JP3174971B2 - Antibacterial material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial material, and more particularly to a polymer material containing an antibacterial component having a phosphonium base ionically bonded to an acidic group. Antibacterial material.

[0002]

BACKGROUND OF THE INVENTION In our surrounding environment, a great variety of antibacterial agents are used, for example, in the industrial, agricultural or food applications.

[0003] Most of the antibacterial agents currently used are synthetic antibacterial agents having a rather high toxicity. But,
In recent years, research aimed at reducing the toxicity of antibacterial agents has been progressing, and immobilized antibacterial agents which are insoluble and show little toxicity have been developed.

A polymer type antibacterial agent which is an immobilized antibacterial agent is
It has been reported that a pendant-type antibacterial agent is fixed to a polymer chain such as polyvinyl, polyacrylate, polymethacrylate, polyester, and polyamide. For example, an alkylpyridinium salt and an alkyldimethylbenzylammonium salt are immobilized on a polyvinyl chain, biguanites are applied on a polyacrylate chain and a polymethacrylate chain, and a quaternary ammonium salt and an alkylpyridinium are applied on a polyester chain and a polyamide chain. Salt is fixed.

For example, Japanese Patent Application Laid-Open No. 54-86584 discloses an antibacterial agent containing an antimicrobial component having a quaternary ammonium base such as alkyltrimethylammonium chloride ionically bonded to an acidic group such as a carboxyl group or a sulfone group. An antibacterial material mainly composed of a molecular substance is described.

Japanese Unexamined Patent Publication (Kokai) No. 61-245378 discloses a polyester copolymer containing at least a basic group such as an amidine group and a guanidine group and an acidic group containing an antibacterial component such as a quaternary ammonium base. An antimicrobial polyester fiber characterized by being present on the fiber surface is described.

[0007] Phosphonium salt compounds, like various nitrogen-containing compounds, are known as biologically active chemicals having a broad activity spectrum against bacteria, fungi and algae. (JP-A-57-204286, JP-A-63-60903, JP-A-62-11490)
No. 3, JP-A-1-93596, JP-A-2-2-2
No. 40090)

[0008]

However, quaternary ammonium salts such as alkyltrimethylammonium chloride and alkyldimethylbenzylammonium disclosed in JP-A-54-86584 and JP-A-61-24537 are disclosed.
No. 8 discloses that the antibacterial component may be any antibacterial compound capable of reacting with an acidic group.
Basic groups such as amidine groups such as -stilbene-dicarboxamidine-diisethionate [stilbamidine isethionate] and guanidine groups such as p- (chlorophenyldiguanidide) -hexane [chlorhexidine]; and benzalkonium chloride And there is no disclosure that a phosphonium salt is ion-bonded to the acidic group in the present invention. Although the antibacterial component has a broad antibacterial spectrum, the antibacterial effect of acting on microorganisms in a short time contact is not yet sufficient.

Further, despite the fact that the above-mentioned phosphonium salt-based compound shows a strong antibacterial action, it is difficult to handle in a solution form and its use is limited, and the phosphonium salt is immobilized on a polymer substance as in the present invention. There is no disclosure or suggestion of trying to expand the use of the device.

In view of the above facts, the inventors of the present invention have conducted intensive studies and as a result, have found that a polymer material mainly containing an antibacterial agent component having an acidic group and a phosphonium base ionically bonded to the acidic group is mainly used. We have found that polymeric materials exhibit excellent antimicrobial activity.

[0011]

That is, the present invention provides an antimicrobial component having an acidic group and a phosphonium base ionically bonded to the acidic group in an amount of 0.1 to 80 mol%.
The present invention relates to an antibacterial material mainly composed of an immobilized polymer substance.

The present invention having the above-mentioned structure exerts excellent effects on preserving and imparting antibacterial properties to polymer molded articles, fibers, films, etc. by fully utilizing and utilizing the inherent properties of the phosphonium salt. .

Hereinafter, the present invention will be described in more detail.

The monomer having an acidic group according to the present invention includes a carboxyl group, a sulfone group, a phosphone group,
A monomer having each acidic group such as a phosphine group and a phenolic hydroxyl group or a salt thereof such as a sodium salt, a potassium salt, and an ammonium salt is exemplified.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, and 3-butene-
Examples thereof include 1,2,3-tricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, and 4-pentenoic acid.

Examples of the monomer having a sulfone group include styrene sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate, 3-chloro-4-vinylbenzine sulfonic acid, and 2-acrylamide-2- Methylpropanesulfonic acid, 2-acryloyloxybenzenesulfonic acid, 2-acryloyloxynaphthalene-2-sulfonic acid, 2-methacryloyloxynaphthalene-2-sulfonic acid, sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid or 4-sulfoic acid And naphthalene-2,7-dicarboxylate.

Examples of the monomer having a phosphonic group include allylphosphonic acid, acid phosphoxyethyl ethyl methacrylate, 3-chloro-2-acid phosphoxypropyl methacrylate, 1-methylvinylphosphonic acid, and 1-phenylvinylphosphonic acid. , 2-phenylvinylphosphonic acid, 2-methyl-2-phenylvinylphosphonic acid, 2- (3-chlorophenyl) vinylphosphonic acid, 2-diphenylvinylphosphonic acid, and the like.

As the monomer having a phosphine group,
For example, allylphosphinic acid and the like can be mentioned, and as the monomer having a phenolic hydroxyl group, for example, ortho-oxystyrene, ortho-vinylanisole and the like can be mentioned.

The other monomer copolymerizable with the acidic group-containing monomer can be selected from a wide range depending on the use of the antibacterial material as the final product. Specific examples thereof include ethylene, Propylene, vinyl chloride,
Allyls such as vinylidene chloride, vinyl acetate, vinyl propionate, vinyl crotonate, acrylate, methacrylate, acrylonitrile, hydroxyethyl acrylate, hydroxymethacrylate, styrene and its derivatives, butadiene, acrylamide and its derivatives, and acrylpropyl ester Compound, vinyl ether, terephthalic acid, isophthalic acid, maleic acid, vinyl pyridine, N-vinyl-2-pyrrolidone, isobutylene, diisobutylene and the like, and these may be used alone or in combination of two or more.

As the polymerization method, any of ordinary polymerization methods such as an emulsion polymerization method, a solution polymerization method, and a bulk polymerization method can be employed. Among them, the emulsion polymerization method has many acidic groups distributed on the surface of the obtained polymer particles. It is particularly preferably used because it tends to do so.

The antibacterial agent having a phosphonium base used in the present invention includes, for example, tetraethylphosphonium bromide, triethylbenzylphosphonium chloride,
Tetra-n-butylphosphonium bromide, tetra-
n-butylphosphonium chloride, tri-n-butylmethylphosphonium iodide, tri-n-butyloctylphosphonium bromide, tri-n-butyloctylphosphonium bromide, tri-n-butylhexadecylphosphonium bromide, tri-n-butyloctadecyl Phosphonium bromide, tri-n-butylallylphosphonium bromide, tri-n-butylbenzylphosphonium bromide, tri-n-octylethylphosphonium bromide, tris (3-hydroxypropyl) octylphosphonium bromide, tris (3-hydroxypropyl) octadecylphosphonium Bromide, tris (3-hydroxypropyl) hexadecylphosphonium bromide and the like can be mentioned.

In the above phosphonium salt, the antibacterial activity is affected by the length of the alkyl group bonded to phosphorus, and for example, ethyl, butyl, octyl, etc., increase the antibacterial activity.
Also, one of the alkyl groups is long, for example, tri-n-
Ethyl octadecyl phosphonium bromide or tri-n
-Butyloctadecylphosphonium bromide and the like exhibit a very high antibacterial activity, and when the above phosphonium salt is used as an antibacterial component in an antibacterial material, it exhibits an excellent antibacterial effect as compared with conventionally used quaternary ammonium salts and the like.

In the present invention, the antibacterial activity is such that the monomer of the phosphonium salt ionically bonded to the acidic group is 0.1 to 80 mol%, preferably 5 to 50 mol%, of the antibacterial material according to the present invention. It is desirable to contain them in proportions. If the amount is less than 0.1 mol%, the antibacterial activity is reduced. If the amount exceeds 80 mol%, the amount of the antibacterial activity is more than necessary, which is economically unfavorable and changes the properties of the resin.

The method for producing the antibacterial material according to the present invention can be produced by any method. For example, as a first method, the phosphonium salt is brought into contact with a monomer having an acidic group to produce the phosphonium salt. It is a method of polymerizing or copolymerizing a monomer having an acidic group and an acidic group.

The second method is a method in which a phosphonium salt is reacted with a polymer having an acidic group to introduce the phosphonium salt into the polymer.

As a third method, an oligomer having a degree of polymerization of 5 to 100 is formed from an acidic group-containing monomer, and then an antimicrobial component having a phosphonium base is brought into contact with the antimicrobial component to introduce the antimicrobial component. And a method of cross-linking to a polymer by using a cross-linking agent such as a methylolated melamine compound, a peroxide, or a zaziridine compound.

As a fourth method, there is a method in which an acidic group-containing monomer is irradiated with an actinic ray on a surface of a polymer substance such as polystyrene to cause graft polymerization, and a phosphonium salt is imparted to the acidic group on the surface.

In any of the above methods, an antibacterial material mainly comprising a polymer substance having an antibacterial component having an acidic group and a phosphonium salt ionically bonded to the acidic group is obtained.

[0029]

EXAMPLES Example 1 5.0 g of dimethyl sodium 5-sulfoisophthalate
(0.017 mol) was dissolved in 200 ml of water, and trinormal butyl dodecyl phosphonium chloride was added thereto.
An aqueous solution obtained by dissolving 9 g (0.017 mol) in 200 ml of water was dropped at room temperature, and reacted for 1 hour. After completion of the reaction, 200 ml of diethyl ether was added to extract the product. The solvent was distilled off and the residue was dried to obtain 9.8 g of dimethyl isophthalate containing a phosphonium salt.

Then, 3.8 g of this compound (0.006
Mol), 3.8 g (0.020 mol) of dimethyl terephthalate, 3.2 g (0.051 mol) of ethylene glycol
A mixture of 8 mg of calcium acetate and 8 mg of antimony oxide was heated to 180 ° C. while introducing nitrogen gas. The reaction was carried out under these conditions for 1 hour, then the temperature and the degree of vacuum were gradually increased to 250 ° C. and 1 Torr, and the reaction was carried out under these conditions for 1 hour. After completion of the reaction, the obtained product is cooled,
By taking out from the reaction vessel, 5.2 g of a polyester copolymer containing a phosphonium salt was obtained.

Example 2 5.0 g of dimethyl sodium 5-sulfoisophthalate
(0.017 mol) was dissolved in 200 ml of water, and an aqueous solution obtained by dissolving 7.3 g (0.017 mol) of trinormal butyltetradecylphosphonium chloride in 200 ml of water was dropped at room temperature and reacted for 1 hour. After completion of the reaction, 200 ml of diethyl ether was added to extract the product. The solvent was distilled off and the residue was dried to obtain 9.6 g of dimethyl isophthalate containing a phosphonium salt.

Then, 3.9 g of this compound (0.006 g)
Mol), 3.8 g (0.020 mol) of dimethyl terephthalate, 3.2 g (0.051 mol) of ethylene glycol
A mixture of 8 mg of calcium acetate and 8 mg of antimony oxide was heated to 180 ° C. while introducing nitrogen gas. The reaction was carried out under these conditions for 1 hour, then the temperature and the degree of vacuum were gradually increased to 250 ° C. and 1 Torr, and the reaction was carried out under these conditions for 1 hour. After completion of the reaction, the obtained product is cooled,
By taking out from the reaction vessel, 6.5 g of a polyester copolymer containing a phosphonium salt was obtained.

Example 3 5.0 g of dimethyl sodium 5-sulfoisophthalate
(0.017 mol) was dissolved in 200 ml of water, and an aqueous solution in which 7.8 g (0.017 mol) of trinormal butylhexadecylphosphonium chloride was dissolved in 200 ml of water was added dropwise at room temperature and reacted for 1 hour. After completion of the reaction, 200 ml of diethyl ether was added to extract the product. The solvent was distilled off and dried to obtain 10.5 g of dimethyl isophthalate containing a phosphonium salt.

Then, 4.1 g of this compound (0.006
Mol), 3.8 g (0.020 mol) of dimethyl terephthalate, 3.2 g (0.051 mol) of ethylene glycol
A mixture of 8 mg of calcium acetate and 8 mg of antimony oxide was heated to 180 ° C. while introducing nitrogen gas. The reaction was carried out under these conditions for 1 hour, then the temperature and the degree of vacuum were gradually increased to 250 ° C. and 1 Torr, and the reaction was carried out under these conditions for 1 hour. After completion of the reaction, the obtained product is cooled,
By taking it out of the reaction vessel, 6.2 g of a polyester copolymer containing a phosphonium salt was obtained.

Example 4 5.0 g of dimethyl sodium 5-sulfoisophthalate
(0.017 mol) was dissolved in 200 ml of water, and an aqueous solution in which 8.3 g (0.017 mol) of trinormal butyl octadecylphosphonium chloride was dissolved in 200 ml of water was added dropwise at room temperature and reacted for 1 hour. After completion of the reaction, 200 ml of diethyl ether was added to extract the product. The solvent was distilled off and the residue was dried to obtain 11.2 g of dimethyl isophthalate containing a phosphonium salt.

Then, 4.3 g of this compound (0.006
Mol), 3.8 g (0.020 mol) of dimethyl terephthalate, 3.2 g (0.051 mol) of ethylene glycol
A mixture of 8 mg of calcium acetate and 8 mg of antimony oxide was heated to 180 ° C. while introducing nitrogen gas. The reaction was carried out under these conditions for 1 hour, then the temperature and the degree of vacuum were gradually increased to 250 ° C. and 1 Torr, and the reaction was carried out under these conditions for 1 hour. After completion of the reaction, the obtained product is cooled,
By taking out from the reaction vessel, 6.9 g of a polyester copolymer containing a phosphonium salt was obtained.

Example 5 5.0 g of dimethyl sodium 5 -sulfoisophthalate
(0.017 mol) was dissolved in 200 ml of water, and trinormal butyl dodecyl phosphonium chloride was added thereto.
An aqueous solution obtained by dissolving 9 g (0.017 mol) in 200 ml of water was dropped at room temperature, and reacted for 1 hour. After completion of the reaction, 200 ml of diethyl ether was added to extract the product. The solvent was distilled off and the residue was dried to obtain 9.8 g of dimethyl isophthalate containing a phosphonium salt.

Then, 0.3 g of this compound (0.005
Mol), 1.9 g (0.010 mol) of dimethyl terephthalate, 1.3 g (0.021 mol) of ethylene glycol, 4 mg of calcium acetate, and 4 mg of antimony oxide were heated to 180 ° C. while introducing nitrogen gas.
The reaction was performed under these conditions for 1 hour, and then the temperature and the degree of vacuum were gradually increased to 250 ° C. and 1 Torr, and the reaction was performed under these conditions for 1 hour. After completion of the reaction, the obtained product is cooled,
By taking out from the reaction vessel, 1.5 g of a polyester copolymer containing a phosphonium salt was obtained.

Comparative Example 1 Polyethylene terephthalate containing no antimicrobial component and prepared from dimethyl terephthalate and eletin glycol was prepared.

Comparative Example 2 5.0 g of dimethyl sodium 5-sulfoisophthalate
(0.017 mol) was dissolved in 200 ml of water, and an aqueous solution of 7.1 g (0.017 mol) of tri-n-butyltetradecylammonium chloride dissolved in 200 ml of water was added dropwise at room temperature and reacted for 1 hour. Was. After completion of the reaction, 200 ml of diethyl ether was added to extract the product. The solvent was distilled off and the residue was dried to obtain 8.9 g of dimethyl isophthalate containing an ammonium salt.

Next, 3.8 g of this compound (0.006 g)
Mol), 3.8 g (0.020 mol) of dimethyl terephthalate, 3.2 g (0.051 mol) of ethylene glycol
A mixture of 8 mg of calcium acetate and 8 mg of antimony oxide was heated to 180 ° C. while introducing nitrogen gas. The reaction was carried out under these conditions for 1 hour, then the temperature and the degree of vacuum were gradually increased to 250 ° C. and 1 Torr, and the reaction was carried out under these conditions for 1 hour. After completion of the reaction, the obtained product is cooled,
By taking it out of the reaction vessel, 6.1 g of a polyester copolymer containing an ammonium salt was obtained. <Antimicrobial activity test> The above synthesized polyester copolymer was formed into a film, and a test piece having a diameter of 2 cm was prepared.

0.5 ml of a bacterial solution having a concentration of Staphylococcus aureus (IFO 12732) and Escherichia coli (IFO 3806) to 10 ⁷ cells / ml was collected on an agar medium and spread uniformly.

Next, a test piece was placed on this agar medium for 3 hours.
The cells were cultured at 7 ° C. for 48 hours, and the growth of the bacteria was visually observed to determine the antibacterial activity. The results were as shown in Table 1.

Judgment: A: There is a growth inhibition zone under and around the sample.

△: There is a growth inhibition zone of about １ ／ below and around the sample.

×: No growth inhibition zone for bacteria.

[0047]

[Table 1]

[0048]

The antibacterial material of the present invention can be used for various bacteria,
It shows a broad spectrum of antibacterial activity that is effective against fungi, algae, viruses, etc., and is particularly remarkable for bacteria.

Furthermore, it is more stable to heat than quaternary ammonium salts and other organic compounds. For example, tetra-n-butylphosphonium bromide has a decomposition temperature as high as about 300 ° C. And is chemically stable. Therefore, the present invention does not decompose even when exposed to a polymer molding temperature (for example, 250 ° C.), and can sufficiently exhibit the original antibacterial performance.

Antimicrobial activity (MIC) of the antimicrobial agent according to the present invention
Although it is not uniform depending on the type of phosphonium salt, the preparation or the type and environment of various fungi, the concentration of the phosphonium salt-based vinyl polymer is 0.1 ppm or more, and the quaternary ammonium salt-based antibacterial is generally used. The antibacterial activity is higher than the agent.

The antibacterial agent according to the present invention may be used in various industrial fields, for example, in slime prevention or control materials in papermaking, water, oils and fats, emulsions, paper, wood, rubber, plastics, fibers, films, paints, etc., depending on the form of the preparation. Preservative and antibacterial functions.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-245378 (JP, A) JP-A-57-204286 (JP, A) JP-A-63-60903 (JP, A) JP-A 54-1984 86584 (JP, A) JP-A-62-114903 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/40

Claims (1)

(57) [Claims] An antibacterial component having an acidic group and a phosphonium base ionically bonded to the acidic group is contained in an amount of 0.1 to 8%.
An antibacterial material mainly composed of a polymer substance fixed at 0 mol% .