JPH09302137A - Antibacterial resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial resin having excellent antibacterial activity effective for exhibiting antibacterial effect on Pseudomonas aeruginosa, MRSA, etc. SOLUTION: This antibacterial resin is composed of a polymer having sulfonic acid group and silver ion bonded to the sulfonic acid group. The amount of the sulfonic acid group of the polymer is 3-7.5mmol based on 1g of the polymer. As an alternative, the antibacterial resin is composed of a polymer having sulfonic acid group and silver ion bonded to the sulfonic acid group and contains 2-10mmol of the silver ion based on 1g of the polymer. The polymer is especially preferably a polymer produced by polymerizing a monomer component composed mainly of an aromatic vinyl monomer and sulfonating the produced vinyl polymer. The antibacterial resin especially preferably has a spherical particle form having an average particle diameter of 0.3-500μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial resin obtained by binding a silver ion to the sulfonic acid group of a polymer having a sulfonic acid group. More specifically, the present invention relates to an antibacterial resin having excellent antibacterial activity against Pseudomonas aeruginosa, MRSA (methicillin-resistant Staphylococcus aureus) and the like.

[0002]

It is a well known fact that silver ions have excellent antibacterial properties, and for example, silver nitrate is widely used as a bactericide. And in recent years, especially Pseudomonas aeruginosa and MRSA
In order to prevent hospital-acquired infections such as, the development of various antibacterial resins containing the above-mentioned silver ion as an active ingredient is under way.

In order to improve the compatibility with various molding materials, organic materials such as fibers and paints, and to suppress the release (release) rate of silver ions to improve the sustainability of the antibacterial effect of silver. An antibacterial resin in which a silver ion is bonded to a sulfonic acid group of a polymer having a sulfonic acid group is known. For example, in JP-A-55-38855, silver ion is added in an amount of 0.0009 to 0.9 mmol per 1 g of the (meth) acrylic acid ester-based polymer containing 0.008 to 2.4 mmol of sulfonic acid group per 1 g of the polymer. There is disclosed an antibacterial resin obtained by ionic bonding of the above to the sulfonic acid group.

[0004]

However, the above-mentioned conventional antibacterial resins have a problem that they are inferior in effective antibacterial power in order to exert an antibacterial effect. In addition, the above-mentioned conventional antibacterial resin has an antibacterial activity for a long period of time under high temperature conditions.
It also has a problem that it is difficult to sustain it stably.

That is, the present invention has been made in view of the above-mentioned conventional problems, and an object thereof is an antibacterial obtained by binding a silver ion to the sulfonic acid group with respect to a polymer having a sulfonic acid group. The purpose of the present invention is to provide an antibacterial resin which is a functional resin and has an excellent antibacterial activity.

[0006]

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention are keenly aware of an antibacterial resin having a sulfonic acid group and a silver ion bonded to the sulfonic acid group. As a result of examination, an antibacterial resin containing 2 to 10 mmol of silver ion per 1 g of the polymer, or an antibacterial resin containing 3 to 7.5 mmol of sulfonic acid group in the polymer per 1 g of the polymer. It has been found that the resin composition has excellent antibacterial activity. Further, they have found that the antibacterial resin obtained by crosslinking the polymer by the bond between the sulfonic acid group and the polyvalent metal ion has excellent antibacterial activity and completed the present invention.

That is, in order to solve the above-mentioned problems, the antibacterial resin of the invention according to claim 1 is an antibacterial resin comprising a polymer having a sulfonic acid group and silver ions bonded to the sulfonic acid group. Resin is characterized by containing 2 to 10 mmol of silver ion per 1 g of the above polymer.

In order to solve the above-mentioned problems, the antibacterial resin according to the second aspect of the present invention is an antibacterial resin comprising a polymer having a sulfonic acid group and silver ions bonded to the sulfonic acid group. Resin, the sulfonic acid group of the polymer is 3 to 7.5 mmol per 1 g of the polymer.

According to each of the above constitutions, the antibacterial resin is excellent in the antibacterial effect of silver effective for exerting an antibacterial effect against Pseudomonas aeruginosa, MRSA and the like.

In order to solve the above-mentioned problems, the antibacterial resin of the invention according to claim 3 is an antibacterial resin in which a silver ion is bonded to the sulfonic acid group with respect to a polymer having a sulfonic acid group. The polymer is characterized by being crosslinked by a bond between the sulfonic acid group and a polyvalent metal ion.

According to the above-mentioned constitution, the antibacterial resin forms a relatively flexible crosslinked structure by binding the sulfonic acid group of the polymer with the polyvalent metal ion by an ionic bond. As a result, in the antibacterial resin, the elution of silver ions is efficiently suppressed, and the antibacterial activity can be stably maintained for a long period of time.

[0012] In order to solve the above-mentioned problems, the antibacterial resin according to the invention of claim 4 is the antibacterial resin according to any one of claims 1 to 3, wherein the polymer is an aromatic vinyl. It is characterized in that a vinyl polymer obtained by polymerizing a monomer component containing a monomer as a main component is sulfonated.

According to the above construction, the antibacterial resin has improved compatibility with various molding materials, organic materials such as fibers and paints.

In order to solve the above-mentioned problems, the antibacterial resin of the fifth aspect of the present invention is the antibacterial resin according to any one of the first to fourth aspects, wherein the average particle diameter is 0.3.
It is characterized in that it is a spherical particle of ˜500 μm.

According to the above construction, the antibacterial activity can be further improved. In addition, handleability can be improved.

In order to solve the above-mentioned problems, the antibacterial resin according to the invention of claim 6 uses a thermogravimetric analyzer to
After heating from 0 ° C to 280 ° C at a heating rate of 4 ° C / min,
The decomposition rate of the organic component when heated at 280 ° C. for 40 minutes is 40% by weight or less.

According to the above constitution, the polymer is excellent in heat resistance, so that it is possible to suppress a decrease in antibacterial activity under high temperature conditions. Accordingly, the antibacterial resin can stably maintain the antibacterial activity under high temperature conditions for a long period of time. Further, when manufacturing an antibacterial article containing an antibacterial resin, it is possible to suppress deterioration of the performance of the antibacterial resin even if it is processed at a high temperature, so that it can be applied to various antibacterial articles. Become.

Hereinafter, the present invention will be described in detail. In the present invention, the decomposition rate of the organic component when heated is a value indicating how much the organic component is decomposed when the antibacterial resin is heated. Specifically, it is determined by measuring a weight change when the antibacterial resin is heated under a predetermined condition and obtaining a weight reduction rate.

The antibacterial resin according to the present invention has a polymer having a sulfonic acid group (hereinafter referred to as a sulfonic acid group-containing polymer) in which silver ions are bonded to the sulfonic acid group.

The amount of silver ion bonded to the sulfonic acid group is preferably 2 to 10 mmol, more preferably 2.2 to 9 mmol, and 2.4 to 1 per 1 g of the sulfonic acid group-containing polymer.
8 mmol is more preferred. If the amount of silver ions is less than 2 millimoles, the antibacterial activity decreases, which is not preferable. On the other hand, if the amount of silver ions exceeds 10 millimoles, it cannot be manufactured at low cost, which is not preferable.

The above-mentioned sulfonic acid group-containing polymer preferably contains 3 to 7.5 mmol of sulfonic acid group, and more preferably 3.5 to 6.6 mmol of sulfonic acid group per 1 g of sulfonic acid group-containing polymer. Preferably 4 to
Even more preferably it contains 5.9 mmol of sulphonic acid groups. When the content of the sulfonic acid group is less than 3 mmol per 1 g, the antibacterial activity of the antibacterial resin decreases, which is not preferable. In addition, the content of sulfonic acid group per 1g
If it exceeds 7.5 millimoles, it cannot be manufactured at low cost, which is not preferable.

The sulfonic acid group-containing polymer can be obtained by a method of sulfonating a polymer having no sulfonic acid group or a method of polymerizing a monomer component containing unsaturated sulfonic acid.

First, a method for producing a sulfonic acid group-containing polymer in which a polymer having no sulfonic acid group (hereinafter referred to as a vinyl polymer) is sulfonated will be described.

The above-mentioned vinyl polymer may be any polymer capable of being sulfonated, but a monomer component containing an aromatic vinyl monomer as a main component (hereinafter referred to as a vinyl monomer component) is polymerized. The polymer thus obtained is particularly preferable. This allows
The compatibility of the obtained antibacterial resin with organic materials such as various molding materials, fibers and paints is improved. That is, since the antibacterial resin can be uniformly mixed with various molding materials, fibers, paints, etc., antibacterial properties can be suitably imparted to these articles.

Specific examples of the aromatic vinyl monomer include styrene, chlorostyrene, methoxystyrene, α-methylstyrene, p-methylstyrene, vinyltoluene and isopropenylstyrene.
Among the compounds exemplified above, styrene, chlorostyrene,
Methoxystyrene is particularly preferred. Only one kind of these aromatic vinyl monomers may be used, or two or more kinds thereof may be appropriately mixed and used.

The vinyl monomer component may contain, in addition to the aromatic vinyl monomer, other monomer copolymerized with the aromatic vinyl monomer (hereinafter referred to as other monomer). Good. The other monomer is not particularly limited as long as it is a compound that copolymerizes with the aromatic vinyl monomer. Specifically, for example, olefins such as ethylene and propylene;
Vinyl halides such as vinyl chloride and vinylidene chloride;
Vinyl esters of saturated monocarboxylic acids such as vinyl acetate; (meth) acrylic acid esters; dienes such as butadiene; (meth) acrylamide and its derivatives; allylated products such as allylpropyl ether; vinyl ethers; acrylonitrile, methacryloyl Unsaturated nitriles such as nitriles can be mentioned. The amount of the other monomer used may be in a range where the aromatic vinyl monomer is the main component,
It is more preferably less than 40%, even more preferably less than 20%.

When carrying out the polymerization of the vinyl monomer component, it is more preferable to add a crosslinking agent. As a result, the resulting polymer can form a cross-linked structure by covalent bonds, and the antibacterial activity of silver ions can be improved.

Examples of the cross-linking agent include a polyvinyl compound which forms a carbon-carbon bond type cross-linking structure by a reaction with a double bond of an aromatic vinyl monomer, and a double bond of an aromatic vinyl monomer. By the reaction of anyl (carbon-
(Nitrogen double bond) type cross-linking structure forming p-dinitrosobenzene, and a sulfur compound which forms a carbon-sulfur bond type cross-linking structure by reaction with a double bond possessed by an aromatic vinyl monomer. . Of these, polyvinyl compounds are particularly preferable.

The above-mentioned polyvinyl compound may be a compound having two or more polymerizable double bonds, and examples thereof include polyvinyl aromatic hydrocarbons such as divinylbenzene and divinyltoluene; ethylene glycol di (meth) acrylate and diethylene glycol. Aliphatic compounds having two or more vinyl groups or allyl groups such as di (meth) acrylate, trimethylolpropane tri (meth) acrylate, N, N'-methylenebisacrylamide, diallyl maleate and diallyl adipate To be Among the above-exemplified compounds, polyvinyl aromatic hydrocarbon is particularly preferable, and divinylbenzene is most preferable. Only one kind of these polyvinyl compounds may be used, or two or more kinds thereof may be appropriately combined and used.

The amount of the crosslinking agent added to 1 mol of the vinyl monomer component is preferably in the range of 0.005 to 1.0 mol, and is 0.02.
It is particularly preferably within the range of to 0.5 mol. The amount of crosslinking agent added
When the amount is less than 0.005 mol, the crosslinking density of the vinyl polymer obtained becomes too small, and the effect due to the crosslinking structure cannot be obtained. Further, the heat resistance of the antibacterial resin may be reduced. On the other hand, when the addition amount of the crosslinking agent is more than 1.0 mol, the obtained vinyl polymer has too high a crosslinking density, and the antibacterial resin may become brittle.

The vinyl monomer component can be polymerized by known polymerization methods such as emulsion polymerization method, suspension polymerization method, cast polymerization method, reverse phase suspension polymerization method, solution polymerization method, thin film polymerization method and spray polymerization method. Can be done using. In order to further improve the antibacterial property, it is particularly preferable to carry out the suspension polymerization method so that an antibacterial resin having an average particle diameter of 0.3 μm to 500 μm can be easily obtained. Specifically, the vinyl monomer component may be dispersed in an appropriate solvent such as water using a dispersant to carry out suspension polymerization. Then, the precipitate generated in the reaction solution may be isolated by, for example, filtration. The amount of solvent used, stirring time,
Polymerization temperature, isolation method, etc. are not particularly limited. The method for producing the antibacterial resin is not limited to the above-exemplified method.

When suspension polymerization is carried out, examples of the dispersant for dispersing the vinyl monomer component in the solvent include polyvinyl alcohol, low molecular weight siloxane, silanol, alkoxysilane, sorbitan monostearate and the like. Only one kind of these dispersants may be used, or two or more kinds thereof may be appropriately mixed and used.

When the vinyl monomer component is polymerized, a polymerization initiator can be used. As the above-mentioned polymerization initiator, a conventionally known polymerization initiator can be used. That is, for example, hydrogen peroxide; persulfates such as sodium persulfate, ammonium persulfate, potassium persulfate; benzoyl peroxide, lauriloyl peroxide, capryloyl peroxide, peracetic acid, t-butylhydroxyperoxide, cumene peroxide, Organic peroxides such as methyl ethyl ketone peroxide and t-butyl perphthalate; azobisisobutyronitrile as polymerization initiator, azobisisobutyramide,
Radical polymerization initiators such as azo compounds such as 2,2′-azobis (2,4-dimethylvalero) nitrile, azobis (α-methylvalero) nitrile and azobis (α-methylbutyro) nitrile may be mentioned. These polymerization initiators may be used alone, or two or more of them may be used as an appropriate mixture.

Further, in carrying out the above polymerization, in order to control the molecular weight of the resin obtained, lauryl mercaptan, dodecyl mercaptan, 2-mercaptoethanol,
A chain transfer agent such as 2-mercaptoacetic acid, carbon tetrachloride or carbon tetrabromide may be added. One of these may be used alone, or two or more of them may be appropriately mixed and used.

To sulfonate the vinyl polymer obtained by the above polymerization, a sulfonating agent may be allowed to act on the vinyl polymer. The sulfonating agent may be selected from conventionally known sulfonating agents and used, and for example, fuming sulfuric acid, chlorosulfuric acid, concentrated sulfuric acid, sulfur trioxide and the like can be used. Of the above examples, fuming sulfuric acid and chlorosulfuric acid are particularly preferable. This makes it possible to easily increase the content of sulfonic acid groups in the antibacterial resin.
When the sulfonating agent is allowed to act on the vinyl polymer, a transition metal salt such as silver oxide, silver sulfate or copper chloride can coexist as a catalyst in order to accelerate the sulfonation reaction. This makes it possible to easily increase the content of sulfonic acid groups in the antibacterial resin. When the sulfonating agent is added, it may be added to the vinyl polymer itself, or may be added to the reaction liquid prepared by mixing the vinyl polymer with a solvent such as tetrachloroethylene.

Next, a method for producing a sulfonic acid group-containing polymer by polymerizing a monomer component containing an unsaturated sulfonic acid (hereinafter, simply referred to as a monomer component) will be described. The unsaturated sulfonic acid may be any sulfonic acid having at least one polymerizable double bond. Specifically, for example, styrene sulfonic acid, allyl sulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate,
3-chloro-4-vinylbenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloyloxybenzenesulfonic acid, 2-acryloyloxynaphthalene-2-sulfonic acid, 2-methacryloyloxynaphthalene-2-sulfone Acid, 2-hydroxy-3-sulfopropyl methacrylate and the like can be mentioned. Among the unsaturated sulfonic acids exemplified above, 3-chloro-4-vinylbenzenesulfonic acid,
2-Acrylamido-2-methylpropanesulfonic acid is particularly preferred. Only one kind of these unsaturated sulfonic acids may be used, or two or more kinds thereof may be appropriately mixed and used. An unsaturated sulfonic acid salt may be used instead of these unsaturated sulfonic acids. As the unsaturated sulfonate, potassium salt, sodium salt, ammonium salt and the like can be used.

The above-mentioned monomer component may contain, in addition to the unsaturated sulfonic acid, an unsaturated carboxylic acid copolymerizable with the unsaturated sulfonic acid. As a result, a sulfonic acid group-containing polymer having a carboxyl group is obtained, so that silver ions can be bonded to both the sulfonic acid group and the carboxyl group. As a result, when the sulfonic acid group-containing polymer is cross-linked with a polyvalent metal ion, an asymmetric salt is formed, and an antibacterial resin having a more excellent antibacterial activity is obtained.

The unsaturated carboxylic acid may be any carboxylic acid having at least one polymerizable double bond. Specifically, for example, acrylic acid, methacrylic acid,
Α, β-unsaturated carboxylic acids such as crotonic acid and cinnamic acid;
4-pentenoic acid, 5-hexenoic acid, 3-methyl-3-butenoic acid,
4-methyl-4-pentenoic acid, oleic acid, undecylenic acid, 3-pentenoic acid, 3-methyl-4-pentenoic acid, 3-oxo-5-methyl-5-hexenoic acid, 3-oxo-4-methyl- 4-hexenoic acid, 2-acryloylacetic acid, 3-acryloylpropionic acid, 2-methacryloylacetic acid, 3-acryloylbutanoic acid, 2-acryloylaminoacetic acid, 3-acryloylaminopropionic acid, 2-methacryloylaminoacetic acid, 2-methacryloylamino acid Propionic acid, 2- (2-butenoyl) aminoacetic acid, 2-acryloylthioacetic acid, 3-acryloylthiopropionic acid, 2-methacryloylthioacetic acid, 2-methacryloylthiopropionic acid, 2- (2-butenoyl) thioacetic acid, 2 -Acryloyloxyacetic acid, 3-acryloyloxypropionic acid, 2-methacryloyloxyacetic acid, 3-methacryloyloxypropionic acid, 4-methacryloyl Unsaturated monocarboxylic acids other than α, β-unsaturated carboxylic acids such as oxycyclohexanecarboxylic acid, 4-methacryloyloxybenzoic acid, 2- (2-butenoyl) oxyacetic acid; 2-acryloyloxyethyl succinate, succinic acid 3 -Saturation of acryloyloxypropyl, 2-methacryloyloxyethyl succinate, 3-methacryloyloxypropyl succinate, 2- (2-butenoyl) oxyethyl succinate, 2-acryloyloxyethyl phthalate, 2-methacryloyloxyethyl phthalate, etc. Mono (meth) acryloyloxyalkyl ester of dicarboxylic acid; maleic acid, fumaric acid,
Itaconic acid, 1,15-dicarboxy-4,9,12-trioxa-
Unsaturated dicarboxylic acids such as 3,8,13-trioxo-6-pentadecene; and unsaturated dicarboxylic acid monoesters such as maleic acid monomethyl ester and maleic acid monoallyl ester.

These unsaturated carboxylic acids may be used alone, but it is more preferable to use a mixture of two or more kinds of unsaturated carboxylic acids. When two or more kinds of unsaturated carboxylic acids are mixed and used, the amount of the unsaturated carboxylic acid used most is relative to the total amount of the unsaturated carboxylic acid.
It is preferably 70 mol% or less. Thereby, the durability of the antibacterial activity and the heat resistance can be improved.

The amount of the unsaturated carboxylic acid used is based on the total amount of the unsaturated sulfonic acid and the unsaturated carboxylic acid.
It is preferably 30 to 70 mol%. Thereby, the durability of the antibacterial activity and the heat resistance can be improved.

In order to further improve the compatibility between the antibacterial resin and the organic substance, the above-mentioned monomer component is used in addition to the unsaturated sulfonic acid and the unsaturated carboxylic acid used as necessary,
It is preferable to contain a monomer copolymerizable with unsaturated sulfonic acid (hereinafter referred to as a copolymerizable monomer).

Specific examples of the copolymerizable monomer include (meth) acrylic acid esters; styrene, α-methylstyrene, paramethylstyrene, vinyltoluene, isopropenylstyrene, chlorostyrene and the like. Aromatic vinyls; olefins such as ethylene, propylene, isobutylene and diisobutylene; dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride,
Vinyl halides such as vinyl bromide and vinyl fluoride;
Unsaturated alcohols such as (meth) allyl alcohol and croton alcohol; vinyl esters of saturated monocarboxylic acids such as vinyl acetate and vinyl propionate; and (meth) of saturated aliphatic monocarboxylic acids such as allyl acetate and allyl propionate Allyl esters; methyl vinyl ether,
Vinyl ethers such as butyl vinyl ether; acrylonitrile, methacrylonitrile, ethacrylonitrile,
Unsaturated nitriles such as phenylacrylonitrile; (meth) acrylamide; 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-diethylamino) ethyl Amino group-containing (meth) acrylates such as acrylates and 2- (N, N-diethylamino) ethyl methacrylate; Ethylenically unsaturated mono-salts such as quaternary salts formed from the above amino group-containing (meth) acrylates and methyl chloride Polymer; 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-
5-vinylpyridine, 2-ethyl-5-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-vinylquinoline, 1-vinylcarbazole, 3-vinylcarbazole, 1-methyl-3-vinylcarbazole, 1-vinyl Vinyl-substituted heterocyclic compounds such as imidazole, 2-vinylimidazole, 4-vinylimidazole, 4-vinylpyrimidine; 1-methacryloylaziridine, 2- (1-aziridinyl) ethyl methacrylate, 4-acryloyloxy-2,2,6 , 6-Tetramethylpiperidine, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-methacryloyloxy-1, 2,2,
6,6-pentamethylpiperidine, 9-aza-3-acryloyloxymethyl-3-ethyl-8,8,10,10-tetramethyl-1,
Examples thereof include ethylenically unsaturated monomers such as heterocyclic (meth) acrylates such as 5-dioxa-spiro [5,5] undecane.

Specific examples of the above-mentioned (meth) acrylic acid esters include methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, Isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate,
Aliphatic esters such as octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate; benzyl (meth) acrylate, (meth) Examples thereof include aromatic esters such as phenyl acrylate.

These ethylenically unsaturated monomers used as the copolymerizable monomer may be used alone, or two or more kinds may be appropriately mixed and used. Among the above-exemplified ethylenically unsaturated monomers, at least one compound selected from the group consisting of (meth) acrylic acid esters and aromatic vinyls is particularly preferable. By copolymerizing the compound with unsaturated sulfonic acid, the compatibility between the obtained antibacterial resin and various molding materials, organic materials such as fibers and paints is improved. In other words, various molding materials and fibers,
Since the antibacterial resin can be uniformly mixed with the paint or the like, the antibacterial property can be suitably imparted to these articles.

The proportion of the copolymerizable monomer in the monomer component is not particularly limited, but is preferably in the range of 25 to 80 mol%. When the above ratio is less than 25 mol%, the compatibility between the antibacterial resin and the organic substance becomes low. On the other hand, if the above ratio exceeds 80 mol%, it becomes difficult to easily and efficiently form a silver salt.

The polymerization of the monomer component may be carried out in the same manner as the above-mentioned polymerization of the vinyl monomer component by using the above-exemplified polymerization initiator, chain transfer agent and the like, if necessary. As the polymerization method in this case as well, suspension polymerization is particularly preferable.

When polymerizing the monomer component, it is more preferable to add a polyvalent metal compound which produces a polyvalent cation. As a result, an antibacterial resin is obtained in which the sulfonic acid group-containing polymer is crosslinked by the bond between the sulfonic acid group and the polyvalent metal ion. That is, the sulfonic acid group of the generated sulfonic acid group-containing polymer is crosslinked by an ionic bond with a polyvalent metal ion, and is more flexible than a covalent bond,
A crosslinked structure is formed by an ionic bond having a weak bond. As a result, in the antibacterial resin, the elution of silver ions is efficiently suppressed and the durability of the antibacterial effect is improved. Therefore, an antibacterial resin obtained by crosslinking a sulfonic acid group-containing polymer by a bond between the sulfonic acid group and a polyvalent metal ion has a silver ion content of less than 2 mmol per 1 g of the sulfonic acid group-containing polymer. Even if it exists, it exerts a sufficient antibacterial effect.

The above polyvalent metal compound reacts with a plurality of sulfonic acid groups contained in the sulfonic acid group-containing polymer to generate a polyvalent cation and crosslinks the plurality of sulfonic acid groups with the polyvalent cation. Anything can be used. Specific examples of the polyvalent metal compound include oxides, hydroxides, nitrates, perchlorates, and chlorides of polyvalent metals. Of these, polyvalent metal oxides and / or hydroxides are particularly preferable. The polyvalent metal may be any as long as it can form polyvalent cations, and examples thereof include zinc, copper and lead. Of these polyvalent metals, zinc is particularly preferable. And, as the polyvalent metal compound, zinc hydroxide and /
Alternatively, it is most preferable to use zinc oxide. This makes it possible to efficiently form a crosslinked structure and further improve the durability of the antibacterial effect.

Regarding the amount of the polyvalent metal compound used,
Although not particularly limited, it is more preferably within the range of 0.5 to 30 mol% with respect to the total amount of the monomer component and the polyvalent metal compound. When the amount of the polyvalent metal compound used is less than 0.5 mol%, a crosslinked structure is less likely to be formed, and the antibacterial activity may not be sufficiently improved in sustainability.
When the amount of the polyvalent metal compound used is more than 30 mol%, the antibacterial activity of the antibacterial resin becomes difficult to be sufficiently exerted.

A cross-linking agent can also be added when the monomer components are polymerized. As a result, the resulting polymer can form a cross-linked structure by covalent bonds, and the antibacterial activity of silver ions can be improved. As the cross-linking agent, the compounds exemplified above can be used, and a polyvinyl compound is particularly preferable. And
In this case, among the polyvinyl compounds exemplified above, N, N'-
Methylenebisacrylamide is particularly preferred.

The addition amount of the cross-linking agent to 1 mol of the monomer component is preferably in the range of 0.0001 to 0.5 mol, and 0.0005 to 0.5 mol.
The range of 1 mol is particularly preferable. Addition amount of cross-linking agent is 0.00
When the amount is less than 01 mol, the cross-linking density of the obtained sulfonic acid group-containing polymer becomes too small, and it becomes difficult to obtain the effect due to the cross-linking structure. On the other hand, the amount of crosslinking agent added is 0.5
If it is more than the molar amount, the crosslinking density of the obtained sulfonic acid group-containing polymer may be too high, and the performance of the antibacterial resin may be deteriorated.

The sulfonic acid group-containing polymer may have various shapes such as particles, irregularly crushed particles, and lumps, but spherical particles are more preferable. When the vinyl monomer component or the monomer component is suspension polymerized, the precipitate obtained after the reaction (after the sulfonation reaction or after polymerizing the monomer component) is filtered and dried to obtain an average. Particle size is 0.
A sulfonic acid group-containing polymer having a thickness of 3 to 500 μm can be produced, but granulation may be carried out if necessary. The granulation method for granulating the sulfonic acid group-containing polymer is not particularly limited.

The antibacterial resin according to the present invention is efficiently produced by the method of reacting the sulfonic acid group-containing polymer obtained as described above with a silver compound.

The above silver compound reacts with the sulfonic acid group of the sulfonic acid group-containing polymer to produce silver ion,
The silver ion is not particularly limited as long as it can bond with a sulfonic acid group. Examples of the silver compound include silver oxide, silver hydroxide, silver nitrate, silver sulfate, silver acetate and the like. Among the above-exemplified silver compounds, silver oxide and / or
Alternatively, it is particularly preferable to use silver nitrate. This allows
It is possible to more efficiently generate silver ions that bond with sulfonic acid groups. The amount of the silver compound used is not particularly limited, and may be appropriately adjusted so that a desired amount of silver ion can be bonded to the sulfonic acid group of the sulfonic acid group-containing polymer. .

In this way, by reacting the sulfonic acid group-containing polymer with the silver compound, silver ions are bonded to the sulfonic acid group to obtain an antibacterial resin. And according to the said method, it is hard to decompose | disassemble even under high temperature conditions, and the antibacterial resin excellent in heat resistance is obtained. Specifically, using a thermogravimetric analyzer, the rate of decomposition of organic components when heated from 280 ° C to 280 ° C at a heating rate of 4 ° C / min for 40 minutes was 40% by weight. % Or less antibacterial resin is obtained. Accordingly, the antibacterial resin can stably maintain the antibacterial activity under high temperature conditions for a long period of time. The decomposition rate of the organic component is a predetermined amount (for example,
About 15 mg) of the antibacterial resin is used and measured under a nitrogen gas stream (for example, a nitrogen gas flow rate of 100 mL / min).

The above-mentioned antibacterial resin may have various shapes such as particles, irregularly crushed particles and lumps, but spherical particles are more preferable. The average particle size of the antibacterial resin is preferably 0.3 to 500 μm, and is 0.5 to 200 μm.
μm is more preferable, and 1.0 to 100 μm is still more preferable. If the average particle size is less than 0.3 μm, it is not preferable because the production is difficult and the handleability is deteriorated.
That is, an antibacterial resin having an average particle size of less than 0.3 μm is difficult to manufacture because it is difficult to remove it from the reaction solution by filtration. Also, when dried, it easily aggregates,
It is difficult to handle and difficult to disperse in molded products. On the other hand, if the average particle diameter exceeds 500 μm, the antibacterial activity of the antibacterial resin is lowered and the antibacterial performance of the molded article containing the antibacterial resin may be lowered, which is not preferable.
In particular, an antibacterial resin having an average particle diameter of 0.3 to 500 μm is suitable for kneading and mixing with various resins.

The antibacterial resin according to the present invention is used in hygiene and medical fields where cleanliness is required, for example, clothes (white coat etc.) for doctors and nurses working in hospitals, bed sheets, various appliances and so-called equipment. It can be suitably used as an antibacterial hygiene material, etc., in the food field, household miscellaneous goods such as telephone receivers,
It can be used in a very wide variety of fields such as various molding materials, fibers, paints, toys and the like. Therefore, the antibacterial resin is
It can be applied to all uses of conventionally known antibacterial resins. The composition of the antibacterial resin may be appropriately set so that the optimum antibacterial activity according to these applications can be obtained.

[0058]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. The antibacterial activity of the antibacterial resin was evaluated by carrying out the following test method.

(A) Measurement of Number of Bacteria by Shaking Contact First, a bacterial solution was prepared as follows. Pseudomonas aeruginosa IFO 3445, which is one of Pseudomonas aeruginosa, was used as a strain, and the above strain was used in a trypticase soy liquid medium.
Subculture was carried out. Then, the subcultured liquid medium (the number of bacteria is approximately 2 × 10 ⁸ cells / ml) was diluted 100 times with physiological saline,
A bacterial solution (the number of bacteria was about 2 × 10 ⁶ cells / ml) was prepared.

On the other hand, the antibacterial resin was dissolved in a 5% aqueous solution of dimethyl sulfoxide (DMSO) to prepare an aqueous solution having a concentration of 1.0 mg / ml. Next, the aqueous solution was diluted 10 times with distilled water to prepare a test solution.

Then, 1 ml of the above-mentioned bacterial solution was added to 20 ml of the above test solution, and the mixture was allowed to stand at 20 ° C. with occasional gentle stirring. Then, 5 minutes, 10 minutes, 30 minutes after the mixture of both solutions, that is, when the antibacterial resin is allowed to act on the bacteria,
The reaction solution was sampled after 1 minute, 3 hours, and 6 hours. The sampled reaction solution was diluted with physiological saline to an appropriate ratio, and then cultured at 37 ° C. for 24 hours using Trypticase Soy agar medium. Then, the number of colonies that grew on the agar medium was counted and the number of bacteria (cells / ml) in the reaction solution was measured.

Example 1 First, a stirrer, a reflux condenser,
In a 3 L four-neck separable flask equipped with a thermometer and 1.2 L of water, 16.0 g of polyvinyl alcohol (Kuraray Poval PVA-205: manufactured by Kuraray Co., Ltd.) as a dispersant was added and dissolved, It was a dispersion liquid. Then, styrene as an aromatic vinyl monomer was added to the dispersion.
260 g (2.5 mol), industrial divinylbenzene as a cross-linking agent (a mixture of Wako Pure Chemical Industries, Ltd., 55% by weight divinylbenzene, 35% by weight ethylstyrene, etc.) 40 g (0.31 mol)
l) and 10 g of benzoyl peroxide as a polymerization initiator were added. Then, using a disperser, 5000 rp
Disperse the contents in the flask at a stirring speed of m and at 75 ° C.
It was polymerized for 10 hours. This produced a precipitate. The precipitate formed was filtered off, washed thoroughly, and dried at 80 ° C. for 10 hours using a hot air drier to obtain 286 g of a spherical polymer crosslinked product as a vinyl polymer.

Then, a 2 L four-necked separable flask equipped with a stirrer, a thermometer, and a dropping funnel was charged with 500 g of 30% by weight fuming sulfuric acid as a sulfonating agent, and the mixture was stirred while stirring with an ice bath. Cooled to ° C. Next, 50 g of the polymer cross-linked product was added over 1 hour to form a uniform dispersion liquid. Then, after removing from the ice bath and stirring at room temperature (20 ° C) for 12 hours, the temperature of the reaction mixture was further raised to 80 ° C,
The sulfonation reaction was carried out by stirring for 5 hours while continuing heating at 80 ° C. Then, the reaction mixture was poured into water at 0 ° C.,
After separating by filtration, it was washed with water and acetone. As a result, a solid sulfonic acid group-containing polymer was obtained.

The ion exchange capacity of the obtained sulfonic acid group-containing polymer was measured by neutralization titration and found to be 5.1 meq / g. That is, the sulfonic acid group-containing polymer is
It contained 5.1 mmol of sulphonic acid groups per gram.

The sulfonic acid group-containing polymer was treated with 4 L (2.35 mol) of a 10 wt% silver nitrate aqueous solution as a silver compound, and then thoroughly washed with water. Then, it was dried at 80 ° C. for 10 hours using a vacuum dryer to obtain an antibacterial resin.

The average particle diameter of the obtained antibacterial resin was measured by using a laser diffraction type particle size distribution measuring device (SALD-1000: manufactured by Shimadzu Corporation), and it was 10 μm. Furthermore, when the content of silver was examined by a fluorescent X-ray analysis method, 95% of the sulfonic acid groups were silver salts. From this, it was found that the antibacterial resin contained 4.8 mmol of silver ion per 1 g of the sulfonic acid group-containing polymer.

Further, the weight change of the antibacterial resin under heating is measured by a thermogravimetric analyzer (thermal analysis system SSC5200).
Series: manufactured by Seiko Denshi Kogyo Co., Ltd.). That is, about 15 mg of the antibacterial resin is placed at 20 ° C. under a nitrogen gas flow (nitrogen gas flow rate 100 mL / min).
To 280 ° C at a heating rate of 4 ° C / min, then 280 ° C
After heating for 40 minutes, the weight change of the antibacterial resin was measured. As a result, the weight of the antibacterial resin after heating was reduced to 90% by weight before heating. In other words, the decomposition rate of organic components is 10
% By weight.

Further, with respect to the obtained antibacterial resin, changes in the number of bacteria (cells / ml) due to the shaking contact were measured. Further, in order to evaluate the persistence and stability of the antibacterial activity of the obtained antibacterial resin, the above antibacterial resin was subjected to heat treatment. That is, the antibacterial resin was immersed in boiling water for 24 hours, and then the antibacterial resin was dried. The change in the number of bacteria (cells / ml) due to the shaking contact was also measured for the antibacterial resin subjected to the heat treatment. The results of these measurements (hereinafter simply referred to as results) are also shown in Table 1. still,
The column of "no treatment" shown in Table 1 shows the measurement result of the antibacterial resin not subjected to the heat treatment, and the column of "heat treatment" shows the measurement result of the heat treated antibacterial resin. .

Example 2 First, a stirrer, a reflux condenser,
In a 3 L four-neck separable flask equipped with a thermometer and 1.2 L of water, 16.0 g of polyvinyl alcohol (Kuraray Poval PVA-205: manufactured by Kuraray Co., Ltd.) as a dispersant was added and dissolved, It was a dispersion liquid. Then, to the dispersion, 300 g of chlorostyrene as an aromatic vinyl monomer, industrial divinylbenzene as a cross-linking agent (manufactured by Wako Pure Chemical Industries, Ltd., divinylbenzene 55% by weight, mixture of ethylstyrene 35% by weight, etc.) ) 30 g and 4 g of azobisisobutyronitrile as polymerization initiator are added. After that, using a disperser, 6500r
Disperse the contents in the flask at a stirring speed of pm and
It was polymerized for 10 hours. This produced a precipitate. The precipitate formed was filtered off, washed thoroughly, and dried at 80 ° C. for 10 hours using a hot air drier to obtain 303 g of a spherical polymer crosslinked product as a vinyl polymer.

Then, in a 2 L four-necked separable flask equipped with a stirrer, a thermometer, and a dropping funnel, 50 g of the polymer crosslinked product and tetrachloroethane 2 as a solvent were added.
50 g was charged and cooled to 0 ° C. with an ice bath while stirring. Then, 500 g of concentrated sulfuric acid (98% by weight aqueous solution) as a sulfonating agent was added to obtain a uniform dispersion liquid (reaction mixture). Then, raise the temperature of the dispersion liquid to 80 ° C.,
The sulfonation reaction was carried out by stirring for 24 hours while continuing heating at ℃. After completion of the reaction, the reaction mixture was poured into water at 0 ° C., the formed precipitate was filtered off, and washed with water and acetone. As a result, a sulfonic acid group-containing polymer was obtained.

The ion exchange capacity of the obtained sulfonic acid group-containing polymer was measured by neutralization titration and found to be 4.1 meq / g. That is, the sulfonic acid group-containing polymer is
It contained 4.1 mmol of sulphonic acid groups per gram.

The sulfonic acid group-containing polymer was treated with 4 L of a 10% by weight silver nitrate aqueous solution as a silver compound, and then thoroughly washed with water. Then, using a vacuum dryer, at 80 ℃
After drying for 10 hours, an antibacterial resin was obtained.

The average particle size of the obtained antibacterial resin was measured by using a laser diffraction particle size distribution measuring device (SALD-1000: manufactured by Shimadzu Corporation), and it was 50 μm. Furthermore, when the content of silver was examined by a fluorescent X-ray analysis method, 91% of the sulfonic acid groups were silver salts. From this, it was found that the antibacterial resin contained 3.7 mmol of silver ion per 1 g of the sulfonic acid group-containing polymer.

Further, the weight change of the antibacterial resin under heating is measured by a thermogravimetric analyzer (thermal analysis system SSC5200).
Series: manufactured by Seiko Denshi Kogyo Co., Ltd.). That is, about 15 mg of the antibacterial resin is placed at 20 ° C. under a nitrogen gas flow (nitrogen gas flow rate 100 mL / min).
To 280 ° C at a heating rate of 4 ° C / min, then 280 ° C
After heating for 40 minutes, the weight change of the antibacterial resin was measured. As a result, the weight of the antibacterial resin after heating was reduced to 88% by weight before heating. In other words, the decomposition rate of organic components is 12
% By weight. Furthermore, various antibacterial activities of the obtained antibacterial resin were measured in the same manner as in Example 1. The results are also shown in Table 1.

Example 3 First, a stirrer, a reflux condenser,
In a 3 L four-neck separable flask equipped with a thermometer and 1.2 L of water, 16.0 g of polyvinyl alcohol (Kuraray Poval PVA-205: manufactured by Kuraray Co., Ltd.) as a dispersant was added and dissolved, It was a dispersion liquid. Then, styrene as an aromatic vinyl monomer was added to the dispersion.
140 g and 133 g of methoxystyrene, 27 g of industrial divinylbenzene (a mixture of 55% by weight of divinylbenzene and 35% by weight of ethylstyrene manufactured by Wako Pure Chemical Industries, Ltd.) as a crosslinking agent, and 10 g of benzoyl peroxide as a polymerization initiator. Was added. Then, the contents in the flask were dispersed using a disperser at a stirring speed of 7,000 rpm, and polymerization was carried out at 75 ° C for 10 hours. This produced a precipitate. The precipitate formed was filtered off, washed thoroughly, and dried at 80 ° C. for 10 hours using a hot air drier to obtain 289 g of a spherical polymer crosslinked product as a vinyl monomer.

Next, 50 g of the polymer crosslinked product was charged into a 2 L four-necked separable flask equipped with a stirrer, a thermometer, and a dropping funnel, and 500 g of concentrated sulfuric acid (98% by weight aqueous solution) as a sulfonating agent was charged. Addition gave a uniform dispersion (reaction mixture). Then, raise the temperature of the dispersion liquid to 80 ° C., and stir for 24 hours while continuing heating at 80 ° C.,
A sulfonation reaction was performed. After the reaction is completed, the reaction mixture is cooled to 0.
The mixture was poured into water at ℃, the precipitate formed was filtered off, and washed with water and acetone. As a result, a sulfonic acid group-containing polymer was obtained.

The ion exchange capacity of the obtained sulfonic acid group-containing polymer was measured by neutralization titration, and it was 4.4 meq / g. That is, the sulfonic acid group-containing polymer is
It contained 4.4 mmol of sulphonic acid groups per gram.

The above sulfonic acid group-containing polymer was treated with 4 L of a 10 wt% silver nitrate aqueous solution as a silver compound, and then thoroughly washed with water. Then, using a vacuum dryer, at 80 ℃
After drying for 10 hours, an antibacterial resin was obtained.

The average particle diameter of the obtained antibacterial resin was measured by using a laser diffraction particle size distribution measuring device (SALD-1000: manufactured by Shimadzu Corporation), and it was 7 μm. Furthermore, when the content of silver was examined by a fluorescent X-ray analysis method, it was found that 82% of the sulfonic acid groups were silver salts. From this, it was found that the antibacterial resin contained 3.6 mmol of silver ion per 1 g of the sulfonic acid group-containing polymer.

Further, the weight change of the antibacterial resin under heating is measured by a thermogravimetric analyzer (thermal analysis system SSC5200).
Series: manufactured by Seiko Denshi Kogyo Co., Ltd.). That is, about 15 mg of the antibacterial resin is placed at 20 ° C. under a nitrogen gas flow (nitrogen gas flow rate 100 mL / min).
To 280 ° C at a heating rate of 4 ° C / min, then 280 ° C
After heating for 40 minutes, the weight change of the antibacterial resin was measured. As a result, the weight of the antibacterial resin after heating was reduced to 90% by weight before heating. In other words, the decomposition rate of organic components is 10
% By weight. Furthermore, various antibacterial activities of the obtained antibacterial resin were measured in the same manner as in Example 1. The results are also shown in Table 1.

Example 4 First, in a 300 mL four-neck separable flask equipped with a stirrer and a thermometer, 104 g (1.0 mol) of styrene as a copolymerizable monomer, and 3-g as an unsaturated sulfonic acid were placed. Chloro-4-vinylbenzenesulfonic acid (65.6 g, 0.3 mol) was charged and heated to 70 ° C. next,
With stirring, zinc hydroxide as a polyvalent metal compound 20.0
g (0.2 mol), 17.2 g (0.2 mol) of methacrylic acid as an unsaturated carboxylic acid and 55.6 g (0.2 mol) of ethylene glycol methacrylate phthalate were added to prepare a reaction solution.

On the other hand, 600 g of ion-exchanged water was placed in a 2 L four-necked separable flask equipped with a stirrer, a reflux condenser, and a thermometer, and polyvinyl alcohol (Kuraray Poval PVA-205: Kuraray Co., Ltd.) as a dispersant was charged. 4.5 g) was added and dissolved to obtain a dispersion liquid. Then, after raising the temperature of the above dispersion liquid to 70 ° C., 150 g of the above reaction liquid was added, and the contents in the flask were dispersed at a stirring speed of 5000 rpm using a disperser to form a uniform suspension. Obtained. Then, 4.5 g of azoisobutyronitrile as a polymerization initiator was added to the above suspension to initiate polymerization. Then, while continuing stirring, heating was carried out at 70 ° C. for 5 hours to carry out polymerization, and then the temperature was further raised to 90 ° C. and heating was carried out at 90 ° C. for 5 hours to carry out polymerization. After completion of the reaction, the solid matter obtained was filtered off and thoroughly washed, and then the hot solid was dried at 80 ° C for 10
After drying for 2 hours, 250 g of a spherical polymer cross-linked product as a sulfonic acid group-containing polymer was obtained.

The ion exchange capacity of the obtained polymer cross-linked product was measured by neutralization titration and found to be 1.1 meq / g. That is, the polymer crosslinked product contained 1.1 mmol of sulfonic acid group per gram.

The above polymer cross-linked product was used as a silver compound.
After treating with 4 L (2.35 mmol) of a 10 wt% silver nitrate aqueous solution, it was thoroughly washed with water. Then, it was dried at 80 ° C. for 10 hours using a vacuum dryer to obtain an antibacterial resin.

The average particle diameter of the obtained antibacterial resin was measured by using a laser diffraction particle size distribution analyzer (SALD-1000: manufactured by Shimadzu Corporation), and it was 10 μm. Furthermore, when the content of silver was examined by a fluorescent X-ray analysis method, it was found that 80% of the sulfonic acid groups were silver salts. This revealed that the antibacterial resin contained 0.9 mmol of silver ion per 1 g of the sulfonic acid group-containing polymer.

Further, the weight change of the antibacterial resin under heating is measured by a thermogravimetric analyzer (thermal analysis system SSC5200).
Series: manufactured by Seiko Denshi Kogyo Co., Ltd.). That is, about 15 mg of the antibacterial resin is placed at 20 ° C. under a nitrogen gas flow (nitrogen gas flow rate 100 mL / min).
To 280 ° C at a heating rate of 4 ° C / min, then 280 ° C
After heating for 40 minutes, the weight change of the antibacterial resin was measured. As a result, the weight of the antibacterial resin after heating was reduced to 70% by weight before heating. In other words, the decomposition rate of organic components is 30
% By weight. Furthermore, various antibacterial activities of the obtained antibacterial resin were measured in the same manner as in Example 1. The results are also shown in Table 1.

Example 5 First, a stirrer, a reflux condenser,
A 2 L four-neck separable flask equipped with a thermometer and a nitrogen gas introduction tube was charged with 1200 g of cyclohexane, and 12 g of sorbitan monostearate as a dispersant was added and dissolved to form a dispersion liquid. The atmosphere was replaced with nitrogen.

On the other hand, 2- (N, N-dimethylamino) ethyl acrylate 7.15 as a copolymerizable monomer was added to the dropping funnel.
g (0.05 mol), 2-acrylamido-2-methylpropanesulfonic acid as unsaturated sulfonic acid 115 g (0.5 mol)
, N, N'-methylenebisacrylamide as a cross-linking agent
0.154 g (0.001 mol) and 318 g of ion-exchanged water were charged to prepare a monomer aqueous solution. Then, in the monomer aqueous solution,
0.4 g of ammonium persulfate as a polymerization initiator was added and dissolved, and nitrogen gas was blown in to remove oxygen dissolved in the monomer aqueous solution. Then, the aqueous monomer solution in the dropping funnel was dispersed in the above dispersion liquid, and heated at 60 to 65 ° C. for 3 hours to polymerize while slightly introducing nitrogen. After polymerization,
Water in the reaction mixture was distilled off by azeotropic distillation with cyclohexane, and the obtained solid was filtered off. Then, the filtered solid matter was dried at 80 ° C. for 10 hours to obtain a polymer cross-linked product as a sulfonic acid group-containing polymer.

The ion exchange capacity of the obtained polymer cross-linked product was measured by neutralization titration and found to be 4.1 meq / g. That is, the polymer cross-linked product contained 4.1 mmol of sulfonic acid group per 1 g.

The above polymer cross-linked product was used as a silver compound.
After being treated with 4 L of a 10 wt% silver nitrate aqueous solution, it was thoroughly washed with water. Then, it was dried at 80 ° C. for 10 hours using a vacuum dryer to obtain an antibacterial resin.

The average particle diameter of the obtained antibacterial resin was measured by using a laser diffraction type particle size distribution measuring device (SALD-1000: manufactured by Shimadzu Corporation), and it was 96 μm. Furthermore, when the content of silver was examined by the fluorescent X-ray analysis method, 90% of the sulfonic acid groups were silver salts. From this, it was found that the antibacterial resin contained 3.6 mmol of silver ion per 1 g of the sulfonic acid group-containing polymer.

Further, the weight change of the antibacterial resin under heating is measured by a thermogravimetric analyzer (thermal analysis system SSC5200).
Series: manufactured by Seiko Denshi Kogyo Co., Ltd.). That is, about 15 mg of the antibacterial resin is placed at 20 ° C. under a nitrogen gas flow (nitrogen gas flow rate 100 mL / min).
To 280 ° C at a heating rate of 4 ° C / min, then 280 ° C
After heating for 40 minutes, the weight change of the antibacterial resin was measured. As a result, the weight of the antibacterial resin after heating was reduced to 61% by weight before heating. In other words, the decomposition rate of organic components is 39
% By weight. Furthermore, various antibacterial activities of the obtained antibacterial resin were measured in the same manner as in Example 1. The results are also shown in Table 1.

[0093]

[Table 1]

As is clear from the results of Examples 1 to 5, it was found that the antibacterial resin according to this example has excellent antibacterial activity. Further, even if the antibacterial resin is subjected to heat treatment, silver hardly elutes from the antibacterial resin into water, and therefore, the antibacterial effect is effective and excellent in durability. all right.

Comparative Example 1 An antibacterial resin for comparison was obtained in the same manner as in Example 1 except that the silver nitrate aqueous solution was not used. Various antibacterial activities of the obtained antibacterial resin were measured, but no antibacterial activity was observed.

Comparative Example 2 An antibacterial resin for comparison was obtained in the same manner as in Example 4 except that the silver nitrate aqueous solution was not used. Various antibacterial activities of the obtained antibacterial resin were measured, but no antibacterial activity was observed.

[0097]

According to the constitution of the present invention, the antibacterial resin is
For example, it exerts an effect that it is excellent in effective antibacterial activity to exert an antibacterial effect against Pseudomonas aeruginosa and MRSA.
The above-mentioned antibacterial resin is not only used in the hygiene field and medical field where cleanliness is required, but also, for example, in the food field, household miscellaneous goods such as telephone handsets, various molding materials, fibers, paints
It can be used in a very wide variety of fields such as toys.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08K 3/22 KAE C08K 3/22 KAE C08L 101/02 C08L 101/02 (72) Inventor Hiroshi Tsuboi Nihon Shokubai Co., Ltd. 1 at 992 Nishikioki, Kohama, Aboshi-ku, Himeji City, Hyogo Prefecture

Claims (6)

[Claims] 1. An antibacterial resin comprising a sulfonic acid group-containing polymer and silver ions bonded to the sulfonic acid group, wherein the silver ion is contained in an amount of 2 to 10 mmol per 1 g of the polymer. Antibacterial resin characterized by 2. An antibacterial resin comprising a sulfonic acid group-containing polymer, and silver ions bonded to the sulfonic acid group, wherein the sulfonic acid group of the polymer is 1 g of the polymer. An antibacterial resin characterized by being 3 to 7.5 mmol. 3. An antibacterial resin comprising a sulfonic acid group-containing polymer, and silver ions bonded to the sulfonic acid group, wherein the polymer comprises a sulfonic acid group and a polyvalent metal ion. An antibacterial resin characterized by being crosslinked by bonding. 4. The polymer according to claim 1, wherein the polymer is formed by sulfonation of a vinyl polymer obtained by polymerizing a monomer component containing an aromatic vinyl monomer as a main component. The antibacterial resin according to item 1. 5. The antibacterial resin according to any one of claims 1 to 4, which is a spherical particle having an average particle diameter of 0.3 to 500 µm. 6. A thermogravimetric analyzer is used to measure the temperature from 20 ° C. to 28 ° C.
After raising the temperature to 0 ° C at a heating rate of 4 ° C / min, the temperature was raised to 4 ° C at 280 ° C.
Decomposition rate of organic components when heated for 0 minutes is 40% by weight
The following is an antibacterial resin.