JPH05255011A - Microbial control agent - Google Patents

Abstract

(57) [Summary] [Objective] To provide a microbial control agent which is insoluble in water and capable of efficiently removing microorganisms. [Structure] A chelate polymer compound having an aminocarboxylic acid group, an aminoalkylenephosphonic acid group, or a metal salt thereof as a chelate-forming group is used. [Effect] The microorganism control agent containing the chelate polymer compound as an active ingredient has a high rate of capturing and removing microorganisms.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microbial control agent exhibiting excellent microbial control performance when removing bacteria from water, air, solid surfaces and the like.

[0002]

2. Description of the Related Art Pool water, cooling tower water, bath water, drinking water,
Various kinds of water such as ultrapure water, futons, carpets, walls,
Removing microorganisms floating or adhering to living spaces such as folds, building materials, or animals, plants, sludge, etc.
Very important.

Conventionally, for the purpose of removing such microorganisms, a method of treating with a microbicide such as chlorine, iodine, hydrogen peroxide, phenol and a bactericidal chemical, a method of sterilizing by ozone treatment or heat treatment, Alternatively, a method of filtering and sterilizing using a membrane or a filter has been adopted. However, in the method using a microbicide, since these harmful microbicides remain, food products, drinking water,
Its use for the purpose of sterilizing pharmaceuticals is greatly restricted. In addition, the method of removing bacteria by ozone treatment, heat treatment, filtration or the like is not necessarily economical because it requires large equipment.

On the other hand, recently as a technique for capturing microorganisms,
A method using a crosslinked poly-N-benzyl-4-vinylpyridinium halide (hereinafter abbreviated as PVP microorganism trapping agent) has been proposed (Japanese Patent Publication No. 62-41641).
This microorganism scavenger is a new attempt in that it does not have the problem of remaining harmful substances such as general microbicides used conventionally.

[0005]

However, when the microorganism trapping agent described in this publication is used, 10 ⁶ cells / ml
It takes 5 hours or more to remove the bacteria from the concentrated bacterial suspension, and there is a drawback that the throughput per unit time is small. Therefore, the emergence of a microbial control agent with a high removal rate is desired. In view of such circumstances, the present inventors have completed the present invention as a result of intensive research to find a microbial control agent that does not have the above-mentioned drawbacks.

[0006]

That is, the present invention provides a chelating polymer compound having an aminocarboxylic acid group, an aminoalkylenephosphonic acid group, and at least one chelate-forming group selected from metal salts thereof as an active ingredient. The present invention provides a microbial control agent. Further, the present invention is
A method for removing a microorganism from a substance in which the microorganism is present is provided using such a microorganism removing agent.

The chelate polymer compound used in the microbial control agent of the present invention may be any one having the above chelate-forming group in the molecule, and its shape, production method, kind of resin substrate, etc. are particularly limited. Not. For example, a resin produced by the following method or other commercially available chelate resin can be used.

A method of reacting a resin having a carbonyl chloride group or a chloromethyl group (hereinafter abbreviated as active chlorine-containing resin) with an aminocarboxylic acid compound. Here, the active chlorine-containing resin is a styrene-divinylbenzene copolymer having a carbonyl chloride group or a chloromethyl group, a phenol resin, a polyolefin resin such as polyethylene or polypropylene, or an acid chloride of poly (meth) acrylic acid. Can be mentioned. Further, as aminocarboxylic acid compounds, iminodiacetic acid, glycine, alanine, valine, methionine, asparagine,
Glutamine, aspartic acid, glutamic acid, 5-amino-3-azapentanoic acid, 8-amino-3,6-diazaoctanoic acid, 11-amino-3,6,8-triazaundecanoic acid, 9-amino-3-azanonanoic acid , Guanidinoacetic acid, and alkali metal or alkaline earth metal salts of these acids.

A method in which an aminated resin obtained by reacting a resin having a nitrile group with an amino compound [hereinafter referred to as aminated resin (1)] is further reacted with a halogenated alkylcarboxylic acid compound or an acrylic acid compound. Examples of the resin having a nitrile group used here include vinyl cyanide such as acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, methacrylonitrile, etaacrylonitrile, fumardinitrile, crotonnitrile, 2-cyanoethyl acrylate, and 2-cyanoethyl methacrylate. Examples thereof include a polymer of a system monomer, or a copolymer of these vinyl cyanide monomers with another ethylenically unsaturated monomer copolymerizable therewith. Examples of the ethylenically unsaturated monomer copolymerizable with the vinyl cyanide monomer include divinylbenzene, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and vinyl acetate. Further, as the amino compound, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine,
Examples thereof include alkylenepolyamines such as tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, hydrazine, guanidine, and ammonia. Among these amino compounds, alkylene polyamines are preferably used. Examples of the halogenated alkylcarboxylic acid compound include monochloroacetic acid, monobromoacetic acid, monochloropropionic acid, monobromopropionic acid, and salts of these carboxylic acids with alkali metals, alkaline earth metals, Ib copper group metals, or IIb zinc group metals. Can be mentioned. Examples of acrylic acid compounds include acrylic acid, methacrylic acid, and salts of these acids with alkali metals, alkaline earth metals, Ib copper group metals, or IIb zinc group metals.

An aminated resin having active hydrogen in a resin obtained by reacting an active chlorine-containing resin with an amino compound (hereinafter referred to as aminated resin (2)) is further prepared by adding a halogenated alkylcarboxylic acid compound or an acrylic acid-based compound. A method of reacting a compound. Specific examples of the active chlorine-containing resin, amino compound, halogenated alkylcarboxylic acid compound and acrylic acid compound used here are the same as those described above.

A method in which a resin obtained by subjecting an acrylic acid-based resin to a condensation reaction with an amino compound [hereinafter, referred to as a condensation reaction acid amide resin] is further reacted with a halogenated alkylcarboxylic acid compound or an acrylic acid-based compound. The acrylic acid-based resin used here is polyacrylic acid,
Mention may be made of polymethacrylic acid and esters of these acids, such as methyl esters, ethyl esters and the like. Specific examples of the amino compound, the halogenated alkylcarboxylic acid compound and the acrylic acid compound are the same as those described above.

Aminating resin (1) or aminating resin
A method of reacting (2) with an alkylene phosphonating agent. Examples of the alkylene phosphonating agent used here include halogenated alkyl phosphorylating agents such as chloromethyl phosphoric acid and chloroethyl phosphoric acid. Further, an alkyleneizing agent such as formaldehyde or trioxymethylene and a phosphorylating agent such as phosphorus trichloride, phosphorous acid or hypophosphorous acid can be used at the same time.

The respective reactions mentioned above will be described in detail below.

Regarding the reaction method of, the reaction between the active chlorine-containing resin and the aminocarboxylic acid compound is carried out in a solvent such as water, N, N-dimethylformamide, methyl alcohol or ethyl alcohol, sodium hydroxide, potassium hydroxide or triethylamine. , N, N-dimethylaniline, N, N-diethylaniline and the like in the presence of a neutralizing agent, about 40 ° C. or higher, preferably about 50 to 90 ° C.
Heat to If the reaction temperature is lower than about 40 ° C., the reaction rate becomes slow and the reaction takes a long time, which is not preferable.

The reaction is carried out at the above temperature for about 0.1 to 7 hours. The optimum time within the range is appropriately determined depending on the reaction temperature, the reaction solution concentration, the solvent used, the type of the aminocarboxylic acid compound, and the like. However, it is possible to react for a longer time. This reaction is generally carried out under normal pressure, but it can be carried out under pressure.

The reaction ratio of the aminocarboxylic acid compound to the active chlorine-containing resin is preferably about 0.25 mol or more, more preferably about 0.3 to 0.5 mol, based on 1 mol of the carbonyl chloride group or chloromethyl group in the resin. Is. The use of more aminocarboxylic acid compounds than necessary involves a recovery process after the reaction, which makes the processing operation complicated. On the other hand, if the amount of the aminocarboxylic acid compound used with respect to the active chlorine-containing resin is less than about 0.25 mol, the ability of the obtained chelate polymer compound to control microorganisms will be deteriorated, which is not preferable.

The neutralizing agent neutralizes and removes hydrochloric acid by-produced by the reaction between the carbonyl chloride group or chloromethyl group and the aminocarboxylic acid compound, thereby promoting the reaction between the carbonyl chloride group or chloromethyl group and the aminocarboxylic acid compound. Used for. However, since the aminocarboxylic acid compound that does not directly react with the carbonyl chloride group or the chloromethyl group also acts as a dehydrochlorinating agent, even if the amount of the neutralizing agent used is less than the molar equivalent to the amount of by-produced hydrochloric acid, there is no particular problem in the reaction. Also, even if the neutralizing agent is used in excess, there is no problem in the reaction. Appropriate amount of the neutralizing agent is determined by preliminary experiments.

Regarding the reaction method of Amination resin (1), N, N-dimethylformamide containing water, or water containing N, N-dimethylformamide, dimethylsulfoxide, toluene, 1 , In a solvent such as 2-dichloroethane,
It is produced at a reaction temperature of 100 ° C or higher, preferably 120 ° C or higher. When the reaction temperature is lower than 100 ° C., the reaction becomes slow and the reaction takes a long time, which is not preferable.

The reaction is generally about 0.5 at the above temperatures.
It is carried out for about 50 hours, preferably for 1 to 12 hours. The optimum time within the range is appropriately determined depending on the reaction temperature, the reaction solution concentration, the solvent used, the type of amino compound, and the like.
However, it is possible to react for a longer time. This reaction is generally carried out under normal pressure, but it can be carried out under pressure.

The reaction ratio of the amino compound to the resin having a nitrile group is preferably about 0.5 mol or more per 1 mol of the nitrile group in the resin. However, if an excessive amount of amino compound is used, a recovery process after the reaction becomes necessary and the process operation becomes complicated. On the other hand, when the amount of the amino compound used for the resin having a nitrile group is small, the amount of the carboxylic acid group introduced in the next step is small, and the microbial control performance of the resulting reaction-produced chelate polymer compound deteriorates. Therefore, about 1 to 6 mol of the amino compound is preferably used with respect to 1 mol of the nitrile group in the resin.

Aminating resin reacted as described above
(1) is then reacted with the halogenated alkylcarboxylic acid compound or the acrylic acid-based compound as it is, or after separating and removing the solvent and the amino compound of the end reaction, or after washing and drying as necessary. Let

The reaction between the aminated resin (1) and the halogenated alkylcarboxylic acid compound is carried out by using water, N, N-dimethylformamide, ethyl alcohol, methyl alcohol,
In the presence of a solvent such as 1,2-dichloroethane and chloroform and a neutralizing agent such as sodium hydroxide, potassium hydroxide, triethylamine, N, N-dimethylaniline and N, N-diethylaniline, the temperature is about 40 ° C or higher, It is preferably heated to about 50 to 90 ° C. Reaction temperature is about 40
If the temperature is lower than 0 ° C, the reaction rate becomes slow and the reaction takes a long time, which is not preferable.

The reaction is carried out at the above temperature for about 0.1 to 7 hours. The optimum time within the range is appropriately determined depending on the reaction temperature, the reaction solution concentration, the kind of the halogenated alkylcarboxylic acid compound, and the like. However, it is possible to react for a longer time. This reaction is generally carried out under normal pressure, but it can be carried out under pressure.

The reaction ratio of the aminated resin (1) and the halogenated alkylcarboxylic acid compound is preferably about 0.5 mol or more of the halogenated alkylcarboxylic acid compound with respect to 1 equivalent of the basic group in the aminated resin (1). , More preferably 1
3 mol. If more halogenated alkylcarboxylic acid compounds are used, a recovery process after the reaction becomes necessary and the process operation becomes complicated. On the other hand, when the amount of the halogenated alkylcarboxylic acid compound used is less than the above with respect to the basic groups in the aminated resin (1), the addition amount of the alkylcarboxylic acid decreases, and the resulting reaction-generated chelate polymer compound microorganism Pest control performance is reduced.

The amount and method of addition of the neutralizing agent differ depending on the reaction conditions between the aminated resin (1) and the halogenated alkylcarboxylic acid compound, so that appropriate addition conditions can be determined by preliminary experiments. However, the neutralizing agent is an aminated resin
The neutralizing agent usually forms a by-product because it serves to neutralize the hydrogen halide and halogenated alkylcarboxylic acid compound by-produced by the reaction between the basic group in (1) and the halogenated alkylcarboxylic acid compound. It is preferable to use the total equivalent amount of the amount of hydrogen halide and the amount of carboxylic acid of the halogenated alkylcarboxylic acid. In general, a carboxylic acid of a halogenated alkylcarboxylic acid compound and an equivalent amount of a neutralizing agent are added in advance to form a salt of a halogenated alkylcarboxylic acid compound, and then the salt of the halogenated alkylcarboxylic acid compound and an amino acid are added. A method of gradually adding a neutralizing agent is adopted according to the amount of hydrogen halide by-produced by the reaction with the chemical resin (1).

The reaction between the aminated resin (1) and the acrylic acid compound is a known reaction known as the so-called Michael addition reaction. The reaction is carried out in a solvent such as water, ethyl alcohol, methyl alcohol, N, N-dimethylformamide or the like at about 40 ° C or higher, preferably about 50-.
It is performed at 100 ° C. When the reaction temperature is lower than 40 ° C., the reaction rate becomes slow and the reaction takes a long time, which is not preferable. The reaction is preferably carried out at the above temperatures for about 0.5-10 hours. This reaction is generally carried out under normal pressure, but it can be carried out under pressure.

The reaction ratio of the aminated resin (1) and the acrylic acid compound is preferably about 0.25 mol or more of the acrylic acid compound with respect to 1 equivalent of the basic group in the resin,
More preferably, it is about 0.5 to 3 mol. If more acrylic acid compounds are used than required, a recovery process after the reaction becomes necessary and the processing operation becomes complicated.On the other hand, if the amount of acrylic acid compounds with respect to the aminated resin (1) becomes about 0.25 mol or less. However, the addition amount of the acrylic acid-based compound decreases, and the microbial control performance of the obtained reaction-generated chelate polymer compound decreases.

When an acrylic acid ester is used as the acrylic acid type compound, a hydrolysis treatment is carried out under the usual ester hydrolysis conditions during or after the above reaction. This hydrolysis treatment is generally carried out at about 80 ° C. in the presence of an alkali metal hydroxide or alkaline earth metal hydroxide in an amount of about 2 times or more, usually about 3 to 10 times the molar amount of acrylic acid ester. Above, preferably at a temperature of about 90 to 150 ° C., for about 0.5 hours or more, preferably about 1 to 8 hours. When the amount of the alkali metal hydroxide or the alkaline earth metal hydroxide, the reaction temperature or the reaction time is lower than the above conditions, the hydrolysis of the ester is not sufficiently performed, which is not preferable. If the reaction temperature exceeds 150 ° C,
The elimination reaction of the acrylic acid group introduced by the reaction occurs simultaneously. The optimum reaction time is appropriately determined depending on the reaction temperature, the amount and concentration of the alkali metal hydroxide or the alkaline earth metal hydroxide within the above range. This reaction is generally carried out under normal pressure, but it can be carried out under pressure.

Regarding the reaction method of the amination resin (2), the synthesis reaction of the aminocarboxylic acid compound is replaced by ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, in place of the aminocarboxylic acid compound.
Except for using amino compounds such as tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and other alkylenepolyamines, hydrazine, guanidine, and ammonia, the reaction between the active chlorine-containing resin and the aminocarboxylic acid compound described above is almost the same. The reaction is carried out under the same conditions, that is, the reaction molar ratio is almost the same, the solvent is used, the reaction temperature, the reaction time and the like.

Aminating resin produced as described above
To the basic group in (2), an alkylcarboxylic acid group is introduced in the same manner as in the reaction of the aminated resin (1) with a halogenated alkylcarboxylic acid compound or an acrylic acid-based compound. A chelate polymer compound having an aminocarboxylic acid group to be used is produced.

Regarding the reaction method of the condensation reaction acid amide resin used in this reaction, the above acrylic acid-based resin is obtained by adding ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine,
Alkylenepolyamines such as tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, amino compounds such as hydrazine, guanidine, and ammonia without solvent or in solvents such as toluene, benzene, xylene, N, N-dimethylformamide, and cyclohexane. Medium, about 130 ° C or higher, preferably about 150-1
Obtained by reacting at 80 ° C. Reaction temperature is 1
When the temperature is 30 ° C. or lower, the dehydration condensation reaction rate of the acrylic acid group, the methacrylic acid group of the acrylic acid resin or the ester group thereof and the amino compound becomes slow, and the reaction takes a long time, which is not preferable.

The reaction is preferably about 0.5 at the above temperature.
It is carried out for 10 hours. The optimum time within that range is appropriately determined depending on the reaction temperature, the reaction solution concentration, the type of amino compound, and the like. However, it is possible to react for a longer time. This reaction can be carried out under normal pressure as long as the temperature is 130 ° C. or higher, but it is generally carried out under pressure.

The reaction ratio of the amino compound to the acrylic resin is preferably about 0.5 mol or more of the amino compound with respect to 1 mol of acrylic acid, methacrylic acid or their ester groups in the resin. But,
If more amino compounds are used, a recovery process after the reaction becomes necessary and the processing operation becomes complicated. On the other hand, if the amount of amino compounds is less than the above, the substitution of amino compounds will be less, and the carboxylic acid group in the next step will be less. Since the amount of introduction becomes small and the microbial adsorption capacity of the obtained reaction-produced chelate polymer compound decreases, it is not desirable. Therefore, more preferably, the amino compound is used in an amount of about 1 to 3 mol per 1 mol of acrylic acid, methacrylic acid or their ester groups in the resin.

For the basic group in the condensation reaction acid amide resin produced as described above, the reaction is similar to the reaction of the amination resin (1) with a halogenated alkylcarboxylic acid compound or an acrylic acid compound. The alkylcarboxylic acid group is introduced to produce a chelate polymer compound having an alkylcarboxylic acid group used in the present invention.

Reaction method of [0035] The reaction between the amination resin (1) or the amination resin (2) used in this reaction and the alkylene phosphonating agent can be carried out by a known method. However, the conditions for the alkylene phosphonation reaction differ depending on the type of the alkylene phosphonating agent used, and the following conditions are usually adopted.

When a halogenated alkyl phosphorylating agent such as chloromethyl phosphoric acid or chloroethyl phosphoric acid is used as an alkylene phosphonating agent, it is basic such as pyridine, N, N-dimethylaniline, sodium hydroxide, potassium hydroxide or sodium carbonate. In the presence of a catalyst, about 1/10 mol or more, preferably 1 to 5 mol, of a halogenated alkyl phosphorylating agent may be used and reacted per 1 equivalent of amino groups in the aminated resin.

The reaction is generally carried out using a solvent such as water, methyl alcohol, ethyl alcohol, propyl alcohol, N, N-dimethylformamide, dimethyl sulfoxide, 1,2-dichloroethane, 1,1,2-trichloroethane or pyridine. Be implemented. The reaction temperature is generally room temperature to 150 ° C, and the reaction time is generally 0.1 to 2
It takes about 4 hours.

When an alkylene phosphating agent such as formaldehyde or trioxymethylene or a phosphorylating agent such as phosphorus trichloride, phosphorous acid or hypophosphorous acid is used, an acidic catalyst such as hydrochloric acid or sulfuric acid is used. Is preferably used. With respect to the reaction molar ratio, the use of the solvent, the reaction temperature, the reaction time, etc., the same ranges as described above may be adopted.

Among the chelate resins having aminocarboxylic acid groups or aminoalkylenephosphonic acid groups produced as described above, in the present invention, the aminocarboxylic acid groups or aminoalkylenephosphonic acid groups are linked via polyaminoalkylene groups. Those bonded to the main chain of the chelate resin are preferably used.

The chelate resin produced as described above can be used as it is, or after washing and drying, for use in controlling the microorganisms of the present invention. If necessary, an aqueous solution of a metal compound such as a hydroxide of an alkali metal, a hydroxide of an alcal earth metal, an alkaline earth metal, a chloride or a sulfate of an Ib copper group metal or a IIb zinc group metal, and the like. After carrying out a contact reaction to form an aminocarboxylic acid and / or aminoalkylenephosphonic acid group into a metal salt, it can be provided for use in controlling the microorganism of the present invention.

The microbial control agent of the present invention can be effectively adsorbed and removed by contacting it with a gas, liquid or solid containing microorganisms. For example, when removing microorganisms present in water or air, the microbial control agent is placed in water or air containing the microorganisms as it is, or water or air containing the microorganisms is placed in a column packed with the microbial control agent. Just pass it. When removing microorganisms adhering to the surface of a solid such as futon or carpet, the microbial control agent of the present invention may be placed on or between the surfaces of these solids. Furthermore, microorganisms adhering to walls, folds, building materials, etc. can also be removed by bringing the microbial control agent of the present invention into contact with these surfaces. In addition, for example, when the wall is put into practice, it can be kneaded into a wall material or woven into a fiber which is a material of a futon or a carpet to control microorganisms which easily adhere to these.

In particular, since the microbial control agent of the present invention is insoluble in water, even when water treatment is performed using this agent, there is no risk that harmful substances will be dissolved in the treated water, and the conventional P
The rate of capturing and controlling microorganisms is higher than that of the VP microorganism capturing agent. Therefore, for the removal of microorganisms contained in drinking water, production water for food, pharmaceuticals, cosmetics, pool water, chemical industrial water such as pulp mills, fermentation plants, various cooling waters, various waste waters, and treated water thereof. It can be used effectively. Further, by passing air through a column filled with the microbial control agent of the present invention, microorganisms floating in the air can be removed. Therefore, it is possible to sterilize the air in a place where pathogenic bacteria are easily spread, such as hospitals and movie theaters, and it is useful for purposes such as environmental hygiene and improving the durability of buildings.

[0043]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples without departing from the gist thereof. In addition,% and parts in the examples are based on weight unless otherwise specified.

Example 1 To 64 parts of an acrylonitrile-divinylbenzene copolymer having a degree of crosslinking of 6 mol%, 206 parts of diethylenetriamine and 36 parts of water were added and reacted at 135 to 150 ° C. for 6 hours, and then the reaction product was filtered. After washing with water, 231 parts (undried) of aminated resin (hereinafter referred to as aminated resin A) was obtained. Next, 23.1 parts of this aminated resin A was mixed with acrylic acid.
14.4 parts and 50 parts of water were added, and the mixture was reacted at 70 ° C. for 6 hours, filtered, and washed with water. The obtained resin is immersed in 50 parts of a 10% aqueous sodium hydroxide solution at room temperature for 30 minutes,
Then, the mixture was filtered and washed with water to obtain 33 parts (undried) of resin. The resin thus obtained is hereinafter referred to as a microbial control agent A. 1g of dried microbial control agent A is taken, and 1 × 10 ⁶ Escherichia coli (Escherichia coli) /
It was added to 10 ml of 37 ° C. physiological saline containing ml concentration, and shaken for 1 minute or 2 hours. The number of Escherichia coli in the saline solution after the treatment was reduced to 400 cells / ml or less after shaking for 1 minute and to 20 cells / ml or less after shaking for 2 hours.

Examples 2 to 5 The same as Example 1 except that the amino compounds shown in Table 1 were used in the amounts shown in Table 1 instead of diethylenetriamine, and the amount of water used was also shown in the table. The same operation was performed to obtain an aminated resin. 10 of the obtained aminated resin
The reaction with acrylic acid was carried out in the same manner as in Example 1 by using one-half amount thereof to synthesize the corresponding microbial control agent. For each of the obtained microbial control agents, the adsorption / removal performance of Escherichia coli was evaluated in the same manner as in Example 1. Table 1 shows the results of synthesizing the aminated resin and the microbial control agent, and the results of examining the number of E. coli after 2 hours using each microbial control agent.

[0046]

Examples 6 to 14 Each of the aminated resins obtained in the reactions of Examples 1 to 5 was used in a one-tenth amount, and Amberlite IRA-4, which is a commercially available ion exchange resin having a polyethylene polyamino group.
5 [made by Rohm and Haas], Diaion CR-20
[Made by Mitsubishi Kasei Co., Ltd.], Sumichelate MC-10 and
Sumichelate MC-20 [above, manufactured by Sumitomo Chemical Co., Ltd.] is used in a dry weight of 20 parts, and sodium monochloroacetate (23.3 parts) and water (50 parts) are added to each to give a pH of 11 to 13 in the reaction system. While pouring 10% sodium hydroxide aqueous solution together, the reaction was carried out at 40 to 50 ° C. for 12 hours. Then, filtration and washing with water gave a corresponding microbial control agent. For each microbial control agent obtained,
The adsorption removal performance of Escherichia coli was evaluated in the same manner as in Example 1. Table 2 shows the results of synthesizing the microbial control agents and the results of examining the number of E. coli after 2 hours using each microbial control agent.

[0048]

Examples 15 to 23 Aminated resins obtained by the reactions of Examples 1 to 5 were each added in a one-tenth amount, and Amberlite IRA-4, which is a commercially available ion exchange resin having a polyethylene polyamino group.
5 [made by Rohm and Haas], Diaion CR-20
[Made by Mitsubishi Kasei Co., Ltd.], Sumichelate MC-10 and
Sumichelate MC-20 [above, manufactured by Sumitomo Chemical Co., Ltd.] was used in a dry weight of 20 parts each, 20% formalin 30 parts, phosphorous acid 16.4 parts and 36% hydrochloric acid aqueous solution 20
Parts were added and reacted at 95 to 100 ° C. for 3 hours. Then, the mixture was filtered, immersed in 100 parts by volume of a 10% sodium hydroxide aqueous solution and kept for 1 hour, then washed and dehydrated to obtain a corresponding microbial control agent. For each of the obtained microbial control agents, the adsorption / removal performance of Escherichia coli was evaluated in the same manner as in Example 1. Table 3 shows the results of synthesizing the microbial control agents and the results of examining the number of Escherichia coli after 2 hours using each microbial control agent.

[0050]

Examples 24 to 32 2 g of each resin having a microbial control function obtained in Examples 1, 6 and 15 was used, and
100 ml of 2N sulfuric acid, 1 g / L of Cu ²⁺ ion
100 ml of an aqueous solution containing pH 3.7 at a concentration of 1, or an aqueous solution of pH 4.3 containing Ag ⁺ ions at a concentration of 1 g / L 1
In addition to 00 ml, the mixture was shaken for 3 hours, filtered, washed with water and dried to obtain a microbial control agent having different functional groups. For each microbial control agent obtained,
The adsorption removal test of Escherichia coli was conducted in the same manner as in Example 1. The results of examining the number of E. coli after 2 hours are shown in Table 4.

[0052]

Comparative Example 1 21 parts of Sumichelate CR-2 [manufactured by Sumitomo Chemical Co., Ltd.], which is a commercially available chelating resin of vinylpyridine-divinylbenzene copolymer, was suspended in 100 parts of ethanol,
Next, 100 parts of benzyl bromide was added and reacted at 80 ° C. for 24 hours, then filtered, washed with water and dried to obtain 32 parts of resin. Hereinafter, this resin is referred to as a microbial control agent X. Using this microorganism control agent X, an adsorbent removal test of Escherichia coli was carried out in the same manner as in Example 1. The number of bacterial cells after shaking for 1 minute was 1.6 × 10 ⁵ cells / ml, and after shaking for 2 hours. The number of bacterial cells was 3.0 × 10 ³ cells / ml. On the other hand, without adding the microbial control agent, keep the physiological saline containing the cells warm at 37 ° C.
The number of cells was examined after 2 minutes and 2 minutes (hereinafter, such a test method is referred to as a control). As a result, the cell count after 1 minute was 1.2 × 10 ⁶ cells / ml, and the cell count after 2 hours was 8.6 × 10 ⁵ cells / ml.

Examples 33-35 and Comparative Example 2 Staphylococcus aureus
us) (Staphylococcus aureus) or Salmonella tifi (Sal
10 ml of 37 ° C. physiological saline containing 1 × 10 ⁶ monella typhi / ml, and Bacillus subtilis or Pseudomonas fluorescens Pseud
100 ml of spore suspension containing omonas fluoresence) at a concentration of 1 × 10 ⁸ cells / ml, and 1 g each of a microbial control agent or resin was added to each solution and the mixture was heated at 27 ° C. for 2 hours.
Time processing was performed. The microbial control agent or resin used is
Microbial control agents A and F obtained in Examples 1, 6 and 15
And O, and the aminated resin A of Example 1 for comparison. For comparison, the same experiment was conducted on a liquid (control) containing no microbial control agent or resin. The number of cells in the liquid after the treatment is shown in Table 5.

[0055]

[0056]

EFFECTS OF THE INVENTION Since the microbial control agent of the present invention is insoluble in water, there is no possibility that harmful substances will remain in the treated water even when water treatment is performed using this agent. In addition, this microbial control agent, when compared with conventional PVP microbial capture agents,
Since the speed of capturing and controlling microorganisms is high, it is possible to effectively remove the microorganisms floating or adhering to liquids such as various kinds of water and wastewater, gases such as air, or solids such as futon, carpet, and wall material. Further, by using the microbial control agent of the present invention inside a futon, carpet, wall material, etc., it is possible to prevent the attachment of microorganisms. Due to these characteristics, the microbial control agent of the present invention has great industrial value.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukio Oguri 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Tomohiro Teramae 4-2-1 Takashi Takarazuka-shi, Hyogo No. Sumitomo Chemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A microbial control agent comprising a chelate polymer compound having an aminocarboxylic acid group, an aminoalkylenephosphonic acid group, and at least one chelate-forming group selected from metal salts thereof as an active ingredient. 2. The microbial control agent according to claim 1, wherein the chelate-forming group is bonded to the main chain of the polymer compound through a polyaminoalkylene group. 3. A method for removing microorganisms, which comprises contacting a substance containing microorganisms with the agent for controlling microorganisms according to claim 1.