JPH02237902A - Microorganism absorbing agent - Google Patents

Abstract

PURPOSE:To obtain a microorganism absorbing agent containing a high- molecular compound obtained by quaternarizing a pyridine group of a copolymer of vinylpyridines, hydrophilic ethylenic unsaturated monomer and crosslinkable monomer as an active ingredient, exhibiting excellent microorganism absorbing properties and exerting no bad influence on a matter to be degerminated. CONSTITUTION:The microorganism absorbing agent containing a high-molecular compound obtained by quaternarizing a pyridine group of a copolymer obtained by copolymerizing (A) vinylpyridines, preferably 2-, 3- or 4-vinylpyridine with (B) hydrophilic ethylenic unsaturated monomer and (C) crosslinkable monomer, e.g. polyfunctional (meth)acrylates or polyfunctional (meth)acrylamides, prefer ably at a molar ratio of component A: component B: component C of 50-90:5-30:5-30 as an active ingredient, exhibiting excellent microorganism absorb ing properties in degermination of water, air, surface of solid, etc., is degerminated and exerting no bad influence on a matter to be degerminated.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a microbial adsorbent that exhibits excellent microbial adsorption properties when disinfecting water, air, solid surfaces, etc., and does not have a negative effect on the target to be disinfected. .

[Conventional technology]

Removal of microorganisms floating in, attached to, and propagating in various types of water, wastewater, the surfaces of buildings, and even the air is extremely important in terms of environmental hygiene and increasing the durability of buildings.

Conventionally, methods using microbicides such as chlorine, microbicides by heating, and filtration methods using membranes and filters have been mainly used for this purpose. However, methods that use microbicides generally leave behind harmful substances and cannot be applied to food production, storage, and transportation equipment or drinking water, and methods that use heating, membranes, and filters require large-scale equipment and are not economical. It was also inconvenient.

Recently, the following formula (in the formula, R is a benzyl group, a C4-CI6 monoalkyl group, or a pentaphenylmethyl group, and X is a chlorine atom or a bromine atom) is used to easily remove microorganisms in the environment. A microbial control agent has been provided which contains as an active ingredient an insoluble polymeric compound having a pyridinium group, which is obtained by polymerizing the above-mentioned compound and a tonodivinyl compound such as divinylbenzene at the vinyl group (Japanese Patent Publication No. 41641/1983).

[Problem to be solved by the invention]

However, when using the microbial control agent described in Japanese Patent Publication No. 62-41641, even if this microbial control agent is brought into sufficient contact with a bacterial suspension of 107 to 10' individuals/ml, all bacteria are removed from the liquid. It takes more than 6 hours to be removed from the inside, and under the same conditions 103-104 individuals/m1
When contacting with a bacterial suspension of

Further, in Japanese Patent Publication No. 62-41641, a polymer having a substituent such as a benzyl group, a butyl group, a hexadecyl group, a dodecyl group, or a pentaphenylmethyl group at the N position is used. However, since these polymers have highly hydrophobic substituents, a problem arises in that their adsorption ability is reduced depending on the microorganism.

[Means to solve the problem]

Under such circumstances, the inventors of the present invention have conducted various studies to obtain a microbial adsorbent that eliminates the above-mentioned drawbacks.
The polymer compound obtained by copolymerizing vinyl pyridines, a woodphilic ethylenically unsaturated monomer, and a crosslinking monomer, and then quaternizing this is highly hydrophilic, and especially has amino groups in the side chain. We have discovered that a resin obtained by copolymerizing a hydrophilic monomer with a hydrophilic monomer has excellent bacteria adsorption properties, and does not have a negative effect on the objects to be sterilized when sterilizing water, air, or solid surfaces.
The invention has been completed.

That is, the present invention copolymerizes vinylpyridines, a hydrophilic ethylenically unsaturated monomer, and a crosslinkable monomer to form a copolymer, and further quaternizes the pyridine group to obtain a polymer compound. The present invention provides a microbial adsorbent as an active ingredient.

The polymer compound used in the microbial adsorbent of the present invention is a copolymer obtained by copolymerizing vinyl pyridines, a hydrophilic ethylenically unsaturated monomer, and a crosslinking monomer, which is then quaternized. Manufactured by

As the vinylpyridines used here, 2-vinylpyridine, 3-vinylpyridine, and 4-vinylpyridine are preferably used, but vinylpyridine derivatives having other substituents may also be used.

Examples of crosslinkable monomers include divinylbenzene; ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, trimethylolbrobantri(meth)acrylate, and pentaerythritol di(meth)acrylate.
meth)acrylate, pentaerythritol tetra (
Polyfunctional (meth)acrylates such as meth)acrylate, polyethylene glycol di(meth)acrylate; methylene bis(meth)acrylamide, brobylene bis(
meth)acrylamide, N,N'-(1,2-dihydroxyethylene)bis(meth)acrylamide, N.
Examples include polyfunctional (meth)acrylamides such as N'-(carboxymethylene)bis(meth)acrylamide.

Examples of hydrophilic ethylenically unsaturated monomers include acrylic acid ester monomers such as methyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and 2-hydroxyethyl acrylate; methyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl Methacrylic acid ester-based 1,000-mers such as methacrylate and 2-hydroxyethyl methacrylate; Polyethylene glycol mono (meth)acrylate; Alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; Vinyl ester-based 1,000-mers such as vinyl acetate and vinyl acetate; (meth) Acrylamide: N-alkyl-substituted (meth)acrylamide such as N-methylacrylamide, N-ethylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide; Nitrile monomers such as acrylonitrile and methacrylonitrile, etc. However, the monomers are not limited to the above monomers as long as they are essentially hydrophilic. These monomers can be used alone or in combination of two or more.

The blending molar ratio in copolymerization of vinylpyridines, hydrophilic ethylenically unsaturated monomers, and crosslinking monomers is 50 to
The ratio is preferably about 90:5 to 30:5 to 30.

Copolymerization methods include conventionally known bulk polymerization, solution polymerization,
Suspension polymerization or the like can be used.

For quaternization of the copolymer thus obtained, for example, C, ~
Alkylating agents such as alkyl halides, aralkyl halides, aralkyl halides such as chloro, bromo or iodine of C Il1 are used. These can be used alone or in combination of two or more.

The reaction between the copolymer and the alkylating agent is carried out by adding 1 to 5 molar equivalents, particularly 1.5 to 4.0 molar equivalents of the alkylating agent to the pyridine group in the copolymer, in a solvent such as methanol or ethanol. This is carried out by mixing in the presence of , under normal pressure and at a temperature of 50 to 70°C.

Furthermore, the obtained crosslinkable polymer compound is subjected to ion exchange according to a known method, and the pyridinium group pair anion is converted into a halogen ion, a halogen ion, a hypohalite ion, a nitrate ion, a nitrite ion, a disulfite ion, It can be converted into monovalent anions such as sulfite ions and phosphate ions.

The microbial adsorbent of the present invention can take the form of powder, granules, fibers, film, etc. depending on the method for producing the polymer compound.

The microbial adsorbent of the present invention can be used, for example, as follows. That is, when removing microorganisms from liquids such as drinking water and various types of water, the microorganism adsorbent of the present invention may be directly added to the water, or a device filled with powdered or granular microorganism adsorbent, or a fibrous or sheet material may be used. The water to be treated can be passed through a device equipped with a type of microbial adsorbent. Furthermore, when removing microorganisms floating in a gas such as air, the gas may be passed through a device equipped with the microorganism adsorbent. Furthermore, in the case of removing microorganisms adhering to the solid surface, this can be accomplished, for example, by lightly wiping the surface with a fibrous microorganism adsorbent.

The microbial adsorbent of the present invention may further contain optional components such as known antibacterial agents and microbicides, if necessary.

〔Effect of the invention〕

The microbial adsorbent of the present invention is brought into contact with either a bacterial suspension of 101 to 10' individuals/ml or a bacterial suspension of 103 to 104 individuals/ml under the conditions described in Japanese Patent Publication No. 62-41641. Even when the microorganisms were removed, the microorganism adsorption performance was superior to that of the active ingredient in the microorganism control agent described in the above-mentioned publication, in that all the bacteria in the suspension were adsorbed within 2 to 3 hours.

Therefore, the microbial adsorbent of the present invention can easily adsorb and remove bacteria in water, air, and solid surfaces by contacting it with drinking water, various types of water, air, and solid surfaces. It is useful for purposes such as improving the durability of objects. Further, the microorganism adsorbent of the present invention can be used as a microorganism immobilization carrier for a bioreactor or a biosensor by taking advantage of its large microorganism adsorption ability.

〔Example〕

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of 1-phenethyl-4-vinylpyridinium bromide/dimethylaminoethyl acrylate/divinylbenzene copolymer: (i) 500 g of water was placed in an 11-separable flask equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube. Add 10g of calcium carbonate powder and boil for 150 rp.
The mixture was stirred at a speed of m to ensure uniform dispersion. In this state, a solution consisting of 105 g of 4-vinylpyridine, 10 g of dimethylaminoethyl acrylate, 13 g of divinylbenzene, 1 g of diisobutylene nitrile, and 100 g of methyl benzoate was added, and the mixture was heated at 80°C while stirring at a speed of 150 rpm. Heated for 3 hours. The obtained polymer beads were filtered and rinsed with 1% acetic acid to dissolve and remove calcium carbonate, followed by repeated washing with water and 1% sodium chloride, and finally washing with ethanol and vacuum drying to obtain 4-vinylpyridine/ Spherical particles of dimethylaminoethyl acrylate/divinylbenzene copolymer {}
is.

Amount of ffl: 123g, average dry smoke particle size of copolymer particles: 250
μm, nitrogen content 12%. These copolymer particles are referred to as vinylpyridine polymer (1).

(ii) Next, the above-mentioned vinylpyridine polymer (1)
21 g was suspended in 100 g of methanol, 120 g of phenethyl bromide was added thereto, and the mixture was heated at 60° C. for 5 hours. After isolation by polymer bead filtration, washing with ethanol,
Next, by vacuum drying, the title polymer particles in which the pyridine group was replaced with an N-phenethylpyridinium group (opposite: bromide ion) were obtained. Yield 43g, bromine content 28%.

Synthesis Examples 2 to 9 By the same operation as Synthesis Example 1 using various vinyl pyridines, hydrophilic ethylenically unsaturated monomers, crosslinking monomers, and phosphor-kylating agents shown in Table 1 below, Spherical particles (average particle size 10 to 800 μm) of vinylpyridium/hydrophilic ethylenic monomer/crosslinkable monomer copolymer were obtained.

Example l Escherichia coli 6. The chickens were suspended in 0.15 molar saline to obtain a concentration of 5 x 10' individuals/mA, and 5 g (dry weight 2 g) of 1-phenethyl-4-vinylpyridinium bromide/dimethylaminoethyl acrylate/divinylbenzene copolymer (polymer particles obtained in Synthesis Example 1) was added, and the mixture was heated at 35-37°C, 100-1
Stirring was continued at a speed of 2 O rpm. the result,
After 1.2 and 3 hours, the number of E. coli in the suspension was 2.5×103.1.5×10′,0 individuals/ml, respectively.
decreased significantly. Of the initial population of E. coli, 99.9
The time required for % to be absorbed by the adsorbent (temporarily taken as the bacterial cell adsorption capacity) was 18 minutes.

Examples 2 to 9 The bacterial adsorption ability of the vinylviridinium/hydrophilic ethylenic monomer/crosslinkable monomer copolymer obtained in Synthesis Examples 2 to 12 was evaluated by the same method as in Example 1. did. The results are shown in Table 2. In Table 2, the polymer particles obtained in Synthesis Examples 2 to 9 are represented as adsorbents 2 to 9, respectively.

The following margin Comparative Example 1 Escherichia coli 6. Number of individuals/mf of 5 x 1 0 7! ．．
Suspend this suspension in physiological saline to a concentration of 20
ml of 1-benzyl-4-vinylpyridinium bromide/divinylbenzene copolymer, which had been swollen with physiological saline at 37°C in advance (2 g dry weight), was added.
37℃. Stirring was continued at a speed of 100-12 O rpm. As a result, after 1, 3.5 and 10 hours, the size of the large intestine in the suspension was 8.2 x 108 and 2. OX1
0' 1. It decreased to IX10'LO x 102.

Furthermore, the adsorption capacity for bacterial cells was 2.5 hours, which was significantly lower than that of the adsorbent of the present invention.

that's all

Claims (1)

[Claims] 1. A polymer compound obtained by copolymerizing vinylpyridines, a hydrophilic ethylenically unsaturated monomer, and a crosslinking monomer to form a copolymer, and further quaternizing the pyridine group as an active ingredient. microbial adsorbent.