JP2003335864A - Antibacterial resin and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antibacterial resin which can effectively exhibits antibacterial properties against various microorganisms (e.g. bacteria and mold) and organisms (e.g. aquatics) and can reduce a load on the environment. <P>SOLUTION: The antibacterial resin comprises a resin carrying through chemical bonding an antibacterial metal component comprising a metal ion or a metal compound, with the antibacterial metal component carrying through chemical bonding an antibacterial organic component comprising at least a pyridinecarboxylic acid or its derivative. The resin may comprise polymer particles having a crosslinked structure containing units which contain at least one atom selected from oxygen, nitrogen and sulfur atoms and has a functional group capable of chemically bonding to the antibacterial metal component, and crosslinking units. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antibacterial resin that effectively exhibits antibacterial properties against various microorganisms (bacteria, fungi, etc.) and organisms (aquatic organisms, etc.), a method for producing the same, and the above antibacterial resin. And an antibacterial composition which is useful as a coating agent and the like and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, from household products and daily life materials to industrial products (hereinafter simply referred to as base materials), microorganisms and organisms [aquatic organisms (animals such as bivalves, plants such as algae, etc.)] Has been subjected to antimicrobial or antifouling (hereinafter simply referred to as antibacterial) treatment in order to suppress the growth of the plant for a long period of time. The applications of these antibacterial treatments and the amount of antibacterial treatments are steadily expanding. On the other hand, it is feared that the use of the antibacterial agent may increase the load on the human body and the natural environment, and there is a demand for a highly safe antibacterial agent having a small environmental load. The antibacterial agents currently used are roughly classified into organic antibacterial agents and inorganic antibacterial agents mainly containing silver ions or copper ions.

Of the above-mentioned antibacterial agents, organic antibacterial agents are widely used because they have antibacterial or antifungal properties, immediate effects, and excellent dispersibility in resins. However, since the retention of the organic antibacterial agent on the base material is usually small, the organic antibacterial agent is released from the base material and loses the antibacterial property in a relatively short period of time. There are problems such as developing drug resistance. In addition, since it has poor heat resistance, it is difficult to knead into plastic.

On the other hand, an inorganic antibacterial agent in which a metal ion having antibacterial activity (silver, zinc, copper, etc.) is carried on an inorganic carrier (particulate inorganic carrier such as zeolite or silica gel), particularly silver ion is inorganic. An inorganic antibacterial agent ion-bonded to a carrier has low toxicity to the human body, has a broad antibacterial spectrum, and is resistant to the emergence of resistant bacteria. Therefore, it is currently used for the antibacterial treatment of many industrial products. .

However, in the antibacterial treatment of the base material, since the inorganic antibacterial agent has a small content of antibacterial components, sufficient antibacterial properties cannot be obtained for a long period unless the used amount is increased, and the organic antibacterial agent is not used. Since the affinity with the base material is low, the processing efficiency of the base material is significantly reduced. Further, since the antibacterial component is ionically supported on the base material, when the base material frequently comes into contact with water, the antibacterial component is eluted, and the base material quickly loses its antibacterial property. Further, although the inorganic antibacterial agent is in the form of fine particles, it has a problem that it cannot be used as a base material that requires transparency because of its large particle size.

Japanese Unexamined Patent Publication (Kokai) No. 11-222402 discloses an antibacterial polymer particle in which an antibacterial metal component composed of a metal ion or a metal compound is supported by being chemically bonded to the polymer particle. The polymer particle has a hydrophilic unit, a unit containing at least one atom selected from oxygen atom, nitrogen atom and sulfur atom, and a unit having a functional group chemically bondable to the antibacterial metal component, and crosslinked. Disclosed is an antibacterial polymer particle composed of a hydrophilic polymer having a crosslinked structure containing a unit. Japanese Patent Application Laid-Open No. 2001-40222 discloses an antibacterial polymer particle in which an antibacterial metal component composed of a metal ion or a metal compound is chemically bonded to and carried by a polymer particle, and oxygen atom, nitrogen Disclosed is an antibacterial polymer particle in which an antibacterial or antifungal organic component containing at least one atom selected from an atom and a sulfur atom is supported by being chemically bonded to the antibacterial metal component.

Such antibacterial polymer particles are
Since it is an inorganic composite particle, it can be used in a wide range of applications and can impart high antibacterial properties to a substrate. However, it is required to further enhance safety and further reduce environmental load.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an antibacterial resin which can effectively and continuously maintain its antibacterial property against various microorganisms and organisms for a long period of time, and has a small environmental load, and a method for producing the same. To do.

Another object of the present invention is to provide an antibacterial resin which is highly safe and free from environmental pollution and a method for producing the same.

[0010]

Means for Solving the Problems The present inventors have focused their attention on the fact that nicotinic acid or its derivatives have high safety and antibacterial properties. When polymer particles in which an antibacterial organic component composed of at least pyridinecarboxylic acid and / or a derivative thereof (particularly nicotinic acid amide) is supported on an organic polymer carrier through a metal component, high antibacterial activity is obtained. It can be maintained for a long time and is highly safe,
We found that a low environmental load antibacterial resin can be obtained,
The present invention has been completed.

That is, in the antibacterial resin of the present invention, an antibacterial metal component composed of a metal ion or a metal compound is supported by being chemically bonded to the resin, and the antibacterial organic component has the above-mentioned antibacterial property. An antibacterial resin that is chemically bonded to and carried by a metal component, wherein the antibacterial organic component is composed of at least pyridinecarboxylic acid or a derivative thereof. In this antibacterial resin, the resin is a crosslinked resin particle, for example, a functional group containing at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom and capable of chemically bonding to an antibacterial metal component. A unit having
It may be composed of polymer particles having a crosslinked structure containing a crosslinking unit. Further, the polymer particle having a crosslinked structure contains a hydrophilic unit and at least one functional group selected from a carboxyl group, a pyridyl group, a mercapto group, a thiocarbamate group and a dithiocarbamate group, and has an antibacterial metal component. It may be composed of a hydrophilic polymer gel containing a unit having a functional group capable of being chemically bound with each other and a crosslinking unit. Further, the antibacterial metal component may be composed of at least one metal component selected from the group consisting of silver, platinum, copper, zinc, nickel, cobalt, molybdenum, chromium, silicon, and iron. The ratio of the pyridinecarboxylic acid or its derivative and the antibacterial metal component (metal conversion) is the former / the latter = 0.1 / 1 to 5
It may be about 1/1 (molar ratio).

More specifically, the antibacterial resin has polymer particles having an oxygen-containing functional group, a nitrogen-containing functional group or a sulfur-containing functional group and having an average particle diameter of 5 nm to 30 μm, and the polymer particles described above. It may be composed of an antibacterial metal component that is chemically bonded to a functional group and is supported and is selected from silver or copper, and nicotinic acid amide that is supported by the antibacterial metal component.

According to the present invention, a resin capable of chemically bonding to a metal component comprises an antibacterial organic component composed of a metal ion or a metal compound and at least pyridinecarboxylic acid or a derivative thereof. It also includes a method for producing an antibacterial resin treated with a component, and an antibacterial composition containing the antibacterial resin. Furthermore, the present invention also includes a method of applying the antibacterial resin to a material to be treated to prevent adhesion of aquatic organisms to the material to be treated.

In the present specification, "antibacterial" means having an inhibitory activity against the growth of microorganisms or the attachment or growth of organisms such as aquatic organisms, and "supporting" of antibacterial metal components means As long as the antibacterial property is exhibited, it means that the antibacterial metal component is retained on the surface and / or the inside of the resin, and "carrying" of the antibacterial organic component means that the antibacterial organic component becomes the antibacterial metal component. Means held.
"Chemical bond" and "chemical bond" are used to mean both an ionic bond such as salt formation and a coordinate bond, and are sometimes simply referred to as "coordination". In addition, "non-crosslinked hydrophilic polymer" and "hydrophilic polymer having a crosslinked structure" may be simply referred to as "hydrophilic polymer".

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION [Antibacterial Resin] An antibacterial resin is composed of a resin and an antibacterial metal component (metal ion or metal compound) supported by being chemically bound to the resin and proliferating microorganisms. And a metal component having an inhibitory activity against the attachment and growth of aquatic organisms), and an antibacterial organic component chemically bound to and carried by the antibacterial metal component, and composed of at least pyridinecarboxylic acid or a derivative thereof. It consists of and. Such an antibacterial resin has a high affinity with organic polymers, can contain antibacterial metal components and antibacterial organic components in high concentration, and has a high antibacterial property even if the content of antibacterial metal components is extremely low. Can be expressed over a long period of time.

[Resin] The resin is not particularly limited as long as it can support the antibacterial metal component, and may be a synthetic resin or a natural resin. The resin may be a hydrophobic resin, but is preferably a hydrophilic resin. When the resin is composed of a hydrophilic resin, the antibacterial property can be effectively exhibited even under high humidity conditions by controlling the degree of hydrophilicity and the like.

In order to chemically bond the antibacterial metal component to the resin, the resin is preferably capable of chemically bonding to the metal component and has a functional group capable of coordinating the antibacterial metal component. Preferably. That is, the preferred resin includes a resin having a functional group capable of chemically bonding to a metal component, for example, an oxygen-containing functional group, a nitrogen-containing functional group, or a sulfur-containing functional group.

Examples of the functional group containing an oxygen atom (particularly a coordinating group) include, for example, a carboxyl group or its derivative group (acid halide group, acid anhydride group, etc.), hydroxyl group, acyl group (formyl, acetyl group, etc.). C _1-4 acyl group), carbonyl group, polycarbonyl group containing acetylacetone structure, ether group, crown ether group, aromatic polyhydroxyl group containing catechol structure, aromatic hydroxycarbonyl group containing salicylic acid structure, phthalic acid Examples thereof include a polycarboxylic acid group having a structure, an epoxy group, an oxygen-containing heterocyclic group (furyl group, chromanyl group, etc.) and the like.

Examples of the functional group containing a nitrogen atom (particularly a coordinating group) include, for example, amino groups, mono- or dialkylamino groups (mono C _1-4 alkylamino groups, di C _1-4 alkylamino groups, etc.), Azo group, amidino group, hydrazino group, hydrazono group, cyano group, nitrogen-containing heterocyclic group (pyrrolyl group,
Examples thereof include an imidazolyl group, a pyridyl group, a bipyridyl group, a piperidinyl group, a piperazinyl group, a quinolyl group, a benzimidazolyl group, a phenanthrolyl group) and an azacrown ether group. An amino group or an imino group is often used as the nitrogen-containing functional group, and the nitrogen-containing functional group may be a heterocyclic group such as a pyridyl group.

The functional group containing sulfur atom (particularly coordinating group) includes mercapto group (thiol group), thioxo group, thienyl group, thioacetyl group, alkylthionyl group, thiocarbamoyl group (thiocarbamate group), dithiocarbamate. Group, sulfonyl group, thiocarboxyl group, sulfonic acid group (sulfo group), sulfinic acid group (sulfino group), thiourea group (thioureido group), thiocrown ether group, thioether group, heterocyclic group (thiophenyl group, etc.), etc. Can be illustrated.

The polymer particles are functional groups having a plurality of atoms selected from oxygen atom, nitrogen atom, sulfur atom and the like,
For example, it may have a functional group containing an oxygen atom and a nitrogen atom. Such functional groups include, for example, nitro groups, ureido groups, amino alcohol groups such as aminohydroxyethyl groups, aminophenol groups, quinolino groups, aminopolycarboxylic acid groups such as imidinoacetic acid groups,
Examples thereof include oxime group, amidooxime group, and heterocyclic group (morpholino group, morpholinyl group, etc.).

A plurality of the above functional groups can be combined. Since the strength of the bond with the metal ion or the metal compound varies depending on the type of the functional group, it is possible to release the antibacterial metal component from the polymer particles by using a plurality of different types of functional groups in combination, and thus the antibacterial organic component. Controlled release.

The type of functional group can be selected according to the type of antibacterial metal component. Preferable functional groups include oxygen-containing functional groups [eg, carboxyl groups], nitrogen-containing functional groups [eg, nitrogen-containing heterocyclic groups (imidazolyl group, pyridyl group, bipyridyl group, etc.)], sulfur-containing functional groups [thiol Group, thioureido group, thiocarbamate group, dithiocarbamate group and the like]. A complex can be effectively formed by combining such a functional group with an antibacterial metal component (for example, a copper component).

The shape of the resin is not particularly limited as long as it can support the antibacterial metal component, and may be particulate or non-particulate.

In the case of particles, the resin may be a non-crosslinked resin that is soluble in a solvent, but since it constitutes a particulate resin that is sparingly soluble or insoluble in a solvent, it is a polymer having a crosslinked structure. It is preferably a particle.

The polymer particles comprise hydrophilic and / or hydrophobic units (preferably at least hydrophilic units),
A coordinating unit containing at least one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and having a functional group (particularly a coordinating group) capable of chemically bonding to an antibacterial metal component, It is composed of a bridging unit. In the hydrophilic polymer particles, the hydrophilic unit and the coordinating unit having a functional group may be the same or different.

As the hydrophilic unit, various hydrophilic fragments and segments can be used. For example, a unit containing a carboxyl group [(meth) acrylic acid, maleic anhydride or the like is formed of a monomer containing a carboxyl group or an acid anhydride group. Unit], a hydroxyl group-containing unit [a vinyl alcohol unit formed by hydrolysis of polyvinyl acetate, a unit formed of a hydroxyl group-containing monomer such as hydroxy C _2-3 alkyl (meth) acrylate], an ether group-containing unit [ Vinyl C
_1-4 Units formed of ether group-containing monomers such as alkyl ether, polyethylene glycol mono- or di (meth) acrylate, polyethylene glycol],
Examples thereof include a nitrogen-containing unit [a unit formed of a nitrogen-containing monomer such as vinylpyrrolidone, vinylpyridine, (meth) acrylamide, methylol (meth) acrylamide, N, N-dialkylaminoalkyl (meth) acrylate]. The hydrophilic polymer may have a plurality of different hydrophilic units, and the hydrophilic units may optionally form a salt.

The preferred hydrophilic unit includes a hydrophilic unit which forms a water-soluble polymer and has an affinity for a hydrophobic resin, and such hydrophilic unit includes a nitrogen atom (particularly an amide group). Alternatively, a unit including an N-substituted amide group (for example, a hydrophilic unit formed of (meth) acrylamide, N-substituted (meth) acrylamide, etc.) can be exemplified. N-substitution (meta)
Examples of acrylamide include N-methyl (meth)
Acrylamide, N-ethyl (meth) acrylamide,
N- butyl (meth) N-C _1-6 alkyl (meth) acrylamides such as acrylamide, etc. N-C _1-6 acyl (meth) acrylamides can be exemplified. When the hydrophilic unit is formed of N—C _1-6 alkyl (meth) acrylamide such as N-butylacrylamide, the polymer particles can be provided with temperature sensitivity.

Examples of the hydrophobic unit include (meth) acrylic acid alkyl esters, (meth) acrylic monomers such as (meth) acrylonitrile, styrene,
Aromatic vinyl monomers such as divinylbenzene, vinyl ester-based monomers such as vinyl acetate, halogen-containing monomers such as vinyl chloride and vinylidene chloride, ethylene,
An example is a unit formed of olefin such as propylene.

The coordinating unit is composed of a unit having a functional group (functional group containing oxygen atom, nitrogen atom, sulfur atom, etc.) capable of chemically bonding to the above metal component.

The cross-linking unit for introducing a cross-linking structure into the hydrophilic polymer particles is composed of condensable groups or fragments such as self-cross-linking polymer particles (eg, cured or cross-linked particles of thermosetting resin). It may be composed of a crosslinking agent. Crosslinked polymer particles have high heat resistance,
It exhibits high resistance even when exposed to high temperatures (for example, about 300 ° C.) such as baking paint.

As the cross-linking agent constituting the cross-linking unit,
In the case of a polymer (vinyl polymerization type polymer) made of a polymerizable unsaturated monomer as a raw material, a polyfunctional polymerizable monomer [divinylbenzene, methylenebis (meth) acrylamide, 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 and the like] are used.

In a hydrophilic polymer (condensation type or addition condensation type polymer) using a condensation or addition reactive monomer as a raw material,
As the crosslinking agent, a compound having two or more reactive functional groups with respect to the functional groups of the polymer can be used.

When the hydrophilic polymer has a plurality of carboxyl groups or acid anhydride groups, examples of the crosslinking agent include polyvalent metal ions (magnesium ion, aluminum ion, zirconium ion, etc.); polyisocyanate;
Examples thereof include polyamines; epoxy compounds having a plurality of epoxy groups; bisoxazoline compounds and the like.

When the hydrophilic polymer has a hydroxyl group, examples of the crosslinking agent include polyisocyanates; polyvalent carboxylic acids or their reactive derivatives (acid halides, acid anhydrides); compounds having a hydrolyzable silyl group (dichloro). Dimethylsilane, dichlorotetramethyldisiloxane,
Methyltrimethoxysilane, methyltriethoxysilane, etc.); compounds having a plurality of methylol groups or alkoxymethyl groups (urea resins, melamine resins, etc.); bisoxazoline compounds and the like.

When the hydrophilic polymer has an amino group, an amide group, etc., for example, polyisocyanate; polyvalent carboxylic acid or its reactive derivative; a compound having a hydrolyzable silyl group; an epoxy compound having a plurality of epoxy groups; A bisoxazoline compound or the like can be used as a crosslinking agent.

The degree of crosslinking of the hydrophilic polymer particles is, for example,
In terms of the content of the crosslinking unit (or crosslinking agent), 0.1 to 0.1
It is 30% by weight, preferably 0.5 to 20% by weight, more preferably about 1 to 10% by weight.

The hydrophilic polymer particles having a crosslinked structure include (i) the coordination unit having hydrophilicity (for example,
The carboxyl group, a nitrogen-containing group such as a nitrogen-containing heterocyclic group, a unit formed of a monomer containing a mercapto group, and a crosslinking unit (for example, a crosslinking monomer or a crosslinking agent such as a polyfunctional polymerizable monomer) Unit formed)
And (ii) the hydrophilic unit (a unit formed of a monomer such as (meth) acrylamide or N-substituted (meth) acrylamide) and the coordinating unit (for example, A copolymer or cocondensate of a unit formed of a monomer containing a carboxyl group, a nitrogen-containing functional group, a mercapto group, etc. and a crosslinking unit (for example, a unit formed of a polyfunctional polymerizable monomer) Is included.

These polymer particles (preferably hydrophilic polymer particles) are further used as a copolymerization unit, for example, (meth) acrylic acid alkyl ester, (meth) acryl-based monomer such as (meth) acrylonitrile, styrene, divinylbenzene. Aromatic vinyl monomers such as, vinyl ester-based monomers such as vinyl acetate, halogen-containing monomers such as vinyl chloride and vinylidene chloride,
It may contain a unit formed of an olefin such as ethylene or propylene, and may be further modified if necessary. By introducing a hydrophobic copolymerization unit (for example, a hydrophobic unit made of methyl methacrylate, styrene, divinylbenzene, etc.) into the hydrophilic unit or the hydrophilic polymer particles, the elution property of the antibacterial agent can be controlled.

Preferable hydrophilic polymer particles include hydrophilic polymer gel [for example, a crosslinked polymer having a coordinating unit (crosslinked polyacrylic acid, crosslinked polyvinylpyridine, etc.), a crosslinked polymer having an acrylamide unit and a coordinating unit. Polymer (crosslinked acrylamide- (meth) acrylic acid copolymer, crosslinked acrylamide-vinylpyridine copolymer, crosslinked acrylamide-mercaptomethyl-substituted styrene copolymer,
Acrylamide- (meth) acrylic acid-vinylpyridine copolymer having a crosslinked structure)].

Functional group of polymer particle (coordinating unit)
The concentration of can be selected according to the amount of antibacterial metal component supported,
For example, it is about 0.01 to 10 mmol, preferably 0.05 to 7 mmol, and more preferably about 0.1 to 5 mmol per 1 g of polymer particles. The amount of the monomer having a coordinating unit is, for example, 5 to 100% by weight, preferably 10 to 100% by weight, more preferably 25 to 100% by weight, based on the total amount of the monomers constituting the polymer particles. You can choose from a range of degrees.

The polymer particles may be porous in order to effectively exhibit the antibacterial activity of the antibacterial component (particularly the antibacterial metal component). The specific surface area of the porous particles is, for example, 10
~1000m ² / g, preferably 50~1000m ² /
g, and more preferably about 100 to 1000 m ² / g.

The shape of the polymer particles may be spherical, plate-like, rod-like, petal-like or the like. The average particle diameter of the polymer particles is, for example, 1 nm to 100 in a dry state.
Can be selected from the range of about μm, usually 5nm ~ 30μm
(For example, 5 nm to 10 μm), preferably 5 nm to 1
μm (for example, 10 nm to 0.7 μm), more preferably 15 nm to 0.5 μm (for example, 20 nm to 0.3 μm)
m), and may be about 25 nm to 0.1 μm.

The particle size of the polymer particles can be selected according to the application, but when nano-sized polymer particles are used, the dispersibility and transparency in the resin composition, the antibacterial metal component and the antibacterial organic component in the resin composition can be improved. The content of can be increased, and high antibacterial properties can be expressed with a small addition amount.

In the case of a non-particulate resin, a non-crosslinked polymer (non-crosslinked resin) which does not use a crosslinking agent is usually used. The resin may be a soluble resin in an aqueous solvent or an organic solvent, or an aqueous dispersion type resin (emulsion type or latex type resin).

When a non-particulate resin is used as an antibacterial resin, it is usually preferable that it has a film-forming ability to form an antibacterial film, and it is a resin for paints to form a coating composition. Preferably. Further, in order to form a hydrolyzable paint (self-polishing or self-polishing antifouling paint), it is preferable that the non-particulate resin has a hydrolyzability, for example, the functional group (oxygen-containing functional group). Group, a nitrogen-containing functional group, a sulfur-containing functional group, etc.) (for example, a vinyl polymer having a carboxyl group, a pyridyl group, an amide group, a mercapto group, etc.) (for example,
Acrylic polymers)) and the like.

[Antibacterial metal component] The resin is chemically bonded with an antibacterial metal component having an inhibitory activity against the growth and adhesion of various microorganisms (bacteria, fungi, etc.) and organisms (aquatic organisms, etc.). It is carried. In particular, the antibacterial metal component is chemically bonded to the resin via the functional group (functional group containing oxygen atom, nitrogen atom, sulfur atom, etc.).

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

As the metal compound having antibacterial properties, silver,
At least one metal compound selected from platinum, copper, zinc, nickel, cobalt, molybdenum, chromium, iron and silicon (particularly silver, platinum, copper, zinc, nickel, cobalt, molybdenum, 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.).

Taking a silver compound as an example, preferred metal compounds include, for example, silver halide (AgCl,
AgBr, etc.), halogenates and perhalogenates (Ag
ClO ₄ , AgClO 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) , Diamine complexes, dichloro complexes, etc.). As the copper compound, compounds corresponding to the above silver compounds can be exemplified.

The antibacterial metal component (copper component etc.) is coordinated to the functional group of the polymer to form a complex (thiol complex, thioureido complex, pyridyl complex, bipyridyl complex, phenanthrolyl complex, histidyl complex etc.). You may. When the antibacterial metal component capable of coordinating with the functional group of the polymer is used, the content of the antibacterial metal component can be increased and the antibacterial activity can be maintained for a long period of time.

The amount of the antibacterial metal component supported may be in a range that does not impair the antibacterial property. For example, it is 0.01 to 70% by weight, preferably 0.
It is 1 to 50% by weight, more preferably 1 to 40% by weight, and especially about 5 to 30% by weight.

[Antibacterial Organic Component] In the antibacterial resin of the present invention, as the antibacterial organic component, an organic component composed of at least pyridinecarboxylic acid or a derivative thereof is supported on the antibacterial metal component by a chemical bond. ing. That is, the antibacterial organic component composed of pyridinecarboxylic acid and / or its derivative is supported on the resin (or resin particles) via the antibacterial metal component.

The antibacterial organic component may contain at least pyridinecarboxylic acid or its derivative. Pyridinecarboxylic acids include picolinic acid, nicotinic acid, isonicotinic acid, pyridinedicarboxylic acid, and the like. Examples of the pyridinecarboxylic acid derivative include amides (picolinic acid amide, nicotinic acid amide, isonicotinic acid amide, etc.), halogen-substituted compounds (for example, nicotinyl chloride, 2-chloronicotinic acid, 6-chloronicotinic acid,
2,6-dichloronicotinic acid, 2-chloroisonicotinic acid and the like), halogen-substituted nicotinic acid amide (for example, 6
-Chloronicotinic acid amide, 2,6-dichloronicotinic acid amide, etc.) and the like. Among pyridinecarboxylic acids or their derivatives, nicotinic acid or its derivatives are preferred. Among the above-mentioned pyridinecarboxylic acids and their derivatives, nicotinic acid or nicotinic acid amide (particularly nicotinic acid amide) is preferable from the viewpoints of safety to the environment and human body and antibacterial properties. These pyridinecarboxylic acids or their derivatives may be used alone or in combination of two or more. Note that nicotinic acid and nicotinic acid amide are widely distributed in the animal and plant kingdoms, and are contained in large amounts in the body, beans, and flour. Therefore, conventional antibacterial organic components (2- (4-thiazolyl) benzimidazole, etc.)
Compared with, the use of nicotinic acid and its derivatives is advantageous in reducing the burden on the environment.

The pyridinecarboxylic acid and its derivative may be used in combination with other antibacterial organic components. The antibacterial organic component that can be used in combination with pyridinecarboxylic acid or its derivative is an antibacterial organic component described in JP 2001-40222 A, for example, at least one atom selected from oxygen atom, nitrogen atom and sulfur atom. As long as it is capable of being supported (chemically bound) to the antibacterial metal component, it has various active components (antibacterial or antifungal) having inhibitory activity against the growth of microorganisms, the attachment of organisms, and the growth of organisms. Organic compounds) can be used. In the antibacterial organic component, as the functional group capable of being supported by the antibacterial metal component, various functional groups (at least one selected from oxygen atom, nitrogen atom and sulfur atom) similar to the coordinating unit of the polymer particles are used. A functional group having one atom). Preferred functional groups include a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, and a functional group having a plurality of different kinds of atoms selected from oxygen atom, nitrogen atom and sulfur atom. More specifically, for example, sulfur-containing functional groups (thiol group, thioxo group, thioacetyl group, etc.), oxygen-containing functional groups (carboxyl group, carbonyl group, tropolone ring group, etc.), sulfur- and nitrogen-containing functional groups (thiazolyl group). , Thiazolinyl group, thiadiazolinyl group, isothiazolinyl group, thiocarbamate group, dithiocarbamate group, thiazolone ring group and the like).

Examples of the antibacterial organic compound (organic antibacterial agent containing natural substances) include compounds having a p-aminobenzenesulfonamide skeleton (sulfamethiazole,
Sulfamethoxazole, sulfisomidine, sulfamonomethoxine, etc.), compounds having a pyridonecarboxylic acid skeleton (nalidixic acid, pyromidic acid, pipemidic acid, etc .; new quinolones such as norfloxacin, enoxacin, etc.), compounds having a pyridine skeleton, hiba Examples include oil. The compound having a pyridine skeleton includes, for example, pyridinecarboxylic acid (picolinic acid, isonicotinic acid, etc.) or a derivative thereof, and examples of the pyridinecarboxylic acid derivative include amides (picolinic acid amide,
Amides such as isonicotinic acid amide, halogen-substituted products such as 2-chloroisonicotinic acid), cyanopyridines (2-, 3- or 4-cyanopyridine, 2-chloro-3-cyanopyridine, 6-chloro) Halogen substitution products such as -3-cyanopyridine, 2-chloro-4-cyanopyridine, etc.), aminopyridines (2-, 3- or 4-aminopyridine, 2-chloro-3-aminopyridine, 6-
Examples thereof include halogen-substituted compounds such as chloro-3-aminopyridine and 2-chloro-4-aminopyridine), aldehydes (2-, 3- or 4-aldehydepyridine etc.), alcohols (pyridoxine etc.) and the like.

Examples of the antifungal organic compounds (organic antifungal agents including natural substances) include, for example, thiocarbamate or dithiocarbamate compounds [tolunaphthate, tolcyclate, zalham (tetramethylthiuram disulfide), farbam, etc.], allylamine. Compounds (butenafine, etc.), imidazole compounds [Imidazole compounds having a substituent such as thiazolyl group, thiazolinyl group, thiadiazolinyl group, isothiazolinyl group (for example, benzimidazole having thiazolyl group)
Etc .; clotrimazole, econazole, miconazole, etc.] and triazole compounds (fluconazole, etc.), organic acid compounds [dehydroacetic acid, sorbic acid, propionic acid, aromatic carboxylic acids (benzoic acid, pyridonecarboxylic acid compounds), etc.] , Thiazolone compounds (1,
2-benzisothiazolin-3-one), tropolone-based compounds (hinokitiol, etc.) and the like.

The antibacterial organic component composed of pyridinecarboxylic acid or its derivative may be bonded to the antibacterial metal component through at least one atom selected from oxygen atom, nitrogen atom and sulfur atom. Many. In particular, it seems to coordinate with a metal component to form a bacterium-resistant complex or form a salt with the metal component.

The ratio of pyridinecarboxylic acid or its derivative to other antibacterial organic components is, for example, former / latter (molar ratio) = 100/0 to 50/50, preferably 100/0.
To 70/30, particularly preferably 100/0 to 80/20
You can choose from a range of degrees.

The ratio of the antibacterial organic component composed of at least pyridinecarboxylic acid or its derivative (particularly pyridinecarboxylic acid or its derivative) and the antibacterial metal component (metal conversion) is, for example, the former / the latter = 0. 1 / 1-5
/ 1 (molar ratio), preferably 0.3 / 1 to 3/1 (molar ratio). For example, the ratio of the antibacterial organic component (particularly pyridinecarboxylic acid or its derivative) is 1 mol with respect to 1 mol of the antibacterial metal compound (metal conversion).
The amount is 0.5 to 2.5 mol, preferably 0.5 to 2 mol, and more preferably 0.5 to 1.5 mol. By combining pyridinecarboxylic acid or its derivative with an antibacterial metal component, the antibacterial organic component can exhibit a high antibacterial activity even in the initial stage, and the antibacterial resin has an antibacterial / antifungal action and prevents the adhesion of organisms such as aquatic organisms. The antibacterial metal component can maintain the antibacterial / antifungal activity and the inhibitory activity against the attachment of organisms such as aquatic organisms for a long time while suppressing the elution. In particular, in water such as seawater, even if the elution amount of metal components is extremely small, high antibacterial activity (that is, activity of preventing aquatic organisms from adhering to water or members that come in contact with seawater) can be sustained, resulting in a large load on the environment. It can be reduced. Further, even if the antibacterial activity is lowered, it can be easily regenerated by immersing the antibacterial deactivated resin in an aqueous solution containing the antibacterial metal ion and the antibacterial organic component.

The antibacterial resin is added via the antibacterial metal component.
At least pyridinecarboxylic acid or a derivative thereof (in particular,
Since the antibacterial organic component composed of nicotinic acid amide is supported on the resin, it has a long-lasting antibacterial activity as well as a fast-acting property, and even when the resin is used as a coating agent in the form of polymer particles. It also has good dispersibility in binders and the like. Furthermore, the loading state of the antibacterial metal component on the resin (for example, the loading state by introducing into the resin a plurality of functional groups having different coordination properties to the antibacterial metal component by copolymerization, etc.) Controls the state of carrying organic organic components (eg, the binding ratio between antibacterial organic components and antibacterial metal components), mixes multiple resins with different functional groups, and binds to antibacterial metal components. By mixing a plurality of different antibacterial organic components, the release of the antibacterial components (antibacterial organic component and antibacterial metal component) can be controlled, and a fast-acting or long-acting antibacterial agent can be obtained.
Furthermore, if the degree of hydrophilicity of the resin (for example, hygroscopicity or swelling property of the resin) is also controlled, the release of the antibacterial component can be controlled according to changes in ambient environmental humidity.

A typical antibacterial resin composed of polymer particles, an antibacterial metal component and nicotinic acid amide (antibacterial organic component) can be schematically represented by the following formula.

P-[(X-M- (NA) n] m (In the formula, P represents a polymer particle, and X is a unit containing at least one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom.) , M is an antibacterial metal component, NA is a nicotinic acid amide, n is a coordination number or bond number of NA with respect to M, and m is an integer of 1 or more) [Method for producing antibacterial resin] Antibacterial The resin is the above resin,
It can be prepared by treating with the antibacterial metal component and an antibacterial organic component composed of at least pyridinecarboxylic acid or a derivative thereof and chemically bonding them.

When the resin is the above-mentioned polymer particles, the polymer particles (hydrophilic polymer particles, particularly crosslinked hydrophilic polymer particles) can be prepared by utilizing a conventional method such as pulverization and classification, suspension polymerization, emulsion polymerization and the like. A typical method for preparing crosslinked hydrophilic polymer particles is a precipitation polymerization method, for example, using a polymerization initiator in a non-aqueous solvent (particularly a mixed solvent of water and a hydrophilic solvent) to prepare a coordinating unit. Monomer to
An example is a method of polymerizing a monomer mixture composed of a monomer corresponding to the hydrophilic unit and a crosslinking agent for forming a crosslinked structure. In this method, the particle size of the hydrophilic polymer particles can be controlled by adjusting the type of hydrophilic solvent and the ratio of water to the hydrophilic solvent, and hydrophilic polymer particles having a nano-order particle size can be efficiently produced. Can be made. As the hydrophilic solvent, alcohols such as methanol, ethanol, isopropanol, butanol, ketones such as acetone, dioxane,
Examples include ethers such as tetrahydrofuran, and mixed solvents thereof. The ratio of water to the hydrophilic solvent can be appropriately selected from the range of, for example, the former / the latter = 1/99 to 70/30 (weight ratio), preferably about 3/97 to 50/50 (weight ratio). In this precipitation polymerization method, the size of the produced particles can be controlled without using a dispersion stabilizer, and the particles can be easily washed and collected, and hydrophilic polymer particles can be obtained at low cost.

The crosslinked polymer particles (particularly, the crosslinked hydrophilic polymer particles) can be prepared by adding and mixing a solution of a polymer having a functional group capable of coordinating an antibacterial metal component to a poor solvent to form the polymer particles in a medium. After formation, a method of adding a crosslinking agent to cure, a mixture of a crosslinking agent and a polymer is added to a poor solvent for the polymer to form polymer particles in a medium, and then a method of curing, crosslinking It can also be obtained by a spray drying method or the like in which a mixture of the agent and the polymer is spray dried. The crosslinked polymer particles of the thermosetting resin having self-crosslinking property can be prepared in the same manner as 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 resin, and is introduced into the produced resin by utilizing a polymer reaction or the like. You may. As a method of introducing the functional group into the resin by utilizing a polymer reaction, for example, a conventional method according to a method for preparing a metal ion-adsorptive resin such as a chelate resin can be adopted. For example, a mercapto group and a bipyridyl group are
Ueyama, N, et al. Inorg. Chem. Acta. 89, 19-23
It can be introduced according to the method described in (1984). The imidazole group can be introduced by, for example, reacting a polymer having a chloromethyl group with, for example, histidine.

To carry the antibacterial component on the resin, (i) the resin is added to and mixed with a solution containing the antibacterial metal component, and the antibacterial metal component is supported on the resin by chemical bonding. The antibacterial organic component may be supported on the metal component by adding and mixing to the solution containing the organic component,
(ii) The resin may be loaded with the antibacterial organic component through the antibacterial metal component by adding and mixing the resin to a solution containing the antibacterial metal component and the antibacterial organic component. The obtained antibacterial component-supporting resin may be washed and dried if necessary. When the resin is polymer particles, the above (i) or (i
If necessary, the polymer particles may be swollen with a solvent before the treatment of i).

In the antibacterial resin, since the antibacterial organic component and the resin are chemically bonded via the antibacterial metal component, high antibacterial activity can be exhibited for a long time from the initial stage. Further, when a hydrophilic resin is used as the resin, the resin swells due to water absorption in a high humidity environment or in water where bacteria and microorganisms are easily proliferated, so that not only the antibacterial organic component on the resin surface but also the inside of the resin It is easy to release antibacterial metal components and has environmental responsiveness. In particular, in the case of polymer particles, in the case of fine particles (for example, nano-sized particles), the distance until the antibacterial metal component inside the particle reaches the particle surface is short, and the surface area of the particle is increased. ,
The contact efficiency between the antibacterial metal component and bacteria, microorganisms, or aquatic organisms can be improved. Furthermore, the antibacterial resin of the present invention can stably carry the antibacterial metal component and the antibacterial organic component, and does not discolor even when irradiated with ultraviolet rays or the like.

Moreover, in addition to the organic polymer as the carrier, the surface of the antibacterial resin carries at least a water-soluble antibacterial organic component composed of pyridinecarboxylic acid or its derivative, and High affinity for both hydrophilic and hydrophilic organic polymers. For example, when used as a coating agent, even if the resin is polymer particles, the dispersibility of the antibacterial resin in the binder resin is high and the transparency is high. It is possible to form a high antibacterial coating film. Therefore, the antibacterial resin of the present invention, particularly the antibacterial resin in which the resin is polymer particles, is a binder resin (for example,
It is useful for forming an antibacterial composition in combination with a binder resin used for UV curable paints and water-based paints.

[Antibacterial Composition] The antibacterial composition of the present invention contains at least the above antibacterial resin. The antibacterial composition may be composed of the antibacterial resin alone, but is usually composed of a combination of the antibacterial resin and components such as a carrier and a binder.

The components are not particularly limited as long as they can be mixed with the antibacterial resin by kneading, dispersing or the like, and the antibacterial performance of the antibacterial resin can be exhibited.
Examples include ceramics, carbon, metal, paper and pulp, cement and concrete, soil and sand. These components may be used alone or in combination.

As a method of mixing the antibacterial resin and the above components, as long as the antibacterial performance of the antibacterial resin can be exhibited,
There is no particular limitation, and the antibacterial resin may be dispersed in the heat-melted component, and the antibacterial resin may be dispersed in a solid component such as powder, granules, plates, and fibers, and if necessary, a binder. It may be fixed with, for example. Further, a dispersed antibacterial composition in which an antibacterial resin is solid or dispersed in a liquid may be used. These dispersion methods may be used alone or in combination. The antibacterial composition is usually a coating resin (binder resin) such as paint.
It is used as a coating composition containing, an adhesive composition containing an adhesive resin, a molding composition containing a molding resin used for molding, and the like.

(Composition for Antibacterial Coating) When the antibacterial composition is a composition for coating, when a coating film (coating film) containing an antibacterial resin is formed on the material to be treated, the surface of the material to be treated is high. The antibacterial activity can be effectively maintained for a long period of time.

When an antibacterial resin composed of a non-particulate resin is used, a binder is not always necessary,
When the resin is polymer particles, it is usually used in combination with a binder. As the binder, a thermoplastic resin [olefin resin (polyethylene, polypropylene,
Polyethylene or modified polypropylene modified with carboxyl group, acid anhydride group, epoxy group, etc.), acrylic resin (polymethyl methacrylate, carboxyl group-containing 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 resin (polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl acetate) -Vinyl chloride copolymer, etc.), vinyl alcohol-based polymer (polyvinyl alcohol, ethylene-
Vinyl alcohol copolymer, etc.), vinyl chloride resin (polyvinyl chloride, etc.), polyester resin (polyalkylene terephthalate, polyalkylene naphthalate,
Copolymerized polyester resin, modified polyester resin, etc.), polyurethane resin, polyamide resin, rubber such as chlorinated rubber], thermosetting resin [epoxy resin, phenol resin, urethane resin, unsaturated polyester resin,
Vinyl ester resin, diallyl phthalate resin, silicone resin, amino resin (urea resin, melamine resin, etc.)
Etc.], photocurable resin [photocurable oligomer such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyfunctional (meth) acrylate, photocurable monomer such as nitrogen-containing monomer] Can be exemplified. In addition, natural resins (for example, rosin or its derivatives (rosin ester, rosin-modified resin, etc.), ester-containing natural resins such as lac, styrax, etc.), fats and oils (glycerides such as flaxseed oil)
Alternatively, a derivative thereof (polymerized oil such as polymerized flaxseed oil) may be used in combination. These binder components can be used alone or in combination of two or more.

The binder may be a water-soluble resin or an organic solvent-soluble resin.

Depending on the type of binder, the coating composition can be used as an antibacterial adhesive.

The form of the antibacterial coating composition is a powder coating agent composed of powder or granules, an aqueous coating agent composed of an aqueous solvent as a solvent (water-soluble paint, aqueous dispersion such as emulsion or colloidal dispersion). Type paint, etc.), a solvent type coating agent in which the solvent is composed of an organic solvent (solvent type paint, non-aqueous dispersion type paint such as organosol), a solventless coating agent such as an ultraviolet curable type paint, etc. Good.

When the resin constituting the antibacterial resin is polymer particles, the amount of the antibacterial resin used can be selected from a wide range, for example, 0.01 to 200 per 100 parts by weight of the binder resin in terms of solid content. Parts by weight, preferably 0.1
To 100 parts by weight, more preferably 0.5 to 50 parts by weight. When the resin constituting the antibacterial resin is non-particulate, the amount of the antibacterial resin to be used can be selected according to the usage pattern of the antibacterial resin. It can be selected from the same range, and when used as a binder resin, it can be selected from the range capable of forming a film.

The antibacterial coating composition may contain an antifouling agent (for example, cuprous oxide, organotin compounds, thiocarbamates, etc.). Further, a compound used as an elution promoter (eg, rosin, copper naphthenate, linseed oil fatty acid copper, dibasic acid, etc.) may be used in combination. Furthermore, the antibacterial coating composition has various additives such as stabilizers (antioxidants, UV absorbers,
(Including heat stabilizers), plasticizers, antistatic agents, flame retardants, dispersants, surfactants, fillers, colorants, viscosity modifiers, preservatives, antifungal agents, leveling agents, etc. Good. Furthermore, when the resin constituting the antibacterial resin is based on a non-particulate non-crosslinking resin, or when the resin constituting the antibacterial resin is polymer particles and the non-crosslinking resin is used as a binder component, a crosslinking agent May be combined with a thermosetting paint to form a thermosetting paint.

The antibacterial coating composition can be prepared by mixing the antibacterial resin with a binder resin, a solvent, an additive, etc., if necessary. For the preparation of the antibacterial coating composition, a conventional device such as a disperser,
A mixer can be used.

The coating film can be formed by applying the coating material to a base material by a conventional coating method and drying (heat curing if necessary) or light irradiation (ultraviolet irradiation etc.).

The thickness of the coating film (antibacterial layer) can be selected according to the application and the type of material to be treated, and is, for example, 1 to 500 μm.
m, preferably from 5 to 300 μm.

As the substrate, paper, wood, plastic,
Ceramics including glass and metals can be used.

When the antibacterial resin is used in the paint or coating agent, the antibacterial agent can be dispersed uniformly and easily with high dispersion stability, and sedimentation and the like can be prevented. Further, even a small amount of antibacterial agent can effectively exhibit the activity of the antibacterial agent. Furthermore, since the affinity and adhesion with the binder are high, it is possible to form a coating film that is uniform and has high mechanical strength and high transparency.

When a coating film (coating film) containing an antibacterial resin is formed on a material to be treated using the composition for antibacterial coating, high antibacterial activity is effectively maintained on the surface of the material to be treated for a long period of time. it can.

(Antibacterial Molding Composition) In the antibacterial molding composition, a composition to which an antibacterial resin is added is
There is no particular limitation as long as mixing (kneading, dispersion, etc.) and molding are possible, and examples include components that can be mixed with the antibacterial resin.

Of the above-mentioned components (carriers, binders, etc.) that can be mixed with the antibacterial resin, in the case of resin, an antibacterial thermoplastic resin may be used alone as the molding resin. It may be used in combination with an antibacterial thermoplastic resin or the like.

When the antibacterial resin of the present invention is used in combination with the above components, the ratio of the antibacterial resin to the non-antibacterial thermoplastic resin can be selected according to the types of other components. For example, when the antibacterial resin of the present invention and a non-antibacterial thermoplastic resin are used in combination, the ratio of the antibacterial resin and the non-antibacterial thermoplastic resin is the former / the latter (weight ratio) =
100/0 to 50/50, preferably 100/0 to 70
/ 30, particularly preferably from 100/0 to 90/10.

For molding, a conventional molding method (injection molding, extrusion molding, etc.) can be used, and for molding, a conventional molding machine (injection molding machine, extrusion molding machine, press molding machine, transfer molding machine, etc.) is used. it can.

The form of the molded product using the molding composition is not particularly limited, and may be one-dimensional form such as fiber, two-dimensional form such as film or sheet, and three-dimensional form such as machine part. Good.

When the antibacterial resin of the present invention is applied to a material to be treated in the form of a coating composition or a molding composition,
While suppressing the load on the environment, high antibacterial activity can be effectively maintained for a long period of time in the material to be treated or on the surface of the untreated material. In particular, the inhibitory activity against the growth of microorganisms or the attachment or growth of organisms such as aquatic organisms is maintained for a long period of time while suppressing the elution of active ingredients such as metal components. In particular, the present invention relates to various aquatic adherent organisms, for example, shellfish (barnacles, mussels, mussels, etc.), polychaetes (eg, Haemonoptera, etc.), mosquitoes (such as hemlockworms), ascidians, hydroids, algae. It is possible to effectively prevent or suppress the adherence of slime or the like (blue seaweeds, seaweeds), slime generated due to bacteria and the like to the material to be treated.

As the material to be treated, various structures and equipment,
Building materials, equipment, household materials, household products, etc. can be mentioned. In particular, various members that come into contact with water or seawater, for example, hulls such as ship bottoms, floating bodies such as buoys, supports or submerged portions in structures such as bridges, jetties, jetty, cooling pipes, water intake pipes, etc. In the case of forming members, stationary nets, ropes, etc., it is effective to prevent aquatic organisms from adhering to these members.

[0093]

INDUSTRIAL APPLICABILITY In the present invention, since the antibacterial organic component is composed of at least pyridinecarboxylic acid or its derivative in combination with the antibacterial metal component, the antibacterial property against various microorganisms and organisms is effective and long-lasting. It can be maintained for a long period of time, has high antibacterial properties, and can significantly reduce the load on the environment. Further, it is highly safe and there is no risk of environmental pollution.

[0094]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

Example 1 In a mixed solvent of 86 ml of ethanol and 6 ml of distilled water,
Acrylamide 4 g, methylenebisacrylamide 2.
4 g, 4-vinylpyridine 1.6 g, and azobisisobutyronitrile 0.05 g were dissolved, and the polymerization was carried out at a temperature of 60 ° C. for 17 hours in an argon stream. The produced fine particles were washed with 300 ml of distilled water by centrifugation to obtain polymer particles.

The obtained polymer particles were mixed with copper (II) sulfate.
160m of dimethylformamide containing 7.6g of pentahydrate
1 was ultrasonically dispersed and then stirred at room temperature for 3 hours, 300 ml of dimethylformamide containing 7.4 g of nicotinic acid amide was further added, and the mixture was stirred at room temperature for 4 hours to obtain fine particles. Next, the obtained fine particles were sequentially washed and filtered with 200 ml of distilled water and 100 ml of methanol and dried under reduced pressure to carry copper ions and nicotinic acid amide to obtain antibacterial polymer particles. When the copper ion content in the polymer particles was measured by thermal analysis, it was 10% by weight. The average particle size of the obtained polymer particles (AB-3NA) was measured by a laser diffraction / scattering method and found to be 91 nm.

[Evaluation of Adhesion Inhibitory Activity of Polymer Particles] The adhesion inhibitory activity of the antibacterial polymer particles prepared in the Examples was
An evaluation system using juveniles (hereinafter referred to as juveniles evaluation system) evaluated as follows.

(1) Specimen Antibacterial polymer particles obtained in Example 1 and two types of commercial cuprous oxide antifouling paints (commercial paint A and commercial paint B) The content of the active ingredient (including cuprous oxide) in the paint seems to be about 30 to 50% by weight.

(2) Preparation of sample mixed solution containing antibacterial polymer particles In order to immobilize the antibacterial polymer particles, butyral resin (“S-REC BL-2”, Sekisui Chemical Co., Ltd.) was used as a mixed solvent (toluene). : Methanol = 1: 1 (weight ratio)) to prepare a binder resin solution having a concentration of 15% by weight. The antibacterial polymer particles were added to the binder resin solution at a predetermined concentration, stirred and mixed to prepare a sample mixed solution.

(3) Preparation of test piece A sample mixture was filtered with a filter paper (“ADVANTEC No. 26”: size 35 m).
m × 35 mm), dried sufficiently, and then overcoated. For commercially available cuprous oxide antifouling paints,
A test piece was prepared by double-coating the cuprous oxide antifouling paint on the filter paper without mixing with the binder resin solution.

(4) Measurement of adhesion-inhibiting activity Disposable weighing dish (made by polystyrene Inei Seieidou:
A test piece was placed in the center of a size 80 mm × 80 mm × 25 mm), 60 ml of seawater was put therein, and 9 mussels juveniles were evenly arranged (length 3 × width 3) on the test piece. After leaving still for 1 hour and 30 minutes, the container was shaken manually, and the number of shells attached to the test piece and the container was counted. In the primary screening, the above test was performed 10 times (90 animals in total).

As a result, a test piece using the mixed solution containing the polymer particles of Example 1 (concentration of solid content: 20% by weight),
The number of individuals (90 animals / 90 animals) attached to the test pieces using the commercially available paints A and B was 0 respectively. Further, when a test piece using a mixed solution containing the polymer particles of Example 1 in a concentration of 5% by weight and 1% by weight in terms of solid content was also examined,
The number of individuals (90/90) attached to the test piece was 0 in each case. In this way, even if the concentration is 5% by weight or 1% by weight, it shows a high adhesion inhibitory activity. Therefore, with a small addition amount, the adhesion of juvenile shellfish is similar to that of the commercially available cuprous oxide antifouling paint (concentration 30 to 50% by weight). It was confirmed to have inhibitory activity.

[Copper elution test in seawater] Using the antibacterial polymer particles prepared in Example 1 and two commercially available cuprous oxide antifouling paints, the elution amount of copper was evaluated as follows. .

That is, the antibacterial polymer particles were contained at a predetermined concentration in an amount of 15% by weight of the binder resin solution (butyral resin (“S-REC BL-2”, Sekisui Chemical Co., Ltd.)).
Solution) and stirred and mixed with a paint shaker to prepare a sample mixed solution. Base the sample mixture on a bar coater (white polyvinyl chloride plate: size 100 mm x
70 mm, after roughening the surface with sandpaper, it was washed with xylene and dried), sufficiently dried, and then overcoated. Regarding the commercially available cuprous oxide antifouling paint, a test piece was prepared by double coating the cuprous oxide antifouling paint on the above base material without mixing with the binder resin solution.

Then, a beaker containing artificial seawater is placed in a constant temperature bath at a water temperature of 20 ° C., the test piece is immersed in artificial seawater at a water temperature of 20 ° C., and while bubbling with an air bubbler, 2
A time dissolution test was performed. The amount of copper eluted is JIS K 0102
52.4 Analysis was performed according to the ICP-AES analysis method. The results are shown in Table 1.

[0106]

[Table 1]

For the antibacterial polymer particles, the elution of copper was below the detection limit of the analysis. From this, it was confirmed that the use of the antibacterial polymer particles has a low elution property and a high durability.

[Seawater Immersion Test] (1) Preparation of Test Film For antibacterial polymer particles, a sample mixture (concentration of antibacterial polymer particles in solid content: 1% by weight) was used in the same manner as the copper elution test in seawater. %, 5% by weight, 10% by weight) and applied on a polyvinyl chloride film with a bar coater to a thickness of about 50 μm after drying, and then immersed in seawater for 1 year. The state of adhesion of marine organisms was visually observed. As a result, almost no adhesion of marine organisms was observed in any of the test films.

Example 2 In a mixed solvent of 86 ml of ethanol and 6 ml of distilled water,
Acrylamide 4g, Methylenebisacrylamide 2
g, acrylic acid 2.1 ml, methyl methacrylate 5.0
8 ml, 2.2 ml of divinylbenzene having a concentration of 55% by weight and 0.1 g of azobisisobutyronitrile were dissolved,
Polymerization was carried out at a temperature of 60 ° C. for 17 hours under an argon stream.
The produced fine particles were washed with 300 ml of distilled water by centrifugation to obtain polymer particles.

The obtained polymer particles were mixed with copper (II) sulfate.
160m of dimethylformamide containing 7.6g of pentahydrate
1 was ultrasonically decomposed, and then stirred at room temperature for 3 hours, 300 ml of dimethylformamide containing 7.4 g of nicotinic acid amide was further added, and stirred at room temperature for 4 hours to obtain fine particles. Then, the obtained fine particles were washed successively with 200 ml of distilled water and 100 ml of methanol, filtered, and dried under reduced pressure to carry copper ions and nicotinic acid amide to obtain antibacterial polymer particles (NA-1). When the content of copper ions in the antibacterial polymer particles (NA-1) was measured by thermal analysis, it was 10% by weight. The average particle diameter of the obtained antibacterial polymer particles was measured by a laser diffraction / scattering method and found to be 91 nm.

In order to immobilize the obtained antibacterial polymer particles, the antibacterial polymer particles were added to the binder resin solution at a concentration of 7.5% by weight to form alumina beads (3 mm).
Diameter) and mixed with a paint shaker for 1 hour to prepare a sample mixed solution. As the binder resin solution, butyral resin (“S-REC BL-2”,
A binder resin solution having a concentration of 15% by weight, in which Sekisui Chemical Co., Ltd.) was dissolved in a mixed solvent (toluene: methanol = 1: 1 (weight ratio)) was used.

The sample mixture thus obtained was applied onto an iron plate which had been pre-coated, to form a dry coating film having a thickness of about 150 μm to prepare sample plate A-1. Sample plate A-1
When was dipped in a test tank for 1 month, the number of attached barnacles after 1 month was 2. In addition, the number of adhering Kanzashigokai was one. In addition, the seawater of the sea area near the Osaka Gas Co., Ltd. Senboku No. 2 factory in Takaishi-shi, Osaka Prefecture was circulated and supplied to the test tank from the water pipe as test seawater.

Comparative Example 1 Antibacterial polymer particles (AB-3) were used in the same manner as in Example 2 except that 6 g of 2- (4-thiazolyl) benzimidazole (TBZ) was used instead of 7.4 g of nicotinic acid amide.
Was synthesized. Furthermore, a sample mixture was prepared using this polymer resin, a sample plate was prepared, and subjected to an immersion test. The number of barnacles attached to the test plate one month after immersion was 10. In addition, the number of adherent Kanzashigokai was 38.

Comparative Example 2 When an iron plate coated only with the undercoat was subjected to the same immersion test as in Example 2, the number of barnacles attached to the iron plate after one month of immersion was 237. In addition, a myriad of mosquitoes were attached.

[Seawater immersion test 2] Antibacterial polymer particles [(AB-3) or (NA-1)], and antibacterial polymer particle mixture [antibacterial polymer particles (AB-3):
Antibacterial polymer particles (NA-1) = 1: 1 mixture (weight ratio)], using a binder resin, a test liquid mixture (concentration of antibacterial polymer particles in solid content 1% by weight, 3% by weight,
5% by weight, 7.5% by weight and 12% by weight) were produced. After applying an undercoat paint on a test piece made of vinyl chloride (width 3 mm, length 300 mm, height 100 mm), the test mixture solution was brush-painted. For comparison, a test piece coated with only the undercoat paint and a commercially available cuprous oxide antifouling paint (commercial paint A and commercial paint B) were applied as they were without undercoating. Seawater is introduced from the sea into the test tank through a pipe equipped with a pump, the test piece is hung in the test tank, and the adhesion status of shellfish (mussel and barnacle) is checked approximately once a month for one year. The subsequent adhesion state was evaluated. The test pieces coated with the undercoat paint were arranged in the uppermost stream, and the test pieces coated with the commercial paint A and the commercial paint B were arranged in the lowermost stream. Normally, the test tank was left with the lid on. The evaluation of the state of attachment of shellfish was quantified by counting the number of attachments of mussels and barnacles. Table 2 shows the evaluation results after one year.

[0116]

[Table 2]

As is clear from Table 2, the antibacterial polymer particles (NA-1) and the antibacterial polymer particle mixture exhibited a high adhesion inhibitory activity at a concentration of 7.5% by weight, which was as high as that of a commercial product. With a small amount of addition, the same effect as the commercial product was obtained. Further, since the content of the active ingredient of the antibacterial polymer particles (NA-1) is a value including the polymer component,
The copper content is about 1/10 of the active ingredient content. Therefore, the load on the environment can be significantly reduced as compared with the commercially available product.
Since the antibacterial polymer particles (NA-1) are nano-order particles supporting an antibacterial metal component or an antibacterial organic component at the molecular level, they have high inhibitory activity and high durability even with a small amount of active ingredient. Conceivable.

[Seawater immersion test 3] Antibacterial polymer particles [(AB-3) or (NA-1)], and antibacterial polymer particle mixture [antibacterial polymer particles (AB-3):
For the antibacterial polymer particles (NA-1) = 1: 1 mixture (weight ratio)], a binder resin was used to prepare a test mixture liquid (concentration of antibacterial polymer particles in solid content of 7.5% by weight). The undercoat paint was applied to the inner surface of the test pipe (200 mm × 0.5 m), and then the test mixture was applied with a brush. Further, as a comparison, a sample coated with only the undercoat paint and a commercially available cuprous oxide antifouling paint (commercial paint A and commercial paint B) were applied as they were without undercoating to prepare a test pipe. Seawater was introduced by a pump into a test pipe coated with paint on the inner surface, and the condition of shellfish adhesion to the inner wall was examined about once a month, and the condition of adhesion one year later was evaluated as follows. . The flow rate of seawater is about 0.5.
It was set to m / sec. The adhesion state was evaluated by visually observing the state of mussel and barnacle attachment.
Table 3 shows the evaluation results after one year has passed.

[0119]

[Table 3]

As is clear from Table 3, the antibacterial polymer particles (NA-1) and the antibacterial polymer particle mixture at the concentration of 7.5% by weight exhibited the same adhesion inhibition effect as the commercially available product.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) A01N 59/00 A01N 59/00 59/16 59/16 59/20 59/20 61/00 61/00 D C09D 5/14 C09D 5/14 7/12 7/12 201/00 201/00 E02B 1/00 301 E02B 1/00 301B (72) Inventor Masahiro Yamada 4-1-2, Hiranocho, Chuo-ku, Osaka F-terms in Gas Co., Ltd. (reference) 2B106 AA06 HA16 HC00 2B121 AA06 AA20 CA02 CA52 CC21 EA01 EA21 FA01 FA07 FA09 FA13 FA16 4H011 AA02 BA04 BB10 BB18 BC19 DA02 DA07 DD01 DH02 DH21 DH22 4J031 BA04 BA05 BA16 BA12 BA07 BA07 BA07 BA07 BA07 BA07 BA07 BA07 BA12 BC19 BD05 BD12 BD17 BD19 BD30 CD24 CD25 CD26 CD28 4J038 CE071 CG172 EA011 EA012 GA06 GA08 GA13 HA066 HA436 JB29 KA02 NA02

Claims (8)

[Claims] 1. An antibacterial metal component composed of a metal ion or a metal compound is supported by being chemically bonded to a resin, and the antibacterial organic component is chemically bonded to the antibacterial metal component. And an antibacterial resin carried by the antibacterial organic component, wherein the antibacterial organic component is composed of at least pyridinecarboxylic acid or a derivative thereof. 2. A resin comprises a unit containing at least one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom and having a functional group capable of chemically bonding to an antibacterial metal component, and a crosslink. And an antibacterial metal component is at least one selected from the group consisting of silver, platinum, copper, zinc, nickel, cobalt, molybdenum, chromium, silicon, and iron. The antibacterial resin according to claim 1, which is composed of a metal component. 3. A polymer particle having a crosslinked structure, which contains a hydrophilic unit and at least one functional group selected from a carboxyl group, a pyridyl group, a mercapto group, a thiocarbamate group and a dithiocarbamate group, and an antibacterial metal. The antibacterial resin according to claim 2, which is composed of a hydrophilic polymer gel including a unit having a functional group capable of chemically bonding to a component and a cross-linking unit. 4. The ratio of pyridinecarboxylic acid or its derivative and antibacterial metal component (metal conversion) is the former / the latter =
The antibacterial resin according to claim 1, which is 0.1 / 1 to 5/1 (molar ratio). 5. An oxygen-containing functional group, a nitrogen-containing functional group, or a sulfur-containing functional group, and having an average particle size of 5 nm to 30 μm.
Polymer particles, an antibacterial metal component supported by being chemically bonded to the functional groups of the polymer particles and selected from silver or copper, and a nicotinic acid amide supported on the antibacterial metal component. The antibacterial resin according to claim 1, which is constituted. 6. A resin capable of chemically bonding to a metal component, an antibacterial metal component composed of a metal ion or a metal compound, and an antibacterial organic component composed of at least pyridinecarboxylic acid or a derivative thereof. The method for producing an antibacterial resin according to claim 1, wherein the treatment is carried out by 7. An antibacterial composition containing the antibacterial resin according to claim 1. 8. A method of applying the antibacterial resin according to claim 1 to a material to be treated to prevent adhesion of aquatic organisms to the material to be treated.