JPH10316514A - Antimicrobial and antimicrobial composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial which possesses fine and sustaining antimicrobial effect and is high in dispersion into a solution by formulating a polyvinyl imidazoline as an active ingredient. SOLUTION: This antimicrobial is obtained by formulating a polyvinyl imidazoline (e.g. 2-vinyl imidazoline polymer, 3-vinyl imidazoline polymer, etc.) having weight-average molecular weight of preferably 1,000-1,000,000 as an active ingredient. The polyvinyl imidazoline is obtained, for example, from a polymer such as acrylonitrile polymer or methacrylonitrile polymer containing nitrile groups and a polyamide. Further, in order to enhance the antimicrobial activity and change the solubility, the polyvinyl imidazoline is used by changing it into the polyvinyl imidazoline complex with a metal ion (e.g. copper, silver, zinc, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial agent and an antibacterial composition, and more particularly, comprises polyvinylimidazoline, which has bactericidal and antibacterial properties against harmful microorganisms such as bacteria and molds, as an active ingredient. The present invention relates to an antibacterial agent and an antibacterial composition using the same.

[0002]

2. Description of the Related Art Various antibacterial agents have been proposed. For example, in inorganic antibacterial agents, metals such as silver, copper, and zinc or compounds thereof are known to have bactericidal properties, so that metals such as silver, copper, and zinc or compounds thereof are zeolites, ceramics, It was used by being supported on a carrier such as glass or activated carbon. In addition, as an organic antibacterial agent, such a metal powder dispersed in a synthetic resin,
Using chelate resin adsorbing metal (Japanese Patent Publication No. Sho 6
JP-A-3-11076) and those using metal salts of N-long-chain acylamino acids (JP-A-3-181403) are also known.

However, when an inorganic antibacterial agent is used in a liquid form, the metal or its compound is immediately separated even if added to the liquid, and the effect of the antibacterial agent cannot be exhibited. In addition, in the case of using a synthetic resin in which metal powder is dispersed or using a chelate resin, when this is used in a paint or the like, the pores of the resin are blocked and the effect is reduced, and the dispersion in water or the like is also reduced. There was a drawback that the property was bad. Further, those using a metal salt of an N-long-chain acylamino acid require a solvent such as aqueous ammonia in order to enhance solubility, and thus have a drawback that the working environment is deteriorated.

As described above, the conventional antibacterial agents have problems in solubility and dispersibility in liquids such as water, stability of a loaded substance, and the like. There was a problem that it was not possible.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an antibacterial agent which has good and long-lasting action under such circumstances and background, and that its dosage form can be combined with various components and equipment. And an antimicrobial composition using the agent.

[0006]

As a result of various studies on the above-mentioned problems, the present inventor has found that 1) an antibacterial agent containing polyvinylimidazoline as an active ingredient can be used without using a solvent such as aqueous ammonia which degrades the working environment. It is easy to dissolve or disperse in water and other solvents, and exhibits good antibacterial properties. 2) Further, the solubility and dispersibility in water and other solvents can be controlled by changing its physical properties with a crosslinking agent. The present inventors have found various facts that the antibacterial spectrum can be broadened and the antibacterial action can be enhanced by being able to bind metal ions, and the present invention has been completed.

That is, the present invention relates to an antibacterial agent containing polyvinylimidazoline as an active ingredient.

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

[0009] The antibacterial agent of the present invention contains polyvinylimidazoline as an active ingredient.

[0010] Here, the active ingredient means a component having an antibacterial action, and the antibacterial agent of the present invention can take various forms such as liquid and solid. In addition, additives such as dispersants, stabilizers, and solidifying agents, and solvents may be included. For example, a surfactant or the like can be used as a dispersant, a compound having an ultraviolet absorbing effect as a stabilizer, and polyethylene glycol or the like can be used as a solidifying agent.

In the antibacterial agent of the present invention, polyvinylimidazoline can be used alone as an active ingredient, but it may be mixed with another polymer or copolymerized with another monomer. Further, a poly (aminoethyl acrylamide) derivative obtained by hydrolyzing polyvinyl imidazoline can be used.

The structure of polyvinylimidazoline includes 2-vinylimidazoline polymer, 3-vinylimidazoline polymer, 4-vinylimidazoline polymer, and N-vinylimidazoline polymer.
Among them, 2-vinylimidazoline polymer is preferably used because of easy production.

Further, the molecular weight is not particularly limited, but considering that the operability is affected by the viscosity,
The weight average molecular weight is preferably from 1,000 to 1,000,000, more preferably from 10,000 to 500,000.

The polyvinylimidazoline used in the antibacterial agent of the present invention is generally prepared from a polyamine containing a nitrile group-containing polymer such as an acrylonitrile polymer or a methacrylonitrile polymer, as described in JP-B-42-6271. it can. At this time, the acrylonitrile polymer or the methacrylonitrile polymer may be a homopolymer or a copolymer.

The monomers copolymerizable with the monomers of the acrylonitrile polymer and the methacrylonitrile polymer include vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride, and vinylidene halides such as vinylidene chloride. , Acrylic acid, methacrylic acid, itaconic acid,
Unsaturated carboxylic acids such as maleic anhydride, and salts thereof, (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, and unsaturated salts such as methyl vinyl ketone and methyl isopropenyl ketone Ketones, vinyl esters such as vinyl acetate and vinyl benzoate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, (meth) acrylamide and its alkyl-substituted products, vinyl sulfonic acid, (meth) allyl sulfonic acid, p-styrene sulfone Acid, 2-acrylamido-2-methylpropanesulfonic acid, unsaturated sulfonic acid such as (meth) acryloyloxyethylsulfonic acid and the like, salts thereof, styrene such as styrene, α-methylstyrene and chlorostyrene, and alkyl or halogen thereof. Substitute, allyl alcohol Le and its esters or ethers, vinyl pyridine, vinyl pyrimidine, vinyl imidazole, dimethyl aminoethyl methacrylate, and the like basic vinyl compounds such as vinyl benzyl dimethylamine.

As the polyamine to be reacted with the nitrile group-containing polymer, 1,2-diamines are preferably used, and ethyleneamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and aminoethylpiperazine are used. , Diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminooctane, diaminononane, diaminodecane, cyclohexylethylenediamine, benzylethylenediamine, phenylethylenediamine, methoxyphenylethylenediamine, dimethylphenylethylenediamine, tolylethylenediamine, N-cyclohexylethylenediamine, N-benzylethylenediamine , N-phenylethylenediamine, N-meth Hydroxyphenyl ethylenediamine, N- dimethyl-phenyl diamine, N- tolyl ethylenediamine, N- methylethylenediamine, N
-Ethylethylenedimine, N-isobutylethylenediamine, N-phenylethylenediamine, N- (2-aminoethyl) ethylenediamine and the like.

As the polyvinyl imidazoline used in the antibacterial agent of the present invention, a cross-linked polyvinyl imidazoline can be preferably used. For example, when the solubility in a solvent is good but the persistence of the effect as an antibacterial agent is poor, or when the viscosity is insufficient, the solubility can be reduced and the viscosity can be increased by crosslinking.

As a method of crosslinking, a crosslinking agent is generally used. As the cross-linking agent, a compound having a functional group capable of forming a cross-linked structure by reacting with an amine can be used, but when the nitrile group of the raw material polymer remains, a compound that reacts with the nitrile group can also be used, and vinylimidazoline or the raw material can be used. A compound that reacts with a monomer copolymerized with a nitrile-containing monomer or a derivative thereof can also be used.

The crosslinking agent is not particularly limited as long as it is a compound capable of forming a crosslinking structure with polyvinyl imidazoline as described above. For example, examples of compounds that can react with amines include carboxylic acids such as acetic acid, sulfonic acids, aldehydes, ketones, halides, alcohols, amines, acid anhydrides, acid halides, and the like. Although used, the carboxylic acids may be monofunctional. As the crosslinking compound, not only a compound forming a covalent bond but also a compound forming an ionic bond can be used. The degree of cross-linking in the molecule can be selected depending on the desired degree of liquid absorption and the strength of the resin after liquid absorption. Further, when producing a polymer containing a nitrile group as a raw material, a crosslinkable monomer may be previously copolymerized. As another crosslinking method, a part of polyvinylimidazoline can be hydrolyzed and the resulting amine can be reacted.

The polyvinyl imidazoline used in the antibacterial agent of the present invention can be used in the form of an amine or an amine salt. When used in the form of an amine salt, salts of inorganic acids and organic acids such as sulfate, hydrochloride, phosphate and acetate can be used as the type of salt.

As the polyvinylimidazoline used in the antibacterial agent of the present invention, a polyvinylimidazoline complex of a metal ion can be preferably used in order to enhance the antibacterial activity and change the solubility. Here, the metal ion is not particularly limited as long as it can coordinate to the amine, for example, silver, cadmium, cobalt, copper, iron, mercury, manganese, nickel, lead, zinc, calcium, germanium, lithium, Examples thereof include magnesium, platinum, thallium, gold, and bismuth. Among them, copper, silver, and zinc have high antibacterial activity and are preferably used. Further, not only one kind of these metal ions may be used alone, but also two or more kinds thereof may be used as a metal complex of polyvinylimidazoline.

When two or more metal ions are used,
As shown below, in addition to adding a mixture of metal ions to polyvinyl imidazoline and its raw material, when using a metal complex of polyvinyl imidazoline manufactured separately for each metal ion, appropriately mix and use the necessary amount, etc. Such,
Any method can be adopted without departing from the purpose of the present invention.

The method for producing the metal complex is not particularly limited. For example, the metal complex can be produced by adding it to a raw material for producing polyvinyl imidazoline or by adding a metal ion to the produced polyvinyl imidazoline. Here, the raw material of the metal ion can be used without particular limitation as long as it can produce a metal complex of polyvinylimidazoline, for example, a salt of an organic acid such as acetic acid,
Salts of inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and oxides of metals are exemplified.

The antibacterial agent of the present invention is Aspergillus
It has antibacterial properties against fungi such as mold, Penicillium and other fungi, algae, bacteria and the like, and can be used for various purposes. For example, by directly adding to water,
Fungi and the like that can be generated in water tanks, pools, baths, coolants and the like can be sterilized and algae-killed. In addition, various products having antibacterial properties can be obtained by applying or impregnating textiles, knits, nets, yarns, strings, cords, ropes, and other fibers, paper, leather, sand, ceramics, glass, and the like. . In particular, the composition containing the antibacterial agent of the present invention can be easily obtained by applying to a material having good impregnating properties such as fiber and paper. For example, the hygiene management can be easily performed by using a product such as a disposable diaper. Is preferable. In addition, resin, paint,
When added to an adhesive or the like, it can be used for various applications such as production of an antibacterial resin, paint having antibacterial properties, and imparting antibacterial properties to various materials by an adhesive.

The device containing the antibacterial agent of the present invention can be impregnated not only on the surface but also inside.
These may be appropriately selected depending on the specific application.

Further, in order to enhance the antibacterial activity or broaden the antibacterial spectrum, it can be used in combination with existing bactericides and antibacterial agents.

Further, the specific amount of the antibacterial agent of the present invention varies depending on the intended use, and cannot be specified unconditionally. However, in principle, it is significantly different from the general use in the intended use. There is no. However, the antibacterial agent of the present invention can be expected to be used unprecedented because of its excellent functions and effects, and it is possible to reduce the amount used to achieve the same level of effect with other antibacterial agents. Needless to say.

[0028]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In addition, evaluation was implemented by the method shown below.

(1) Zinc Content The zinc content was measured by ICP-AES.

(2) Mold resistance test A test was conducted with reference to JIS-Z2911. That is,
In a solution containing polyvinyl imidazoline, 5 cm x 5
The filter paper (made by Toyo Roshi, 5C) cut into cm was added and impregnated. Then, the filter paper was placed on a petri dish containing a medium (glucose, peptone, agar medium: Nippon Pharmaceutical, GP, trade name: "Digo"), and the mold spore suspension was sprinkled evenly. This was cultured at 28 ° C. (± 1 ° C.) in a wet manner, and the state of mycelial growth was observed.

(3) Measurement of Molecular Weight The molecular weight of polyvinyl imidazoline was measured by GPC by high performance liquid chromatography to determine the weight average molecular weight.

Example 1 Polyacrylonitrile 1 was placed in a stainless steel autoclave.
13. g, ethylenediamine 448 g and zinc acetate
5 g was added and heated at 130 ° C. for 6 hours. Ammonia was generated and the reaction pressure increased. When the reaction solution was taken out and poured into acetone, a zinc complex of polyvinylimidazoline was obtained. The zinc content in the polyvinyl imidazoline was 3% by weight as measured by the method described above. The molecular weight was measured by the method described above, and was found to be about 20,000 in weight average molecular weight. Next, the filter paper was impregnated with a 5% aqueous solution of the polyvinylimidazoline zinc complex and dried.

Using the filter paper impregnated with the polyvinylimidazoline zinc complex, the mold resistance test described above was carried out. As shown in Table 1, even after 2 weeks, the test piece (filter paper) portion and the sample piece were in contact with each other. No hyphal growth was observed in any part.

[0034]

[Table 1]

Example 2 Copper (II) chloride was added to an aqueous solution of polyvinylimidazoline hydrochloride.
Was added to obtain a polyvinylimidazoline copper complex. This polyvinyl imidazoline copper complex partially became insoluble in water and became fine particles. The copper content was 3% by weight calculated from the charged amount. In the same manner as in Example 1, the polyvinyl imidazoline copper complex was impregnated into a filter paper, and the above-described mold resistance test was performed. The results are shown in Table 1. As a result, even after one week, the growth of hypha was not observed in the test piece (filter paper) portion and the portion in contact therewith, and the growth area of the hypha did not exceed 1/3 of the test piece even after two weeks.

Example 3 When silver chloride was added to an aqueous solution of polyvinyl imidazoline acetate, a silver polyvinyl imidazoline complex was obtained. A part of the polyvinyl imidazoline silver complex was insoluble in water and turned into fine particles. The silver content was 1% by weight calculated from the charged amount. In the same manner as in Example 1, the polyvinyl imidazoline copper complex was impregnated into a filter paper, and the above-described mold resistance test was performed. The results are shown in Table 1. As a result, even after 2 weeks, the growth of hypha was not observed in the test piece (filter paper) portion and the contact portion.

Example 4 5 g of polyacrylonitrile, 13.4 g of ethylenediamine, 6 g of ammonium chloride and 40 g of n-butanol were placed in a flask and heated at 95 ° C. for 6 hours. The reaction solution was taken out and poured into acetone to obtain a polyvinyl imidazoline hydrochloride. This molecular weight was measured by the method described above and found to be about 20,000 in weight average molecular weight. A filter paper was impregnated with a 5% aqueous solution of polyvinylimidazoline hydrochloride and dried. The mold resistance test described above was carried out in the same manner as in Example 1, and the results are shown in Table 1. as a result,
Even after two weeks, no growth of hypha was observed in the test piece (filter paper) portion and the portion in contact therewith.

Example 5 Polyvinylimidazoline crosslinked with acetic acid was suspended in water and impregnated into filter paper. Use this test piece (filter paper)
The mold resistance test described above was carried out in the same manner as in Example 1,
The results are shown in Table 1. As a result, even after one week, the growth of hypha was not observed in the test piece (filter paper) portion and the portion in contact therewith.
Did not exceed 3.

Comparative Example 1 A filter paper was immersed in sterilized distilled water, and the mold resistance test described above was carried out in the same manner as in Example 1. The results are shown in Table 1. As a result, after 5 days, hyphal growth was observed in an area exceeding one third of the test piece, and after one week, hyphal growth was observed over the entire surface.

From the above results, it can be seen that in Example 1 under the condition that the growth of bacteria progresses for a certain period as seen in Comparative Example 1,
As shown in No. 5 to 5, it was found that the growth of bacteria was not observed on the filter paper containing polyvinylimidazoline or the growth was suppressed.

[0041]

The antibacterial agent of the present invention has a good and long-lasting antibacterial effect, and has a high dispersibility in a solution. It can be used not only as it is added to the solution as it is, but also in combination with various equipments. This is extremely useful because it is also possible.

Claims (5)

[Claims] An antibacterial agent comprising polyvinylimidazoline as an active ingredient. 2. The antibacterial agent according to claim 1, wherein the polyvinylimidazoline is a 2-vinylimidazoline polymer. 3. The antibacterial agent according to claim 1, wherein the polyvinylimidazoline is crosslinked. 4. The antibacterial agent according to claim 1, wherein the polyvinylimidazoline is a complex with one or more metals selected from the group consisting of zinc, copper and silver. 5. An antibacterial composition obtained by impregnating a fiber or paper with the polyvinylimidazoline according to any one of claims 1 to 4.