JP3085310B2 - Microbial removal material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a microorganism removing material that adsorbs and removes microorganisms, and more particularly to a microorganism removing material that can efficiently remove microorganisms in water or air.

[Prior Art] Conventionally, as a microorganism removing material capable of effectively collecting microorganisms in the field of water treatment and the like, an insoluble polymer compound comprising a crosslinked polyvinylpyridinium halide has been proposed (Japanese Patent Publication No. 62-41641). Gazette). However, the above-mentioned crosslinked polyvinylpyridinium halide is insoluble and can be handled only as a solid, and is difficult to process. Therefore, there is a problem that the adsorption efficiency per unit weight of the compound is poor. Further, the crosslinked polyvinylpyridinium halide catches microorganisms in a living state, so that adsorbed microorganisms proliferate and clogging is promoted, so that the service life is short.

On the other hand, in the field of air purification such as masks and air filters, adsorbents such as activated carbon and zeolite are used to adsorb microorganisms contained in the air together with other dust. There was no ability to adsorb selectively and selectively, and the adsorbing power of microorganisms was not sufficient.

[Problems to be Solved by the Invention] The present invention has been made to solve the above-mentioned drawbacks of the prior art, and has a high ability to adsorb microorganisms, is unlikely to cause clogging by the adsorbed microorganisms, and has a long service life. The task is to provide materials.

[Means for Solving the Problems] The present invention provides a compound represented by the general formula: (Where R ₁ is a benzyl group, a C ₄ -C ₁₆ alkyl group or a pentafluorophenylmethyl group, R ₂ is a hydrogen atom or a C ₁ -C ₃ alkyl group, X is a halogen atom, Y is a hydrogen atom , C ₁ -C _{3 represents} an alkyl group, a benzyl group, an ether group, a carboxyl group, a carboxylate group or an aryl group, and n and m in the formula represent n: m
Represents 10:90 to 90:10. The present invention relates to a microorganism-removing material, characterized in that a vinyl copolymer represented by the formula (1) is attached to the surface of a substrate and a bactericide is present in the substrate.

[Action] That is, the above-mentioned vinylpyridinium-based copolymer used in the microorganism-removing material of the present invention is soluble in an organic solvent despite having the same excellent microorganism-adsorbing ability as a crosslinked polyvinylpyridinium halide. Thus, it is possible to process other substrates, such as impregnation or coating, which was impossible with the crosslinked polyvinylpyridinium halide. Therefore, by attaching a vinylpyridinium-based copolymer having an excellent ability to adsorb microorganisms to the surface of a substrate, a portion not used for adsorption of microorganisms can be eliminated, and the ability to adsorb microorganisms per unit weight can be increased. In particular, when a porous substrate having a large surface area is used as the substrate, a high microorganism adsorption ability can be obtained in addition to the filtration function of the porous substrate.

In the present invention, since the vinylpyridinium-based copolymer is adhered to the substrate surface and the bactericide is present in the substrate, the adsorbed microorganisms die or the growth is suppressed. In addition, no clogging occurs due to the propagation of microorganisms on the microorganism removing material.

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

Wherein R ₁ is a benzyl group, a C _{4 to} C ₁₆ alkyl group or a pentafluorophenylmethyl group, R ₂ is a hydrogen atom or a C _{1 to} C ₃ alkyl group, X is a halogen atom, Y is a hydrogen atom, alkyl group C ₁ -C _3, a benzyl group, an ether group, a carboxyl group, a carboxylic acid ester group or an aryl group. The vinyl copolymer is a random copolymer or a block copolymer.

Monovinyl monomers used for copolymerization include ethylene, propylene, butene and other monoolefins, styrene, vinyl acetate, acrylic acid, acrylate,
Examples include, but are not limited to, methacrylic acid, methacrylic acid esters, aliphatic vinyl esters, acrylonitrile, and derivatives thereof, and various substances can be used alone or in combination.

The ratio of 4-vinylpyridine to monovinyl monomer, that is, the ratio of n: m, varies depending on the type of monovinyl monomer used and the degree of polymerization, but is generally about 10: 9.
Desirably, it is in the range of 0 to 90:10. 4 more than this range
If the proportion of vinylpyridine is small, sufficient microbial adsorptivity cannot be obtained, and if it is higher than this, the resulting copolymer becomes highly water-soluble and cannot be used in the field of water treatment. In particular, the preferred ratio of n: m is 10:90 to 70:30
It is.

Further, the polymerization degree of the vinyl copolymer is at least 30.
It is desirably 0 or more. If the degree of polymerization is lower than 0, the resulting vinyl copolymer becomes water-soluble and cannot be used in the field of water treatment.

The copolymer of a monovinyl monomer and 4-vinylpyridine is reacted with a halide such as an alkyl halide, a benzyl halide, or a pentafluorophenylmethyl halide to quaternize pyridine to obtain a functional group represented by the following formula. Form a group.

Formula: X ^- R ₁ -N ^{+ It is considered that} this functional group mainly acts to adsorb the microorganism while maintaining the active state.
Although the mechanism is not clear, this functional group is positively charged and the cell surface of microorganisms is generally negatively charged, so it is presumed that electrostatic interaction is one important factor. You.

The vinylpyridinium-based copolymer thus obtained is insoluble or hardly soluble in water but soluble in an organic solvent, and is used as a solution by dissolving in an organic solvent. As the organic solvent, alcohols, esters, phenols, ethers and the like can be used, but it is preferable to use alcohols from the viewpoint of easy handling.

Next, the solution in which the vinylpyridinium-based copolymer is dissolved is applied to the substrate by means such as impregnation, spraying, or coating. Thereafter, the vinylpyridinium-based copolymer is adhered to the base material through a drying step.

The adhesion amount of the vinylpyridinium-based copolymer to the substrate is not particularly limited, but the adhesion thickness of the vinylpyridinium-based copolymer is desirably in the range of 0.001 to 1 μm. It is preferable that the adhesion amount is weight%. If the amount is smaller than this, a sufficient effect of adsorbing microorganisms is difficult to obtain, and if the amount is larger than this, although the amount of the vinyl copolymer used is increased, the adsorbing effect is not improved and the economy becomes uneconomical.

On the other hand, a germicide is present in the substrate used for the microorganism removing material of the present invention. The germicide according to the present invention is a germicide in a broad sense that includes both a bactericidal agent that kills microorganisms and an antibacterial or bacteriostatic agent that prevents or suppresses the growth of microorganisms. Examples of the bactericide used in the present invention include polymyxin antibiotics, positive surfactants such as quaternary ammonium salts, amphoteric surfactants such as alkylaminoethylglycine, chlorhexidine, and piguanides such as polyhexamethylenepiguanidine; Suitable are higher fatty acids such as undecylenic acid, metals and metal ions, phenols and the like. These disinfectants may be adhered to the surface of the substrate or contained in the substrate so as to be present in the substrate. For example, when the substrate is a nonwoven fabric, a bactericide may be attached to the surface of the fiber constituting the nonwoven fabric, or a germicidal fiber or a bactericidal fiber containing the above bactericide may be added to the constituent fibers of the nonwoven fabric to form a bactericide. May be contained in the base material.

In the case of using the microorganism removing material of the present invention in a gas, the bactericide to be used is not particularly limited, but water treatment,
In particular, in water treatment of waterworks, it is not desirable that the disinfectant component is dissolved in water, so it is preferable to use a water-insoluble or sparingly soluble disinfectant. Examples of such a bactericide include powders of gold, silver, copper, and the like; antibacterial zeolites obtained by replacing zeolites with metal ions having bactericidal properties; and piguanide or quaternary quaternary polymer chains such as polyvinyl, polyacrylate, polyester, and polyamide. A polymer-type immobilized bactericide having an ammonium salt immobilized thereon, and a silicone-type immobilized bactericide such as 3- (trimethoxysilyl) -propyltrimethyloctadecyl ammonium chloride can be suitably used.

When the disinfectant is attached to the substrate, the attachment may be performed at any time in principle, even before or after the vinylpyridinium-based copolymer is attached to the substrate, the vinylpyridinium-based copolymer may be used. It may be simultaneous with the attachment.
In addition, the disinfectant may be adhered to the base material as it is, or may be dissolved or dispersed in an appropriate organic solvent, impregnated, sprayed, or coated on the base material, and then adhered by blowing off the organic solvent. May be. In particular, when the vinylpyridinium-based copolymer is attached to the substrate at the same time as the vinylpyridinium-based copolymer, a disinfectant dissolved or dispersed in an organic solvent solution of the vinylpyridinium-based copolymer may be attached to the substrate.

When a bactericide is contained in the base material, the bactericide may be contained in the constituent materials such as fibers, foams, films, and resin sheets constituting the base material, or the bactericide may be added to the constituent materials. What has derived the functional group which has this may be used.

The amount of the disinfectant to be attached may be appropriately selected according to the type of the disinfectant and the disinfecting power, but it is necessary to attach at least such an amount that the adsorbed microorganisms do not grow.

Substrates to which the above-mentioned vinylpyridinium-based copolymer is adhered include porous materials such as nonwoven fabrics, woven fabrics, knits, papers, foams, ceramics sintered bodies, organic or inorganic particles, honeycombs, multi-stages, etc. A structure such as a plate is used. Among them, the porous body is suitable as a microorganism removing material because of its large surface area. Among them, a nonwoven fabric having a three-dimensional structure is preferable because it has an excellent function as a filter.

The microorganisms to be removed by the microorganism removing material of the present invention include bacteria, fungi, algae, viruses, and the like.

The microorganism-removing material of the present invention adsorbs microorganisms present in water or in the air with high adsorption efficiency, and kills them with a bactericide or prevents them from growing. Have.

When the microorganism-removing material of the present invention is used in a gas, since the microorganism-adsorbing ability of the vinylpyridinium-based copolymer is not sufficiently exhibited unless water is present, a gas having a high humidity is used as the gas to be treated. It is preferable to use a humectant or a humectant in combination, and it is particularly preferable to use the humidifier in combination with a humidifier such as a humidifier to increase the humidity of the gas to be treated. As the humectant, for example, calcium chloride, alkaline earth metal salts such as magnesium chloride and lithium chloride,
Deliquescent substances such as potassium metasilicate and titanium sulfate, water-soluble polymers such as polyvinyl alcohol, polyacrylate and polyvinylpyrrolidone, silica gel, zeolite, collagen, ethylene glycol, diphosphorus pentoxide, magnesium oxide, calcium oxide, etc. Can be used.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples.

(Example 1) 4-vinylpyridine and styrene were copolymerized at a ratio of 1: 3 mol, and then quaternized with 4-vinylpyridine and an equimolar amount of benzyl bromide to obtain a vinyl copolymer. Was.

On the other hand, a fibrous web made of rayon fiber (denier 1.5 denier) is subjected to hydroentanglement treatment to give a basis weight of 90 g / m ² and a thickness of 0.5 mm.
Was obtained.

An ethanol solution (vinyl polymer and antibacterial zeolite fine powder) in which the above-mentioned vinyl copolymer is dissolved in this hydroentangled nonwoven fabric and antibacterial zeolite fine powder (Bakutekira, trade name, manufactured by Kanebo Co., Ltd.) is dispersed. Weight ratio with: 97:
After impregnating with 3), drying was performed at 75 ° C. to obtain a microorganism removing material having an adhesion rate of the copolymer to the nonwoven fabric of 1.5% by weight.

A 5 cm × 50 cm spirally wound microbial removal material is placed in a container, and 200 ml of a solution of Escherichia coli suspended in 0.85% sterile saline at a concentration of 1 × 10 ² cells / ml is further placed in the container.
The mixture was stirred with a magnetic stirrer. Two hours later, the number of viable bacteria remaining in the solution was measured using an agar plate pour method and found to be 0 cells / ml, and 2 × 10 ⁴ cells (1 ×
It was confirmed that E. coli (10 ² cells / ml × 200 ml) was adsorbed.

Next, the microorganism-removing material to which E. coli was adsorbed was taken out,
Cut 5cm x 5cm, place on SDC agar medium
After culturing at 48 ° C. for 48 hours, the number of E. coli colonies on the agar was measured and found to be 2.

(Comparative Example 1) A microorganism removing material was produced in exactly the same manner as in Example 1 except that the antibacterial zeolite fine powder was not used.

Using this microorganism-removing material, an adsorption experiment of Escherichia coli was performed in the same procedure as in Example 1. After 2 hours, the number of viable bacteria remaining in the solution was 0 cells / ml. 10 ⁴ of E. coli was confirmed that it has been adsorbed.

Next, the microorganism-removing material to which E. coli was adsorbed was taken out,
Cut 5cm x 5cm, place on SDC agar medium
After culturing at 48 ° C. for 48 hours, the number of E. coli colonies on the agar was measured and found to be 328.

From these results, it was found that the microorganism-removing materials of Example 1 and Comparative Example 1 were both excellent in the ability to adsorb Escherichia coli, but only Example 1 had an action of sterilizing the adsorbed Escherichia coli. . From this fact, it was revealed that the microorganism removing material of Example 1 can efficiently remove bacteria in water without causing clogging due to propagation of bacteria.

(Example 2) 4-vinylpyridine and styrene were copolymerized at a ratio of 1: 2.5 mol, and then quaternized with 4-vinylpyridine and an equimolar amount of benzyl bromide to obtain a vinyl copolymer. Was.

On the other hand, a fiber web made of splittable fibers (fineness of about 0.3 denier after splitting) composed of a polyester component and a nylon component is subjected to a hydroentanglement treatment to split the fibers,
The fabric was entangled to obtain a nonwoven fabric having a basis weight of 100 g / m ² and a thickness of 0.6 mm.

This hydroentangled nonwoven fabric is impregnated with an ethanol solution obtained by dissolving and dispersing the vinyl copolymer, the antibacterial zeolite fine powder and lithium chloride in a ratio of 100: 3: 150, and then drying at 75 ° C. Thus, a microorganism removing material having an adhesion rate of the copolymer to the nonwoven fabric of 1.5% by weight was obtained.

Then, a 10 cm square filter unit was prepared by pleating the microorganism removing material 10 cm x 120 cm, a coliform spray box was installed upstream of the filter unit, and a membrane with a pore diameter of 0.45 μm that did not allow E. coli to pass downstream. A suction pump was installed through the filter.

After passing sterilized humidified air for 30 minutes in advance to sufficiently absorb the microorganism-removing material, a diluted saline of Escherichia coli is sprayed in a spray box, and the air containing Escherichia coli is sucked by a suction pump.
Suction was performed at a rate of 10 liter / min for 2 minutes.

Thereafter, a filter unit made of a microorganism-removing material to which Escherichia coli was adsorbed was taken out, cut into 5 cm × 5 cm, placed on an SDC agar medium, cultured at 32 ° C. for 48 hours, and the number of Escherichia coli colonies on the agar was measured. However, there were three.

(Comparative Example 2) A microorganism-removing material was produced in exactly the same manner as in Example 2 except that the fine antibacterial zeolite powder was not used.

Using this microorganism-removing material, an adsorption experiment of Escherichia coli in the air was performed in the same procedure as in Example 2. Then, a unit filter made of the microorganism-removing material to which Escherichia coli was adsorbed was taken out, cut into 5 cm × 5 cm, and then After culturing at 32 ° C. for 48 hours on an SDC agar medium, the number of E. coli colonies on the agar was measured to be 285.

From these results, it was found that the microorganism-removing materials of Example 2 and Comparative Example 2 were both excellent in the ability to adsorb Escherichia coli, but only Example 2 had the action of sterilizing the adsorbed Escherichia coli. . From this fact, it became clear that the microorganism removing material of Example 2 can efficiently remove bacteria in the air without causing clogging due to propagation of bacteria.

[Effects of the Invention] The microorganism removing material of the present invention, as described above, is capable of killing or inhibiting the growth of microorganisms collected by a specific vinylpyridinium-based copolymer having a microorganism-adsorbing ability with a bactericide. Thereby, microorganisms can be efficiently removed from the object. Further, since the vinylpyridinium-based copolymer used in the microorganism-removing material of the present invention is soluble in an organic solvent and can be adhered to various substrate surfaces, it can be used for microorganism adsorption without waste,
It has excellent ability to adsorb microorganisms per unit weight of the copolymer. In particular, when a porous body is selected as the base material, a large surface area can be obtained, and in addition to the filter effect of the porous body,
Excellent microorganism removal can be expected. Furthermore, as described above, the microorganisms trapped in the bioremoval material of the present invention are killed or their growth is suppressed by the action of the fungicide. Does not occur and the service life is long.

As described above, since the microorganism removing material of the present invention can efficiently remove microorganisms in a liquid or a gas, it is suitable for use as a water treatment material for water and sewage or as a mask or an air filter.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C12N 11/08 C12N 11/08 (56) References JP-A-2-88504 (JP, A) JP-A-63-310803 (JP) JP-A-1-258609 (JP, A) JP-A-2-88505 (JP, A) JP-A-2-88506 (JP, A) JP-A-58-154502 (JP, A) Patent 2814266 (JP, A) JP, B2) US Patent 2,487,829 (US, A) UK Patent 883,750 (GB, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 43/40 101 C08F 226/06 A01N 37/12 CAPLUS (STN)

Claims (2)

(57) [Claims] (1) a general formula, (Where R ₁ is a benzyl group, a C ₄ -C ₁₆ alkyl group or a pentafluorophenylmethyl group, R ₂ is a hydrogen atom or a C ₁ -C ₃ alkyl group, X is a halogen atom, Y is a hydrogen atom , C ₁ -C _{3 represents} an alkyl group, a benzyl group, an ether group, a carboxyl group, a carboxylate group or an aryl group, and n and m in the formula represent n: m
Represents 10:90 to 90:10. A) a vinyl copolymer which is insoluble or hardly soluble in water and soluble in an organic solvent and adhered to the surface of a substrate, and a bactericide is present in the substrate. Microorganism removing material. 2. The microorganism removing material according to claim 1, wherein the disinfectant is water-insoluble.