adsorbed by the humectant, and the ability to adsorb microorganisms can be maintained at a high level. For this reason, it is desirable that the gas to be treated is humidified, and more preferably, the gas phase microbial adsorbent of the present invention is used in combination with a device that humidifies the gas to be treated.

(Example) After copolymerizing 4-vinylpyridine and styrene in a ratio of 1:2.5 mole, quaternization treatment was performed with benzyl bromide in an equimolar amount to 4-vinylpyridine to obtain a vinyl copolymer. I got it.

On the other hand, a fibrous web made of splittable composite fibers (fiber size after splitting: 0.3 denier) made of polyester and polyamide components was subjected to water bonding treatment to separate the fibers and entangle them. A nonwoven fabric of 0.5- was obtained.

This hydroentangled nonwoven fabric was impregnated with an ethanol solution in which the vinyl copolymer and lithium chloride were dissolved in a weight ratio of 100:150, and then dried at 75°C to reduce the adhesion of the copolymer to the nonwoven fabric. A microbial adsorbent for gas phase with a content of 1.5% by weight was obtained.

This gas phase microbial adsorbent 10CTII x 120cm
A 10 cm square filter unit was made by pleating the filter unit, and a box for spraying E. coli was installed on the upstream side of the filter unit, and a hole diameter of 0 was installed on the downstream side to prevent E. coli from passing through.
．． A suction pump was installed through a 45 μm membrane filter, and a test device was prepared in which these were connected.

First, with the filter unit removed as a blank, dilute physiological saline containing E. coli was sprayed using a spray box, air containing E. coli was sucked in at a rate of 10 liters/min for 2 minutes using a suction pump, and E. coli was placed on the membrane filter. was collected.

Next, after passing sterilized humidified air for 5 minutes to allow the filter unit to absorb moisture, dilute physiological saline containing E. coli was sprayed in a spray box. The air containing E. coli was sucked in for 2 minutes at a speed of 10 liters/min using a suction bow pump.
E. coli that passed through the filter unit was collected on a membrane filter.

A blank membrane filter and a membrane filter passed through the filter unit were impregnated with a liquid medium, cultured at 32° C. for 24 hours, and the number of colonies in each was measured. The eradication rate of E. coli was calculated from this number of colonies and is shown in Table 1.

(Comparative example) A gas phase microbial adsorbent was prepared in the same manner as in the example except that lithium chloride was not used, and by conducting the same experiment as in the example, the number of blank colonies and the gas phase The number of colonies when the sample passed through a filter unit made of a microbial adsorbent was measured, and the sterilization rate was determined and shown in Table 1.

Table 1 As is clear from Table 1, the gas-phase microbial adsorbent of the example has a superior ability to adsorb E. coli compared to the comparative example that does not use a humectant, and it efficiently removes microorganisms from the air. It can be seen that it can be adsorbed well.

[Effects of the Invention] As mentioned above, the gas-phase microbial adsorbent of the present invention is made by adhering a vinyl copolymer having excellent microbial adsorption ability in the presence of moisture to a base material together with a humectant. . Therefore, in the microorganism adsorbent of the present invention, the microorganism adsorption ability is maintained even in the gas phase by the moisture adsorbed by the humectant, so that microorganisms in the gas can be efficiently collected. Furthermore, since the vinyl copolymer used in the present invention is soluble in solvents, it can be easily applied to the surface of various substrates, such as porous substrates. By selecting a base material with a large surface area, it is possible to obtain an adsorbent that has a high ability to adsorb microorganisms and is less prone to problems such as clogging.

The gas-phase microbial adsorbent of the present invention adsorbs microorganisms with specific functions present in the gas in a living state or in a highly active state, and then activates the enzymes contained in these microorganisms to react. It can be used in bioreactors and biosensors for obtaining products and sorting substances. Further, the gas-phase microorganism adsorbent of the present invention can be used as a mask or an air filter as it is or in combination with a sterilizer to prevent the adsorbed microorganisms from multiplying on the adsorbent.

As described above, the gas-phase microbial adsorbent of the present invention can efficiently capture microorganisms in gas, and is suitable for use in biosensors, microbial holders for bioreactors, masks, air filters, etc. It is something that

Patent applicant Nippon Vilene Co., Ltd.

Claims (1)

[Claims] (1) General formula, ▲Mathematical formula, chemical formula, table, etc.▼ (However, in the formula, R_1 is a benzyl group, C_4 to C_1_
6 alkyl group or pentafluorophenylmethyl group, R_2 is a hydrogen atom or C_1 to C_3 alkyl group, X is a halogen atom, Y is a hydrogen atom, C_1 to C_3 alkyl group, benzyl group, ether group, carboxyl group, carbon A microbial adsorbent for gas phase use, characterized in that a vinyl copolymer represented by an acid ester group or an aryl group and a humectant are attached to the surface of a base material.