JPH10287506A - Antimicrobial agent, antimicrobial resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial agent capable of improving dispersibility in a resin composition such as a coating agent, compatibility with a resin and coating characteristics, and having a high antimicrobial activities by using an antimicrobial metal component. SOLUTION: This antimicrobial agent is constituted of polymer particles comprising a polymer having a functional group containing an oxygen atom, a nitrogen atom, a sulfur atom, etc., (having 0.1 nm to 100 μm average particle diameter with a crosslinking structure), and an antimicrobial metal component (such as silver component) fixed thereon by forming a chemical bond to the functional group. The carrying amount of the antimicrobial metal component is about 0.01-50 wt.% in terms of the metal based on the whole amount. The antimicrobial agent has a good compatibility with the resin and useful as an antimicrobial resin composition (such as a resin composition for coating).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial agent which effectively exhibits antibacterial activity against various microorganisms (bacteria, molds, etc.), a method for producing the same, and a useful antibacterial agent containing the antibacterial agent as a coating agent. The present invention relates to an antibacterial resin composition.

[0002]

2. Description of the Related Art In recent years, antibacterial treatment of various products has been studied due to an increase in cleanliness. This antibacterial treatment
Usually, an antibacterial agent is kneaded into a plastic, or a method of coating a paint containing the antibacterial agent is used. Antibacterial agents can be roughly classified into organic antibacterial agents and inorganic antibacterial agents in which metal ions having antibacterial activity (silver, zinc, copper, etc.) are supported on a particulate inorganic carrier such as zeolite or silica gel. Organic antibacterial agents have excellent antibacterial effects, quick-acting properties, and dispersibility in organic base materials, but they elute from base materials,
There are problems in terms of safety to the human body, development of drug resistance in bacteria, heat resistance, and the like. In contrast, inorganic antibacterial agents
It has various advantages such as heat resistance, broad antibacterial spectrum, difficulty in acquiring drug resistance, and excellent safety to the human body, and is currently the mainstream of antibacterial agents.

On the other hand, the antibacterial activity of an antibacterial agent appears only on the surface of a product containing the antibacterial agent. Therefore, in order to efficiently use expensive antibacterial agents, it is effective to coat the surface of the product with the antibacterial agents.

However, when an inorganic antibacterial agent is applied to a coating on the surface of a substrate, various problems occur. For example, since an inorganic antibacterial agent basically uses a hydrophilic zeolite, silica gel or the like as a carrier, if it is mixed with a coating agent, it is difficult to i) disperse the antibacterial agent uniformly in the coating agent; ii) Since the carrier particle size and specific gravity are relatively large, they settle in the coating agent and are easily separated, and it is necessary to mix a large amount of antibacterial agent in order to increase the frequency of contact with bacteria and express a sufficient antibacterial effect . And iii)
Due to poor adhesion to the organic binder, the antibacterial agent easily falls off the surface of the coating film, and also reduces the mechanical strength of the coating film, and iv) impairs the transparency of the coating film.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an antibacterial agent capable of effectively exhibiting high antibacterial activity and an antibacterial resin containing the antibacterial agent despite the use of an inorganic antibacterial metal component. It is an object of the present invention to provide compositions and methods for their production. Another object of the present invention is to provide an antibacterial agent having excellent dispersibility, affinity with organic polymers, coating properties, and an antibacterial resin composition containing the same, even when used as a resin composition such as a coating agent, and the like. It is to provide a manufacturing method of.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, when an antibacterial metal component is supported on an organic polymer carrier, an antibacterial metal useful as an antibacterial coating agent or the like is obtained. The inventors have found that a conductive resin composition can be obtained, and have completed the present invention. That is, in the antibacterial agent of the present invention, an antibacterial metal component composed of a metal ion or a metal compound is supported by being chemically bonded to polymer particles. In this antibacterial agent, oxygen atom, nitrogen atom,
The antimicrobial metal component is chemically bonded to the polymer particles via a functional group containing at least one atom selected from the group consisting of a sulfur atom and a phosphorus atom. The polymer particles may have a crosslinked structure or may be porous. The average particle size of the polymer particles is 0.1 n
m to about 100 μm. Antibacterial metal components include silver,
It contains at least one metal component selected from platinum, copper, zinc, nickel, cobalt, molybdenum, chromium, etc., and the amount of the antibacterial metal component carried is about 0.01 to 70% by weight in terms of metal. It is. In the method of the present invention,
An antimicrobial agent is manufactured by chemically bonding an antimicrobial metal component composed of a metal ion or a metal compound to a functional group of a polymer particle and supporting the functional group. The present invention also includes a resin composition containing the antibacterial agent and a resin, and a coating resin composition containing the antibacterial agent and a binder resin. The antibacterial resin composition can be produced by mixing an antibacterial agent and a resin (binder resin).

[0007] In the present specification, "supporting" the antibacterial metal component means that the antibacterial metal component is held on the surface and / or inside the polymer particles as long as the antibacterial property is exhibited.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

[Polymer Particle] The type of the polymer particle is not particularly limited as long as it is insoluble (difficult or insoluble) in a binder resin or a solvent of the resin composition. The polymer constituting the polymer particles includes, for example, a synthetic polymer, a natural polymer,
An inclusion compound is exemplified, and a synthetic polymer is preferable.

The synthetic polymer constituting the polymer particles includes, for example, a modified olefin resin [ethylene- (meth) acrylic acid copolymer, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, epoxy-modified polyethylene, epoxy-modified polyethylene Polypropylene, etc.),
Styrene resin [polystyrene, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid alkyl ester copolymer, styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene- Maleic anhydride copolymer, acrylonitrile-styrene copolymer (AS resin), styrene-butadiene copolymer (SB resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), etc.), acrylic resin [(meta ) Acrylic acid- (meth) acrylic ester copolymers, homo- or copolymers of (meth) acrylic esters such as methyl methacrylate], polyvinyl alcohol, vinyl acetate resins [polyvinyl acetate, ethylene-
Vinyl acetate copolymers, etc.], vinyl ether resins [polyvinyl methyl ether, polyvinyl isobutyl ether, vinyl methyl ether-maleic anhydride copolymer, etc.], halogen-containing resins [polyvinyl chloride, polyvinylidene chloride, etc.], polyesters (poly C _2-4 alkylene terephthalate, poly C _2-4 alkylene naphthalate,
In addition to thermoplastic resins such as copolymerized polyester resins and modified polyester resins, polyamides (including copolymerized polyamide resins and modified polyamide resins), thermoplastic polyurethanes, polycarbonates, and polyamino acids, thermosetting or crosslinkable resins [non- Examples include saturated polyester resin, diallyl phthalate resin, vinyl ester resin, silicone resin, epoxy resin, thermosetting polyurethane, phenolic resin, amino resin (polyurea (urea resin), guanamine resin, melamine resin, etc.), polysilane, etc. .

Examples of the natural polymer include cellulose, partially hydrophobized (eg, acetylated) cellulose, starch, chitin, chitosan, gelatin, polypeptide, polynucleotide and the like. Examples of the inclusion compound include cyclodextrin, crown ether derivatives, cyclophan derivatives and the like. These polymers can be used alone or in combination of two or more.

[0011] In order to effectively exhibit the antibacterial activity of the antibacterial metal component, the polymer particles may be porous. The specific surface area of the porous polymer particles is, for example, 10 to 1000.
m ² / g, preferably from 50~1000m ² / g, more preferably 100~1000m ² / g approximately.

The polymer constituting the powdery polymer particles is usually a functional group capable of chemically bonding to the antibacterial metal component, for example, a halogen atom (particularly chlorine or bromine atom),
In particular, it has a functional group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom. Examples of the functional group containing an oxygen atom include a carboxyl group or a derivative group thereof (an acid halide group, an acid anhydride group and the like), a hydroxyl group, an acyl group (a C _1-4 acyl group such as a formyl and acetyl group), Carbonyl group, polycarbonyl group containing acetylacetone structure, ether group, polyether group containing polyethylene glycol structure, crown ether group, aromatic polyhydroxyl group containing catechol structure, aromatic hydroxycarbonyl group containing salicylic acid structure, phthalic acid structure And a polycarboxylic acid group, an epoxy group, a heterocyclic group (furyl group, chromanyl group, etc.).

Examples of the functional group containing a nitrogen atom include:
Amino group, monoalkylamino group (mono C _1-4 alkylamino group such as methylamino, ethylamino group, etc.),
Dialkylamino group (such as diC _1-4 alkylamino group such as dimethylamino and diethylamino group), azo group, amidino group, hydrazino group, hydrazono group, cyano group, nitrogen-containing heterocyclic group (pyrrolyl group, imidazolyl group, pyridyl Group, bipyridyl group, pyrrolyl group, piperidinyl group, piperazinyl group, quinolyl group, benzimidazolyl group, phenanthrolyl group, etc.), and azacrown ether group.

Examples of the functional group containing a sulfur atom include a mercapto group (thiol group), a thioxo group, a thienyl group, a thioacetyl group, an alkylthionyl group, a thiocarbamoyl group, a sulfonyl group, a thiocarboxyl group, and a sulfonic acid group (sulfo group). , A sulfinic acid group (sulfino group), a thiourea group (thioureido group), a thiacrown ether group,
Examples thereof include a thioether group and a heterocyclic group (such as a thiophenyl group). Examples of the functional group containing a phosphorus atom include a phosphoric acid group.

Examples of the functional group containing an oxygen atom and a nitrogen atom include a nitro group, an amide group, an imide group, an ureido group, an amino alcohol group such as an aminohydroxyethyl group, an aminophenol group, a quinolino group and an imidinoacetic acid group. Such as aminopolycarboxylic acid group, oxime group, amide oxime group, and heterocyclic group (morpholino group, morpholinyl group, etc.).

A plurality of the above functional groups can be combined. Since the bonding strength with a metal ion or a metal compound varies depending on the type of the functional group, the release of the metal ion or the metal compound from the polymer particles can be controlled by using a plurality of different types of functional groups in combination.

The type of the functional group can be selected according to the type of the antibacterial metal component. Preferred functional groups include an oxygen-containing functional group [eg, a carboxyl group, a polycarbonyl group, a crown ether group, a polycarboxylic acid group, etc.], a nitrogen-containing functional group [eg, an azacrowntel group, a nitrogen-containing heterocyclic group (imidazolyl) Group, a pyridyl group, a bipyridyl group, etc.), and a sulfur-containing functional group [a thiol group, a thioureido group, a thiocarbamoyl group, etc.]. When such a functional group is combined with an antibacterial metal component (for example, a silver component), a complex can be effectively formed.

The functional group concentration of the polymer particles is, for example, about 0.01 to 10 mmol per 1 g of the polymer particles.

The polymer particles may have a crosslinked structure. The polymer particles having a crosslinked structure may be self-crosslinked polymer particles (for example, cured or crosslinked particles of a thermosetting resin) or crosslinked polymer particles using a crosslinking agent. Such crosslinked polymer particles have high heat resistance and exhibit high resistance to exposure to high temperatures (for example, about 300 ° C.), such as baking paints and extrusion molding. The cross-linking agent can be selected according to the type of the functional group of the polymer. For example, in the case of a polymer using a polymerizable unsaturated monomer as a raw material (vinyl polymerizable polymer), a polyfunctional polymer is usually used as a copolymerizable monomer. Polymerizable monomer [divinylbenzene,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate Etc.] are used.

As the polymer (condensation type or addition condensation type polymer) using a condensation or addition reactive monomer as a raw material, a compound having two or more functional groups reactive to the functional group of the polymer can be used. When the polymer has a plurality of carboxyl groups or acid anhydride groups, for example, polyvalent metal ions (such as magnesium ions, aluminum ions, and zirconium ions); polyisocyanates (such as tolylene diisocyanate);
Hydrazine, phenylenediamine, etc.); an epoxy compound having a plurality of epoxy groups (such as an epoxy resin); a bisoxazoline compound (1,3-bis (oxazoly-2)
-Yl) benzene and the like.

When the polymer has hydroxyl groups,
For example, polyisocyanates (such as tolylene diisocyanate); polycarboxylic acids or reactive derivatives thereof (acid anhydrides such as adipic acid, phthalic acid, these acid halides, maleic anhydride, and phthalic anhydride); hydrolyzable silyl Compounds having a group (dichlorodimethylsilane, dichlorotetramethyldisiloxane, methyltrimethoxysilane, methyltriethoxysilane, etc.); compounds having a plurality of methylol groups or alkoxymethyl groups (urea resin, melamine resin, etc.); bisoxazoline compounds (E.g., 1,3-bis (oxazoli-2-yl) benzene) and the like.

When the polymer has an amino group, an amide group, etc., for example, polyisocyanate (tolylene diisocyanate, etc.); polycarboxylic acid or a reactive derivative thereof (adipic acid, phthalic acid, these acid halides, maleic anhydride) , An acid anhydride such as phthalic anhydride); a compound having a hydrolyzable silyl group (dichlorodimethylsilane,
Dichlorotetramethyldisiloxane, methyltrimethoxysilane, methyltriethoxysilane, etc.); an epoxy compound having a plurality of epoxy groups (epoxy resin, etc.); a bisoxazoline compound (1,3-bis (oxazoli-2-yl) benzene, etc.) ).

The polymer particles having a crosslinked structure include:
For example, crosslinked polymer particles (crosslinked styrene resin particles, crosslinked acryl resin particles, etc.) using a polyfunctional polymerizable monomer such as divinylbenzene as a crosslinking agent, crosslinked thermosetting resin particles (crosslinked silicone resin particles, epoxy resin Particles, crosslinked guanamine resin particles, crosslinked melamine resin particles, etc.).

The degree of crosslinking of the polymer particles is, for example, 0.1 to 30% by weight, preferably 0.5 to 20% in terms of a crosslinking agent.
%, More preferably about 1 to 10% by weight.

The polymer particles enhance the antibacterial activity,
If necessary, the composition may further contain an organic antibacterial agent.
The shape of the polymer particles may be spherical, plate-like, rod-like, petal-like, or the like. The average particle size of the polymer particles is, for example, 0.1 nm to 100 μm, preferably 1 n.
m to 30 μm (for example, 1 nm to 5 μm), more preferably about 5 nm to 10 μm (particularly, 10 nm to 1 μm), and may be about 10 to 500 nm.

The particle size of the polymer particles can be selected from the above range according to the intended use. When nano-sized polymer particles are used, the polymer particles can be uniformly dispersed in the resin composition. The content of components can be increased, and a high antibacterial effect can be obtained with a small amount of addition. Further, the state of the antibacterial metal component carried on the polymer particles (such as introduction of functional groups having different coordination properties to the antibacterial metal component into the polymer particles), the surrounding environment of the antibacterial metal component (hydrophilic or hydrophobicity of the polymer particles) The release of the antibacterial metal component can be controlled by the control of (3), and a fast-acting or persistent antibacterial agent can be obtained.

[Antimicrobial Metal Component] In the antimicrobial agent of the present invention, the antimicrobial metal component is supported by being chemically bonded to polymer particles. In particular, the antimicrobial metal component is chemically bonded to the polymer particles via the functional group (particularly, a functional group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom). doing. The terms “chemical bond” and “chemical bond” are used to include both ionic bonds and coordinate bonds.

The antimicrobial metal component is composed of a metal ion and a metal compound having antimicrobial properties, and these antimicrobial metal components can be used alone or in combination of two or more. Examples of the metal ions having antibacterial properties include silver ions (silver (I) or (II) ions), platinum ions, copper ions, zinc ions, nickel ions, cobalt ions, molybdenum ions, and chromium ions. . Preferred antimicrobial metal ions are silver (I) ions, copper ions and zinc ions, especially silver ions.

The metal compounds having antibacterial properties include silver,
At least one metal compound selected from platinum, copper, zinc, nickel, cobalt, molybdenum and chromium can be exemplified, and usually, a metal compound reactive or coordinating with the functional group of the polymer can be used. The metal compound may be a metal complex, and the metal complex may be anionic, cationic or neutral. In the case of an anionic complex, the counter cation is preferably a quaternary ammonium having antibacterial properties (phenyldimethylalkylammonium, didecyldimethylammonium, cetyltrimethylammonium, tetramethylammonium, etc.).

Preferred metal compounds include silver compounds, for example, silver halides (AgCl, AgBr, etc.), halides and perhalates (AgClO ₄ , AgCl
O ₃ , AgBrO ₃ , AgIO _3, etc., inorganic acid salts (silver sulfate, silver nitrate, silver carbonate, etc.), organic acid salts (silver acetate, silver oxalate, etc.), complexes (dicyano complex, dithiosulfite complex, diammine complex) , Dichloro complexes, etc.). The antimicrobial metal component is preferably capable of reacting or coordinating with a functional group of the polymer. For example, the antimicrobial metal component (eg, silver component) coordinates with a functional group of the polymer to form a complex (eg, thiol complex, thioureido complex, pyridyl complex, bipyridyl complex, phenanthrolyl complex, histidyl complex). You may.

The loading amount of the antibacterial metal component may be within a range that does not impair the antibacterial property. For example, it is 0.01 to 70% by weight, preferably 0.05% by weight of the total weight of the polymer compound fine particles in terms of metal. -30% by weight, more preferably 0.1-1%
5% by weight.

The preferred antibacterial agent of the present invention has, for example, a crosslinked structure, an oxygen-containing functional group, a nitrogen-containing functional group, a sulfur-containing functional group, etc., and an average particle diameter of 1 nm.
10 μm (for example, 1 nm to 3 μm, preferably 10 nm
Polymer particles (such as crosslinked styrene resin particles) of about 500 to 500 nm, particularly about 50 to 500 nm, and an antibacterial silver component that is carried by chemically bonding (particularly coordinating) to the functional group of the polymer particles. It is composed of In this antibacterial agent, the supported amount of the antibacterial silver component is about 0.05 to 30% by weight (preferably 1 to 10% by weight) in terms of silver.

[Method for producing antibacterial agent] The antibacterial agent of the present invention comprises:
The antibacterial metal component can be prepared by chemically bonding to a functional group of a polymer particle to be supported. The polymer particles can be prepared by using a conventional method such as pulverization and classification, suspension polymerization, emulsion polymerization and the like. The polymer particles having a crosslinked structure are obtained by a polymerization granulation method [a monomer composed of a crosslinker for forming a crosslinked structure, and a polymerizable monomer having a functional group capable of chemically bonding to an antibacterial metal component. A suspension polymerization method in which the mixture is polymerized in an aqueous medium in the presence of an emulsifier, ii)
Emulsion polymerization method in which polymerization is carried out in an aqueous medium in the presence or absence of an emulsifier, iii) dispersion polymerization method in which polymerization is carried out in a non-aqueous medium in the presence of a dispersion stabilizer, etc.]; in-liquid curing method [iv) antibacterial property A method of adding a polymer solution containing a functional group capable of chemically bonding to a metal component to a poor solvent for the polymer to form polymer particles in a medium, and then adding a crosslinking agent to cure the polymer, v A) a method of adding a mixed solution of a crosslinking agent and a polymer to a poor solvent for the polymer to form polymer particles in a medium, followed by curing]; a dispersion granulation method [vi) a mixture of the crosslinking agent and the polymer Spray-drying method for spray drying). The crosslinked polymer particles of a thermosetting resin having self-crosslinking properties can be prepared in the same manner as described above without using a crosslinking agent.

The functional group capable of chemically bonding to the antibacterial metal component may be derived from the above-mentioned monomer or cross-linking agent which is a raw material of the polymer. May be introduced. As a method of introducing the functional group into a polymer using a polymer reaction, for example,
A conventional method according to a method for preparing a metal ion-adsorbing resin such as a chelate resin can be adopted. For example, mercapto groups and bipyridyl groups are described in Ueyama, N, et al. Inorg. Chem.
Acta. 89, 19-23 (1984). The imidazole group can be introduced, for example, by reacting a polymer having a chloromethyl group with, for example, histidine.

The antimicrobial metal component is supported on the polymer particles by, for example, swelling the polymer particles with a solvent as necessary, adding and mixing a solution containing the antimicrobial metal component, and chemically bonding the antimicrobial metal component to the polymer. It can be carried out. After supporting the antibacterial metal component, the polymer is washed with a poor solvent and a good solvent, and then dried,
The antibacterial agent of the present invention is obtained.

The antibacterial agent of the present invention exhibits high antibacterial activity over a long period of time because the antibacterial metal component and the polymer particles are chemically bonded. In addition, since the polymer particles function as a carrier, the polymer particles have high affinity with the organic polymer. Therefore, the antibacterial agent of the present invention is useful for constituting an antibacterial resin composition in combination with a resin.

[Antimicrobial Resin Composition] In the antimicrobial resin composition, the resin can be selected from a wide range depending on the application. Examples of the resin include thermoplastic resins [olefin resins (polyethylene, polypropylene, polyethylene and modified polypropylene modified with carboxyl groups, acid anhydride groups, epoxy groups, etc.), acrylic resins (polymethyl methacrylate, containing carboxyl groups). Acrylic resin, hydroxyl group-containing acrylic resin, epoxy group-containing acrylic resin, etc., styrene resin (polystyrene, AS resin, ABS resin, copolymer of styrene and (meth) acrylic monomer, etc.), vinyl acetate Resins (polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl acetate-vinyl chloride copolymer, etc.), vinyl alcohol polymers (polyvinyl alcohol, ethylene-vinyl alcohol copolymer, etc.), vinyl chloride resins (poly Vinyl chloride, etc.), polyester resin (poly Alkylene terephthalate, polyalkylene naphthalate, copolymerized polyester resin, modified polyester resin, etc.), polyurethane resin, polyamide resin, rubber, etc.), thermosetting resin [epoxy resin, phenolic resin, urethane resin, unsaturated polyester resin, vinyl ester Resin, diallyl phthalate resin, silicone resin, amino resin (urea resin, melamine resin, etc.)], photocurable resin [photocurable oligomers such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, etc. And photo-curable monomers such as polyfunctional (meth) acrylates and nitrogen-containing monomers]. The resin may be a water-soluble resin or an organic solvent-soluble resin. Further, the resin can be used as an aqueous dispersion (emulsion, latex, etc.) or a non-aqueous dispersion (organosol, etc.). These resins can be used alone or in combination of two or more.

The resin composition of the present invention includes an antibacterial molding resin composition containing a molding resin used for molding such as extrusion molding and injection molding, and a resin composition containing an adhesive resin. Preferably, the coating resin composition contains a resin for a coating agent such as a paint (organic binder resin).

The resin composition for coating may be in the form of a powder coating agent composed of powder and granules, an aqueous coating agent composed of an aqueous solvent as a solvent, a solvent type coating agent composed of an organic solvent as a solvent, and the like. Any of them may be used. Examples of the aqueous solvent include water alone, and a mixed solvent of water and a water-soluble organic solvent (such as alcohols, ketones, ethers, and cellosolves). Examples of the organic solvent include aliphatic hydrocarbons such as hexane, and the like. Alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene,
Examples thereof include esters such as ethyl acetate, ketones such as methyl ethyl ketone, ethers, and mixed solvents thereof.

Since the antimicrobial agent contains polymer particles having a high affinity for the resin, even if it is added in a large amount to the resin composition, it is possible to suppress the deterioration of the properties of the resin composition. Therefore, the amount of the antibacterial agent to be used can be selected from a wide range.
To 200 parts by weight, preferably 0.1 to 100 parts by weight, more preferably about 0.5 to 50 parts by weight.

The antimicrobial resin composition of the present invention contains various additives such as stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), plasticizers, antistatic agents, flame retardants, dispersants, It may contain a surfactant, a filler, a colorant, a viscosity modifier, a preservative, a fungicide, a leveling agent, and the like.

The antibacterial resin composition (or coating resin composition) can be prepared by mixing the above antibacterial agent, a resin or a binder resin, and if necessary, a solvent or an additive. For the preparation of the resin composition, a conventional apparatus, for example, a kneader, a disperser, a mixer, or the like can be used depending on the form of the resin composition.

Such an antibacterial resin composition can maintain a high antibacterial activity for a long period of time. In particular, in order to effectively exhibit antibacterial properties on the surface of a product, it is advantageous to form a coating film (coating film) containing an antibacterial agent. The thickness of the coating film is, for example, 1 to 500 μm, preferably 5 to 3 μm.
It can be appropriately selected from a range of about 00 μm. The coating film is obtained by applying a coating resin composition to a substrate by a conventional coating method (spray coating, roll coating, gravure roll coating, etc.) and drying (heat curing as necessary) or light irradiation (ultraviolet irradiation, etc.). Can be formed. Paper, paper,
Wood, plastics, ceramics including glass, metals and the like can be used.

When the antibacterial agent of the present invention is used in a coating agent such as a paint, the antibacterial agent can be dispersed uniformly and easily, the dispersion stability is high, and sedimentation and the like can be prevented. Therefore, the activity of the antibacterial agent can be effectively exhibited even with a small amount of the antibacterial agent. Furthermore, since it has high affinity and adhesion to an organic binder, a coating film having high mechanical strength and high transparency can be formed.

[0045]

According to the present invention, since the antibacterial metal component of the antibacterial agent is chemically bonded to the polymer particles, a high antibacterial activity can be effectively achieved for a long period of time despite the use of the inorganic antibacterial metal component. It can be expressed throughout. Further, even when used as a resin composition such as a coating agent, the antibacterial agent is excellent in dispersibility, affinity with organic polymers, and film properties.

[0046]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 [Preparation of chlorine-containing crosslinked polystyrene fine particles] Styrene (7.8 g, 0.075 mol), chloromethylated styrene (3.5 g, 0.023 mol) and ethylene glycol dimethacrylate (0.4 g, 0.1 g). 002 mol) is subjected to soap-free emulsion polymerization using potassium persulfate (0.2 g) to obtain chlorine-containing crosslinked polystyrene (styrene-chloromethylated styrene copolymer) fine particles having a particle diameter of 200 to 300 nm. Was.

[Preparation of Silver Complex-Supported Polymer Fine Particles] After thiourea (2.85 g) was dissolved in a mixed solvent of dioxane (27 g) and acetone (30 g), the chlorine-containing crosslinked polystyrene fine particles (5 g, chlorine (A content of 7 mmol) was dispersed and refluxed for 3 hours. After cooling the reaction mixture, the solvent was distilled off under reduced pressure, and the polymer particles were redispersed in tetrahydrofuran. Then, a sodium hydroxide / methanol mixture was added, and the mixture was refluxed for 3 hours. After cooling the reaction mixture, 0.1N hydrochloric acid was added until the mixture became weakly acidic, and the mixture was stirred at room temperature for 0.5 hour. Next, water was added to the reaction mixture under argon gas flow until the polymer particles shrinked, the liquid layer was removed by decantation, and methanol was added to wash the polymer particles twice. The swelling with tetrahydrofuran and the washing with shrinkage with methanol were repeated five times, followed by drying under reduced pressure to obtain thiol group-introduced polymer particles.

After swelling the obtained polymer fine particles with tetrahydrofuran, 20 ml of a solution of silver perchlorate (1.5 g) in tetrahydrofuran was added, and the mixture was stirred for 1 hour, followed by swelling with tetrahydrofuran and shrink-washing with methanol. Was repeated 5 times and dried under reduced pressure to obtain silver complex-carrying polymer fine particles. The silver content in the polymer fine particles was 10.5% by weight.

Example 2 Using fine particles (5 g) of crosslinked chlorine-containing polystyrene (styrene-chloromethylated styrene copolymer) prepared in the same manner as in Example 1, and a mixed solution of hydrogen bromide / acetic acid, bromine was used. Containing crosslinked polystyrene (styrene-bromomethylated styrene copolymer) fine particles were obtained. The polymer fine particles (5 g) were dispersed in 30 ml of tetrahydrofuran, and bipyridyl (0.75 g, 4.8 mmol) was dissolved.
A hexane solution of butyllithium (4.8 mmol) was added, and the mixture was stirred at room temperature for 6 hours. Water was added to the reaction mixture until the polymer particles contracted, the liquid layer was removed by decantation, and methanol was added to wash the polymer particles twice. Next, the swelling with tetrahydrofuran and the shrinking and washing operation with methanol were repeated five times, followed by drying under reduced pressure to obtain polymer particles into which bipyridyl groups had been introduced. Then, thiourea (1.
5g) to introduce a thiol group.

After swelling the obtained polymer fine particles with tetrahydrofuran, 20 ml of a solution of silver perchlorate (1.5 g) in tetrahydrofuran was added, and the mixture was stirred for 1 hour, followed by swelling with tetrahydrofuran and shrink-cleaning operation with methanol. Was repeated 5 times and dried under reduced pressure to obtain silver complex-carrying polymer fine particles. The silver content in the polymer fine particles was 8.9% by weight.

Example 3 A thiol group was introduced in the same manner as in Example 1 using chloromethylated polystyrene beads (divinylbenzene, 2% by weight, overseas, chlorine content: 0.97 mmol / g, manufactured by Nacalai Tesque, Inc.). Then, it was reacted with silver ions to obtain silver-loaded polymer beads. The silver content in the beads is 4.3% by weight
Met.

Example 4 Methyl methacrylate (7.8 g,
Except for using 0.078 mol), chlorine-containing crosslinked polymer fine particles were prepared in the same manner as in Example 1, and then thiol groups and subsequently silver ions were introduced to obtain silver-loaded polymer fine particles. The silver content in the polymer fine particles was 9.8% by weight.

Example 5 Chlorine-containing crosslinked polystyrene fine particles (5 g) prepared in the same manner as in Example 1 were treated with dimethylformamide (DMF) 3
The mixture was dispersed in 0 ml, and L-histidine methyl ester (2.8 g, 14 mmol) was added to the mixture and reacted at 50 ° C. for 6 hours. After cooling the reaction mixture, polymer fine particles were separated from the reaction mixture by centrifugation. After the collected polymer fine particles were swollen with a small amount of DMF, methanol was added to shrink the polymer particles. This swelling / shrinking operation was repeated five times to wash the polymer fine particles and dried under reduced pressure to obtain imidazole group-introduced polymer fine particles. This polymer fine particle and silver perchlorate (1.5 g) were used in Example 1.
The reaction was carried out in the same manner as described above to obtain silver complex-carrying polymer fine particles. The silver content in the polymer fine particles was 5.1% by weight.

The test strain (S. aureus ATCC 538,
And E. coli ATCC 8739) were evaluated for antibacterial activity by the pour method, and all the antibacterial agents (silver-loaded polymer particles) obtained in Examples 1 to 5 showed antibacterial activity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 57/00 A01N 57/00 Z

Claims (12)

[Claims] An antibacterial agent in which an antibacterial metal component composed of a metal ion or a metal compound is supported by being chemically bonded to polymer particles. 2. The antimicrobial metal component chemically binds to the polymer particles via a functional group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom. The antibacterial agent according to claim 1. 3. The antibacterial agent according to claim 1, wherein the polymer particles have a crosslinked structure. 4. The antibacterial agent according to claim 1, wherein the polymer particles are porous. 5. The polymer particles have an average particle diameter of 0.1 n.
The antibacterial agent according to claim 1, which has a size of m to 100 µm. 6. The antibacterial agent according to claim 1, wherein the antibacterial metal component is at least one metal component selected from the group consisting of silver, platinum, copper, zinc, nickel, cobalt, molybdenum and chromium. 7. The antibacterial agent according to claim 1, wherein the supported amount of the antibacterial metal component is 0.01 to 70% by weight in terms of metal. 8. A polymer particle having an oxygen-containing functional group, a nitrogen-containing functional group or a sulfur-containing functional group, having a cross-linked structure, and having an average particle diameter of 1 nm to 30 μm, and It is composed of an antibacterial silver component supported by chemical bonding, and the carried amount of the antibacterial silver component is
The silver content is 0.05 to 30% by weight of the whole.
Antibacterial agent as described. 9. A method for producing an antibacterial agent in which an antibacterial metal component composed of a metal ion or a metal compound is chemically bonded to a functional group of a polymer particle and supported. 10. A resin composition comprising the antibacterial agent according to claim 1 and a resin. 11. A coating resin composition comprising the antibacterial agent according to claim 1 and a binder resin. 12. A method for producing an antibacterial resin composition, comprising mixing the antibacterial agent according to claim 1 and a resin.