JPH0761927B2 - Antibacterial agent - Google Patents

Description

TECHNICAL FIELD The present invention relates to an antibacterial agent, and more particularly to an antibacterial agent suitable for imparting antibacterial activity to paints and the like having excellent dispersibility.

[Conventional technology]

Conventionally, paints having antibacterial activity have been known. For example, there are paints containing organic tin (JP-A-59-140271), paints containing metal powder (JP-A-59-135267) and paints containing antibacterial zeolite (JP-A-60-202162). Are known.

Among them, the coating containing the above-mentioned antibacterial zeolite is excellent in that the antibacterial activity can be maintained for a long time even if it is left in water or air.

[Problems to be Solved by the Invention]

However, if the antibacterial zeolite is contained in a paint or the like having a strong cohesive force in the coating film, the dispersibility is poor, and the formed coating film may have insufficient antibacterial activity to prevent the growth of bacteria and mold. For example, when the antibacterial zeolite is sufficiently mixed with a coating material and applied to a metal or the like, the antibacterial zeolite particles may aggregate with each other, resulting in poor dispersibility.

Therefore, an object of the present invention is to provide an antibacterial aluminosilicate that can be uniformly dispersed in a coating composition having a strong cohesive force of a coating film without aggregating, and as a result can provide a resin composition having a high antibacterial activity. To provide.

[Means for Solving the Problems]

The present invention relates to an antibacterial agent obtained by treating an antibacterial aluminosilicate with a coupling agent, and a coating composition and an adhesive containing the antibacterial agent.

The present invention will be described below.

In the present invention, the antibacterial aluminosilicate includes antibacterial zeolite and antibacterial amorphous aluminosilicate. As the antibacterial zeolite, for example, JP-A-59-133235,
No. 60-180023, No. 59-37956 and Japanese Patent Application No. 60-290144 are all restricted to zeolites in which the ion-exchangeable ions in the zeolite are replaced with antibacterial metal ions and / or ammonium ions. Can be used without. or,
Examples of the antibacterial amorphous aluminosilicate include those disclosed in
An amorphous aluminosilicate obtained by substituting an ion-exchangeable ion in the amorphous aluminosilicate described in No. 61-174111 with an antibacterial metal ion and / or an ammonium ion can be used.

In the present invention, for example, an ion-exchangeable ion in zeolite, such as sodium ion, calcium ion, potassium ion, magnesium ion, antibacterial metal ion and ammonium ion partially or wholly replaced with antibacterial metal ion and ammonium ion Zeolites can be used.

Here, as the zeolite, both natural zeolite and synthetic zeolite can be used. Zeolites is generally an aluminosilicate having a three dimensional framework structure, represented by _{XM 2 / n O · Al 2} O 3 · YSiO 2 · ZH 2 O as a general formula. Where M
Represents an ion-exchangeable ion and is usually a monovalent or divalent metal ion. n is the valence of the (metal) ion. X and Y are each metal oxide, silica coefficient,
Z represents the number of crystal waters. Specific examples of the zeolite include A-type zeolite, X-type zeolite, and Y.
-Type zeolite, T-type zeolite, high silica zeolite, sodalite, mordenite, analcime, talinoptilolite, chabazite, erionite and the like can be mentioned. However, it is not limited to these. The ion exchange capacity of these exemplified zeolites is A-type zeolite 7meq / g, X-type zeolite 6.4meq / g, Y-type zeolite 5meq / g, T-type zeolite 3.4meq / g, sodalite 11.5meq / g, Mordenite 2.6 meq / g, Anal Sime 5 meq / g, Clinoptilolite 2.6 meq / g, Chabasite
It is 5 meq / g and erionite 3.8 meq / g, both of which have sufficient capacity for ion exchange with ammonium ions and silver ions. Examples of antibacterial metal ions include silver,
Mention may be made of copper, zinc, mercury, lead, bismuth, cadmium, chromium or thallium ions, preferably silver, copper or zinc ions.

From the viewpoint of antibacterial property, it is suitable that the antibacterial metal ion is contained in the zeolite in an amount of 0.1 to 15%. An antibacterial zeolite containing 0.1 to 15% of silver ion and 0.1 to 8% of copper ion or zinc ion is more preferable. Further, in addition to the antibacterial metal ions, ammonium ions, alkaline earth metals, manganese, amines, and thiosulfate ions which form complex ions with silver ions can be contained in the zeolite. Ammonium ions are 20
%, The content of ammonium ion in the zeolite is 0.5 to 5%, preferably 0.5
It is suitable to be 2% from the viewpoint of effectively preventing discoloration of the resin containing the zeolite.

The amine ions include primary amine (RNH ₂ ) ion, secondary amine (R ₂ NH) ion, and tertiary amine (R ₃ NH 3) ion.
N) ions and quaternary ammonium (R ₄ N ⁺ ) ions. In addition, R represents a hydrocarbon group, and as the hydrocarbon group, an aliphatic hydrocarbon group [a linear or branched alkyl group (for example, having 1 to 16 carbon atoms, preferably 1 to 11 carbon atoms, more preferably 1 to 5 carbon atoms) is used. An alkyl group), the alkyl group may have a substituent (for example, a carboxyl group, a hydroxyl group, etc.), an unsaturated aliphatic group, an alicyclic group (for example, a carbon number of 3 to 3).
6 cycloalkyl group)] and an aromatic hydrocarbon group which may have a substituent. R ₂ NH, R ₃ N, R ₄ N
Each R in ⁺ may be the same or different. Specific examples of amines include aliphatic primary amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, cetylamine; dimethylamine, diethylamine, dipropylamine, diisopropyl. Aliphatic secondary amines such as amines, dibutylamine and diamylamine; aliphatic tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine and triamylamine; aliphatic unsaturated amines such as allylamine, diallylamine and triallylamine;
Alicyclic amines such as cyclopropylamine, cyclobutylamine, cyclopentylamine and cyclohexylamine; aromatic amines such as aniline, methylaniline, ethylaniline, diethylaniline, toluidine, benzylamine, diphenylamine and naphthylamine can be mentioned.

Amine ions can be contained in the zeolite up to 20%, but the content is 0.5 to 15%, preferably 0.5.
It is suitable that the content of -5% is from the viewpoint of effectively preventing discoloration of the resin containing the zeolite.

Examples of compounds that form complex ions with silver ions (hereinafter referred to as complex-forming compounds) include thiosulfate compounds, thiocyanate compounds, cyan compounds, fluorophosphoric acid compounds, fluorosilicic acid compounds, fluoroboric acid compounds, ammonia and pyridine. can do. Specifically, the thiosulfate compound is sodium thiosulfate, barium thiosulfate, and the thiocyanate compound is calcium thiocyanate, sodium thiocyanate, barium thiocyanate;
Examples of cyanide compounds include potassium cyanate, sodium cyanate, and sodium hexafluorophosphate for fluorophosphate compounds; sodium hexafluorosilicate for fluorosilicate compounds; sodium tetrafluoroborate for fluoroborate compounds. Can be mentioned. The silver complex ions formed from the complex-forming compound and silver ions include [Ag (S ₂ O ₃ ) ₂ ] ³⁻ and [Ag (SC
N) ₂ ] ⁻ , [Ag (CN ₂ ] ⁻ , Ag [PF ₆ ] ⁺ , Ag [B
F ₄ ] ⁺ , Ag [SiF ₆ ] ⁺ , [Ag (NH ₃ ) ₂ ] ⁺ , [Ag (C ₅ H
₅ N) ₄ ] ^{+ and the} like.

The complexing compound is 0.1 to 5% in the zeolite, preferably
The content of 0.3 to 3% is suitable from the viewpoint of preventing discoloration of the resin containing the zeolite.

In the present specification,% means 110% by weight on a dry basis.
Say.

The method for producing the antibacterial zeolite will be described below.

The antibacterial zeolite used in the present invention is prepared by contacting the zeolite with a mixed aqueous solution containing antibacterial metal ions such as ammonium ions and silver ions, copper ions, zinc ions, etc., which have been prepared in advance, and ion exchangeable ions in the zeolite. And the above ions are replaced. The contact can be performed at 10 to 70 ° C., preferably 40 to 60 ° C. for 3 to 24 hours, preferably 10 to 24 hours by a batch system or a continuous system (for example, a column method). The pH of the mixed aqueous solution is appropriately adjusted to 3 to 10, preferably 5 to 7. By this adjustment, it is possible to prevent precipitation of silver oxide or the like on the zeolite surface or in the pores, which is preferable. Further, each ion in the mixed aqueous solution is usually supplied as a salt. For example, ammonium ion is ammonium nitrate, ammonium nitrate, ammonium acetate, ammonium perchlorate, ammonium thiosulfate, ammonium phosphate, etc.
Copper ions such as silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, and diammine silver sulfate are copper nitrate (I
I), copper perchlorate, copper acetate, potassium tetracyanocuprate, copper sulfate, etc., zinc ions are zinc (II) nitrate, zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate, etc. Mercury chlorate, mercury nitrate, mercury acetate, etc., tin ion is tin sulfate, etc., lead ion is lead sulfate, lead nitrate, etc.
Bismuth ions include bismuth chloride, bismuth iodide, etc.
Cadmium ions are cadmium perchlorate, cadmium sulfate, cadmium nitrate, cadmium acetate, etc.Chromium ions are chromium perchlorate, chromium sulfate, ammonium sulfate chromium, chromium nitrate, etc.Thallium ions are thallium perchlorate, thallium sulfate, Thallium nitrate, thallium acetate, etc. can be used.

The content of ammonium ions and the like in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed aqueous solution. For example, when the antibacterial zeolite contains ammonium ion and silver ion,
The ammonium ion concentration in the mixed aqueous solution is 0.2 M /
〜2.5M / silver ion concentration 0.002M / 〜0.15M /
%, Antibacterial zeolite having a silver ion content of 0.1 to 5% can be obtained. Further, when the antibacterial zeolite further contains copper ions, zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1 M / to 0.85 M /, and the zinc ion concentration is 0.1.
By setting the content to 5 M / to 1.2 M /, an antibacterial zeolite having a copper ion content of 0.1 to 8% and a zinc ion content of 0.1 to 8% can be obtained.

Ion exchange can also be carried out by using an aqueous solution containing each ion alone in addition to the mixed aqueous solution as described above and sequentially bringing each aqueous solution into contact with zeolite. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.

The zeolite after the ion exchange is thoroughly washed with water and then dried. Drying is preferably performed at 105 ° C. to 115 ° C. under normal pressure or 70 ° C. to 90 ° C. under reduced pressure (1 to 30 Torr).

Ion exchange of ions or organic ions without a suitable water-soluble salt such as tin or bismuth can be carried out by using a solution of an organic solvent such as alcohol or acetone so that a sparingly soluble basic salt is not deposited.

In the present invention, an antibacterial amorphous aluminosilicate obtained by substituting a part or all of the ion-exchangeable ions in the amorphous aluminosilicate with an antibacterial metal ion (hereinafter referred to as AAS) is used as the antibacterial aluminosilicate. be able to. The AAS (amorphous aluminosilicate) used as a raw material here is not particularly limited, and those conventionally known can be used as they are. AAS is generally of the formula xM ₂
Appear in _{O · Al 2 O 3 · ySiO} 2 · zH 2 O, where M is typically an alkali metal element (such as sodium, potassium, etc.). X, y, and z are metal oxide, silica,
The molar ratio of crystal water is shown. Unlike crystalline aluminosilicates, which are called zeolites, AAS is an amorphous substance that does not show a diffraction pattern in X-ray diffraction analysis, and the synthesis process produces extremely fine zeolite crystals of several tens of amperes. However, it is considered to have a structure in which an amorphous substance in which SiO ₂ , Al ₂ O ₃ , M ₂ O, etc. are complicatedly combined adheres to the surface. AAS
In general, is produced by reacting an aluminum salt solution, a silicon compound solution and an alkali metal salt solution at a predetermined concentration in a low temperature range of 60 ° C. or lower, and washing with water before crystallization proceeds. As a manufacturing method, for example, Japanese Examined Patent Publication No. 52-58099,
There is a method described in JP-A-55-162418.

AAS obtained by the above method has an alkali metal oxide of 10
% Or more is included. The AAS can be used as it is for the production of antibacterial AAS, but the M ₂ O content of 10% or less, preferably 8% or less is a discoloration with time of the resin or the like when added to the resin or the like. Is particularly preferable from the viewpoint of effectively preventing However, it is not limited to this range.

Furthermore, the AAS is ion-exchanged with antibacterial metal ions. Examples of antibacterial metal ions may include silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium or thallium ions, preferably silver, copper or zinc ions.

Of the antibacterial metal, the amount of silver added is 0.1 to 50%, preferably
0.5 to 5% is appropriate from the viewpoint of exhibiting excellent antibacterial properties. In addition, copper, zinc, mercury, tin, lead,
It is preferable to contain 0.1 to 10% of one or more metals selected from bismuth, cadmium, chromium and thallium.

Further, the antibacterial AAS may contain ammonium ions, alkaline earth metals, manganese, amines, and thiosulfate ions forming complex ions with silver ions by ion exchange in addition to the above antibacterial metals. Ammonium ions can be contained in AAS up to 15%, but the content of ammonium ions in AAS is 0.5 to 5%.
And preferably 0.5-2% from the viewpoint of effectively preventing discoloration of the AAS.

The antibacterial AAS can be produced, for example, by the following methods (1) and (2).

(1) Amorphous aluminosilicate having a content of M ₂ O (M is an alkali metal) of preferably 10% or less is brought into contact with an antibacterial metal ion to allow ion exchange in the amorphous aluminosilicate. The antibacterial AAS can be produced by exchanging the ions with the antibacterial metal ions.

(2) The pH of the amorphous aluminosilicate slurry is preferably adjusted to 6 or less, and then the amorphous aluminosilicate in the slurry and the antibacterial metal ion are brought into contact with each other to perform ion exchange in the amorphous aluminosilicate. An antibacterial AAS can be produced by exchanging possible ions with antibacterial ions.

Amorphous aluminosilicate (AAS) in the method of (1)
The M ₂ O content is preferably 10% or less. AAS obtained in the usual way contains more than 10% M ₂ O. Therefore, the AAS obtained by the above-mentioned method is suspended in, for example, water, and then an aqueous acid solution is added dropwise to the obtained slurry while stirring to obtain the alkali metal and / or
Alternatively, the M ₂ O content can be adjusted to 10% or less by neutralizing the alkaline earth metal. 0 as an aqueous acid solution.
It is preferable to use a dilute aqueous solution having a concentration of 1 N or less and to perform the dropping at a rate of 100 ml / 30 minutes or less, which may vary depending on the stirring conditions and the reaction scale. Furthermore, the pH of the slurry is 3 for neutralization.
It is preferable to be in the range of -6, preferably 4-5.
Examples of the acid that can be used for neutralization include inorganic acids such as nitric acid, sulfuric acid, perchloric acid, phosphoric acid and hydrochloric acid, and organic acids such as formic acid, acetic acid, oxalic acid and citric acid.

The neutralized AAS having an M ₂ O content of 10% or less can be filtered, washed with water and used as a slurry as it is in the method (1), or can be dried to have an M ₂ O content of 10%. A below
It may be AS.

In the method (1), preferably, a slurry of AAS having an M ₂ O content of 10% or less is mixed with an antibacterial metal ion-containing aqueous solution to contain antibacterial metal ions such as silver ions, copper ions and zinc ions. AAS is brought into contact with the mixed aqueous solution to replace the ion exchangeable ions in AAS with the above ions. The contact can be performed at 5 to 70 ° C, preferably 40 to 60 ° C for 1 to 24 hours, preferably 10 to 24 hours by a patch system or a continuous system (for example, a column method).

Each of the ions in the mixed aqueous solution is usually supplied as a salt. The salt used may be the same as the salt that can be used in the production of the antibacterial zeolite.

The content of ammonium ions and the like in AAS can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed aqueous solution. For example, when the antibacterial AAS contains silver ions, the silver ion concentration in the mixed aqueous solution is set to 0.
By setting the amount to 01 M / to 0.30 M /, an antibacterial AAS having a silver ion content of 0.5 to 6% can be appropriately obtained. When the antibacterial AAS further contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.05 M / to 0.4 M.
By setting the zinc ion concentration to 0.05 M / to 0.4 M /, an antibacterial AAS having a copper ion content of 1 to 8% and a zinc ion content of 1 to 8% can be obtained.

It is also possible to perform ion exchange by using an aqueous solution containing each ion alone in addition to the mixed aqueous solution as described above and sequentially contacting each aqueous solution with AAS. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.

The AAS after the ion exchange is thoroughly washed with water and then dried. Drying at 105 ℃ ~ 115 ℃ under normal pressure, or reduced pressure (1 ~ 30
Torr) at 70 ° C to 90 ° C.

Ion exchange of ions or organic ions without a suitable water-soluble salt such as tin or bismuth can be carried out by using a solution of an organic solvent such as alcohol or acetone so that a sparingly soluble basic salt is not deposited.

On the other hand, in the method (2), the pH of the slurry of AAS obtained by a conventional method is 6 or less, preferably 3 to 6, more preferably 4
The content of M ₂ O in AAS can be adjusted to 10% or less by adjusting to 5 or less. For the adjustment of the pH, the method exemplified in the above method (1) can be similarly used.

Next, the pH-adjusted slurry and the antibacterial metal ion-containing solution can be mixed to ion-exchange AAS in the slurry. For the ion exchange method and the like, the same method as the method (1) can be used as it is.

The coupling agent used in the antibacterial agent of the present invention is selected from the group consisting of organoaluminum compounds, organosilicon compounds and organotitanium compounds.

As the organic aluminum compound, acetoalkoxyaluminum diisopropylate, monoSEC-butoxyaluminum diisopropylate, aluminum ethylate, aluminum ethylacetoacetate diisopropylate, aluminum tris (ethylacetoacetate), aluminum bisethylacetylacetate monoacetylacetonate. Can be illustrated.

Examples of the organosilicon compound include vinylmethoxysilane, vinyltrichlorosilane, trimethylchlorosilane, ethyltrichlorosilane, bis (trimethylsilyl) acetamide, and N, N'-bis (trimethylsilyl) urea.

Examples of the organic titanium compound include tetraisopropoxy titanium, tetra-n-butoxy titanium, tetrastearoxy titanium, alkoxypoly titanyl acylate, diisopropoxy-bis (acetylacetonato) titanium, bidroxy-bis (lactato) titanium, and isopropyltriethyl. An example is sostearoisotitanate.

The antibacterial agent of the present invention can be obtained by directly mixing the coupling agent with the antibacterial aluminosilicate, or by immersing the antibacterial aluminosilicate in a solution in which the coupling agent is once dissolved in a solvent. . Specifically, the former is a mixer such as a kneader or a ball mill for mixing the antibacterial aluminosilicate and the coupling agent, for example, at room temperature to about 50 ° C.
It can be carried out by mixing for 1 to 10 hours.
The latter may be any solvent as long as it has good solubility in the coupling agent, and butanol, toluene, ethyl acetate, isopropanol, hexane and the like are preferable. Add and dissolve so that the solution viscosity is 2000 cP or less, preferably 1200 to 5 cP, and add antibacterial aluminosilicate to the solution at room temperature.
It can be performed by soaking for 10 minutes to 2 hours.

The amount of coupling agent added is 100 antibacterial aluminosilicates.
From 5 to 100 parts by weight, preferably from 10 to 80 parts by weight, is preferable from the viewpoint of exhibiting good dispersibility and antibacterial properties.

The antibacterial agent of the present invention can be used in various fields. It can be applied to resins used for plastics, films, fibers, rubbers, papers, pulps, leathers, paints and adhesives.

In particular, it can be favorably used also in the field of paints and adhesives where the resin film has a strong cohesive force.

In the paint field, oil paints, lacquers, varnishes, alkyl resins, aminoalkyd resins, vinyl resins, acrylic resins, epoxy resins, polyurethane resins, water-based, powder-based, chlorinated rubber-based, phenol-based, etc. It is possible to add antibacterial, mildew-proof and algae-proof functions to the coating film by directly mixing with or coating on the surface of the coating film. The applications to which these paints can be applied include buildings, stone materials, wood, vehicles, ships, ship bottoms, equipment, signs, electrical equipment, etc., and further chemical resistance, photoconductivity, photoelasticity, antistatic property. , Radio wave absorption, electromagnetic shielding, dew condensation prevention, soundproofing, vibrationproofing, radiation protection, fireproofing, heat resistance, temperature indication,
Luminous properties can also be imparted. As a painting method, brush,
Spraying, roll, flow coater, dipping, electrostatic coating and the like can be mentioned, and any method can be applied.

In the adhesive field, for example, thermo-effective resin adhesives (phenolic resin, resorcin resin, furan resin, urea resin, melamine resin, polyester resin, polyurethane resin, epoxy resin, silicone resin, etc.), thermoplastic resin adhesives (polyacetic acid) It can be used for vinyl, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral, polyacrylic ester, nitrocellulose, etc.), elastomer adhesives (butadiene acrylonitrile rubber, neoprene etc.) and natural adhesives. Applications of these adhesives include adhesive tapes, sealing materials, plywood, woodwork, construction, civil engineering, paper, packaging, automobiles, shoes, leather shoes, electrical appliances, textile products, rubber products, abrasives, optical equipment, etc. However, the present invention is not limited to these.

The antibacterial agent of the present invention can be directly kneaded or surface-coated with the above-mentioned paint and adhesive. From the viewpoint of adding antibacterial / mildew-proof / algae-proof functions to the above-mentioned paints and the like, it is appropriate that the amount of the antibacterial agent of the present invention is 0.05 to 80%, preferably 0.1 to 60%.

If necessary, the antibacterial agent of the present invention includes a pigment, a plasticizer, a curing agent,
Various additives such as a bulking agent, a filler, an antiaging agent, a thickening agent, a surface active agent, an antiseptic agent and an antibacterial agent can be appropriately used in combination.

Reference Example 1 (Preparation of Antibacterial Synthetic Zeolite) A-type zeolite heated at 110 ° C. (composition ratio Na ₂ O.Al ₂
O ₃ · 1.9SiO ₂ · XH ₂ O, average particle size 1.5 μm) Add water to 1 kg of powder to make 1.3 slurry, then stir to defoam, and add an appropriate amount of 0.5N nitric acid solution and water. pH 5 to 7
And a total volume of 1.8 was obtained. Next, for ion exchange, a mixed aqueous solution 3 of 0.15 M / concentration silver nitrate and 1.5 M / concentration ammonium nitrate was added to bring the total volume to 4.
8, the slurry liquid was maintained at 40 to 60 ° C., and the equilibrium state was reached while stirring for 10 hours. After the completion of ion exchange, the zeolite phase was filtered and washed with room temperature water or warm water until excess silver ions in the zeolite phase were eliminated. Next, it was heated and dried at 110 ° C. to obtain a sample of antibacterial synthetic zeolite.
The silver content in the sample was 4.8% and the ammonia content was
The water content was 0.9% and 18.2%.

Reference Examples 2 and 3 (Preparation of antibacterial synthetic amorphous aluminosilicate and antibacterial natural zeolite) Antibacterial synthetic amorphous aluminosilicate and antibacterial natural zeolite were prepared in the same manner as in Reference Example 1 under the conditions shown in the following table. Prepared.

Examples 1 to 12 and Comparative Examples 1 to 3 The antibacterial aluminosilicates obtained in Reference Examples 1 to 3, various coupling agents, and solvents were mixed in the formulations shown in Table 1 to prepare antibacterial agents, and then the antibacterial agents were used. The antibacterial composition was obtained by kneading the properties with a paint and the like with a double-arm kneader.

Preparation is performed by adding the coupling agent alone or by dissolving the coupling agent in a solvent into the antibacterial aluminosilicate and kneading (10 minutes at 50 rpm), then adding paint or adhesive for 80 minutes at 50 rpm. Kneaded

Example 13 The antibacterial composition obtained in Examples 1 to 12 and Comparative Examples 1 to 3 was applied to the surface of an aluminum plate plate (50 x 50 x 50 mm) to a thickness of about 100 µ.
It was applied to m to obtain a test plate. Similarly, paint and adhesive samples containing no antibacterial property were also prepared under the same conditions (Comparative Example 4).
~Ten).

Dispersion sample is powder gauge (Yoshimitsu Seiki 0-10μ
m, 0-25 μm type) was used to measure dispersibility. The measurement was performed by a method according to JIS K5400. The results are shown in Table 2.

Example 14 (antibacterial activity test) Escherichia coli solution (10 ⁵ cells / ml) 15 ml was added to the test plate obtained in Example 13.
It got down and cultured at 37 ° C. for 24 hours. The bacterial solution was washed away with physiological saline, and the number of E. coli present in this solution was measured. The results are shown in Table 2.

Example 15 (antibacterial endurance test) A test plate similar to that used in Example 14 was dipped in soap, rubbed with a nylon scrubbing brush for a predetermined number of times, and then thoroughly rinsed with running water to remove water, and the sample was drained in the same manner as in Example 14. The antibacterial test was conducted. The results are shown in Table 2.

[Effects of the Invention] According to the present invention, it is possible to provide an antibacterial agent which disperses well in a paint and an adhesive and exhibits a high antibacterial activity.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji Sugiura 1489-10 Sasahara, Nonami, Tenami-cho, Tenshiro-ku, Nagoya, Aichi Prefecture (56) References JP-A-59-133235 (JP, A) JP-A-53 -142455 (JP, A)

Claims (3)

[Claims] 1. An antibacterial agent obtained by treating an antibacterial aluminosilicate with at least one coupling agent selected from the group consisting of organoaluminum compounds, organosilicon compounds and organotitanium compounds. 2. A coating composition containing the antibacterial agent according to claim 1. 3. An adhesive containing the antibacterial agent according to claim 1.