JP2965488B2 - Antimicrobial composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides a novel antibacterial composition, which is useful not only for antibacterial and antibacterial treatment of various aqueous systems, but also for antifouling, anti-algae, anti-slimming, and deodorizing. The present invention relates to the use of a water-soluble composition and a water treatment method. The antibacterial composition according to the present invention has a higher mechanical strength than conventional water treatment agents, and has excellent abrasion resistance, water resistance and heat resistance,
It is based on a specific silica gel composed entirely of inorganic substances.

[0002]

2. Description of the Related Art Inorganic antibacterial agents have high safety and many have been published. For example, antibacterial agents in which antibacterial metal ions such as silver, copper, and zinc are supported on crystalline zeolite by ion exchange (JP-A-60-181002, JP-B-63-54013) and amorphous aluminosilicate Supported antimicrobial agent (JP-A-62-702)
No. 21, JP-B-63-54013) Also, an antibacterial agent in which antibacterial metal ions are bonded to aluminosilicate and ion-bonded to the surface (pore surface) of the silica gel matrix to immobilize the antibacterial aluminosilicate layer Agents (JP-A-3-252308, JP-A-4-295406)
No. 6-39368, U.S. Pat. No. 5,244,677, European Patent 444939), and an antimicrobial agent in which silver is retained on perconium phosphate as an antimicrobial metal (Japanese Patent Laid-Open No. 3-83905).
, Calcium phosphate, and antibacterial agent having silver supported on glass are listed as typical inorganic antibacterial agents. Most of these antibacterial agents are prepared in powdery to fine particle form and used for antibacterialization of polymers.

The antibacterial agent in the form of powder or fine particles has problems such as difficulty in handling and large pressure loss, and cannot be used in an aqueous system as it is. for that reason,
An antibacterial agent powder is molded using a binder, and is used as a molded product such as beads and pellets. However, even with a molded article prepared by such means, as the immersion time in water increases, the pulverization of the molded article gradually progresses and the performance deteriorates, so that the conventional article does not withstand long-term use in an aqueous system. there were. Antibacterial as an aqueous water treatment agent
In addition to sterilization, it is desired to have functions such as antifouling, anti-algae, anti-slimming, and odor prevention. In addition to the above-mentioned properties, it is essential that the water treatment agent has excellent mechanical strength and water resistance. It is. However, a preferred water treatment agent having such properties has not yet been obtained.

[0004]

SUMMARY OF THE INVENTION A novel inorganic antibacterial composition which solves the above-mentioned problems of the water treatment agent and has more excellent mechanical strength, abrasion resistance, water resistance and heat resistance. It is an object of the present invention to provide a water treatment agent and to provide a water treatment method which is excellent in effects such as antibacterial to sterilization, antifouling, anti-algae, anti-slimming, and deodorization for various types of water using the same. Is the purpose.

[0005]

The antimicrobial composition based on silica gel which was carried out earlier by the present inventors (Japanese Patent Publication No. 6-3936)
8, US Patent 5,244,667, European Patent 444939
By improving the physical properties and chemical properties of No. 1) and adapting it to aqueous treatment, the aforementioned unsolved problems can be solved and an antibacterial composition having more preferable properties as a water treatment agent can be obtained. The present invention has been completed and the present invention has been completed.

That is, the present invention provides at least 0.2c
m ³ / g pore volume (PV), at least 70 m ² / g
g of silica, having a specific surface area (SSA) of 65 g and a SiO ₂ content of 65-90% by weight as a main base material, and silver, copper and The present invention relates to an antibacterial composition which is a sintered body of particles having an antibacterial aluminosilicate layer holding at least one antibacterial metal ion selected from the group consisting of zinc.

[0007] In the antimicrobial composition of the present invention is preferably a pore volume (P.V.) is at least ^{0.2cm 3 / g, 0.3cm 3 /} g or more things more preferably, have . More preferably, 0.3 cm ^{3 /} g to 1.5.
cm ³ / g, most preferably 0.7 cm ³
/ G to 1.0 cm ³ / g. Specific surface area (S.
S. A) is at least 65m considering the reactivity of the material
It is preferably at least ² / g, more preferably at least 90 m ² / g.

In the present specification, the value of the pore volume can be measured by a mercury porosimeter, and the specific surface area can be measured by N ₂ adsorption according to the BET method. It is a value measured by the method. Further, the density can be easily measured by various general densitometers. Further, in the antibacterial composition of the present invention, the average pore diameter (PD) is preferably as large as possible, preferably at least 50 Å, more preferably at least 200 Å.

The apparent density when the average particle size is 1 to 10 μm is preferably 0.35 to 0.8 g / cm ³ , more preferably 0.40 to 0.70 g / c.
m ³ , most preferably 0.50 to 0.60 g / c
m is ^3. The detailed method of measuring the apparent density will be described in Examples below, but unless otherwise specified, the values of the apparent density referred to in the specification are those at the time of vibration filling,
The numerical values described in the claims are those at the time of vibration filling. Since the apparent density slightly varies depending on the particle size, it is necessary to measure the average particle size as 1 to 10 microns. In addition, the above description does not mean that it is necessary to be in the above apparent density range in all of the particle size range of 1 to 10 microns, and it is sufficient if the above apparent density range is in any of the particle size ranges. The purpose of this is. The apparent density serves as a scale for evaluating the degree of firing, and it can be considered that firing increases as the apparent density increases. If the apparent density is too large, baking proceeds too much, and the antibacterial activity tends to decrease. On the other hand, when the apparent density is too small, sintering has not progressed, and the effect of the present invention cannot be sufficiently obtained.

In the antibacterial composition of the present invention, when the antibacterial metal ion is only silver, copper or zinc ion, the content of each is at least 0.2%, 0% of the anhydrous antibacterial composition. It is preferably 0.5 or 3%. Furthermore, when the antibacterial metal ion in the antibacterial composition is composed of at least one antibacterial metal ion selected from the group consisting of copper and zinc, and silver ion, the weight of the anhydrous antibacterial composition is based on the weight of the anhydrous antibacterial composition. The content of silver is at least 0.1% and the content of at least one antibacterial metal ion selected from the group consisting of copper and zinc is at least 2%;
%. By being used in the above range, the strength of the antibacterial composition is further increased, the water resistance is increased, and the diffusion of the antibacterial metal ions in the pores is smoothed, and the antibacterial effect, anti-algae, deodorant, etc. Can be exhibited in a preferable state. The “anhydrous state” refers to a state in which there is no water bound to the antibacterial composition and no water attached to the surface.

The antibacterial composition of the present invention is obtained by chemically treating porous silica gel with an alkali solution and an aluminate solution.
Form a non-antibacterial layer made of aluminosilicate ion-bonded to the surface of silica gel (micropores or macropores), and then perform ion exchange using antibacterial metal ions to replace the antibacterial layer with the antibacterial layer. And the resulting antibacterial composition can be produced by heat treatment. That is, specifically, the antibacterial composition of the present invention comprises: 1) treating silica gel with an alkali solution and an aluminate solution to form an aluminosilicate layer containing an ion-exchangeable metal on the active surface of the pores of the silica gel matrix. Substantially immobilized, 2) then treated with a salt solution containing at least one metal ion selected from the group consisting of silver, copper and zinc to ionically bind the germicidal metal ions to the aluminosilicate layer; Form an antibacterial layer,
3) It can be produced by heat-treating the obtained antibacterial composition at 350-800 ° C.

The silica gel used as a starting material of the antibacterial composition of the present invention may be any of powder, particle, crushed or molded into pellets, tablets and the like.
When powdered silica gel is used as a raw material, an antibacterial composition powder is prepared using the silica gel, then molded in the presence of an organic binder, and then heat-treated to form an antibacterial composition. do it.

Examples of the organic binder include cellulose powders such as methylcellulose and cellulose derivatives such as carboxymethylcellulose, water-soluble binders such as polyvinyl alcohol, starch and gelatin, hydroxyethylcellulose, hydroxypropylcellulose and polyvinylpyrrolidone. Alcohol-soluble binders such as can be used.

Raw material silica gel (SiO ₂ ) x · (H ₂ O)
y (where x and y represent the coefficients of SiO ₂ and H ₂ O, respectively) has an innumerable number of internal pores developed, and in consideration of reactivity, is a porous material having a large pore diameter and a large specific surface area. Active ones are preferred. Silica gel is commercially available in the form of granules, spheres, crushed products, powders, molded products (pellets, tablets) and the like. Many of them have an SiO ₂ content of 9
9% or more, in which some impurities such as Na
_It contains ₂ O, Fe ₂ O ₃ , MgO, CaO, Al ₂ O _{3 and the} like. Silica gel having the above-mentioned properties and suitably used in the present invention is commercially available in Japan, for example, from Fuji Silysia Chemical Ltd., Asahi Glass Co., Ltd., Water Chemical Industry Co., Ltd., Toyota Chemical Co., Ltd., and other countries. Grace (Grac)
e Chem. Co) and many more varieties are on sale.

As the alkaline solution, for example, NaOH, K
Using a hydroxide solution of an alkali metal such as OH or LiOH, a slurry solution containing silica gel is prepared by, for example, 9.
By maintaining the pH in the range of 5 to 12.5, the alkali treatment of the silica gel surface is performed. Then NaAl
Chemical treatment with an aluminate solution of an alkali metal such as O ₂ , KAlO ₂ , and LiAlO ₂ is performed at room temperature or under heating. By this chemical treatment, SiO ₂ present on the surface of the pores of the silica gel reacts with the aluminate, and an aluminosilicate layer containing an ion-exchangeable metal is formed on the active surface of the pores of the silica gel. Aluminosilicate layer of the are no antimicrobial, represented by the general formula _{X M 2 / n O · Al} 2 O 3 · ySiO 2 · zH 2 O. Where x and y are the coefficients of the metal oxide and silicon dioxide, M is the ion-exchangeable metal,
N represents the valence of M, and z represents the number of water molecules. M is usually L
It is a monovalent metal such as i, Na, or K, and may be NH ₄ ⁺ . This is further converted to, for example, Mg, Ca, Sr, Ba, M
Partial or complete substitution using a divalent metal such as n, Ni, Co or Fe by ion exchange may be used.

The thickness and composition of the antimicrobial layer made of aluminosilicate, which is fixed by ionic bonding on the surface of the silica gel matrix obtained by the above method, depends on the physical properties of the silica gel material, the amount used, the alkali concentration, the alumina It can be arbitrarily adjusted by adjusting factors such as the amount of the acid salt added, the reaction temperature and the reaction time.

Next, the ion-exchangeable metal M in the non-antibacterial layer is obtained by using a solution containing at least one antibacterial metal ion selected from the group consisting of silver, copper and zinc as an antibacterial to bactericidal metal ion. An antimicrobial composition can be obtained by ion exchange using the currum method, the batch method, or a combination of both. By ion exchange, a part or all of the above-mentioned M is replaced with an antibacterial metal ion, and an antibacterial layer which is ion-bonded to the surface (pore surface) of the silica gel matrix and is not easily separated from the matrix is formed. The metal ions of the obtained antibacterial layer are distributed in a thin layer in the pores and macropores of the silica gel in a homogeneous and favorable state.

In the heat treatment step, the treatment conditions vary depending on the type and physical properties of the antibacterial composition, but usually a heat treatment at 350 to 800 ° C. is performed for a predetermined time. When the antibacterial composition is in powder form, the sintering density does not increase in the treatment in the temperature range of 350 ° C. or less, and in the treatment in the temperature range of 800 ° C. or more, the antibacterial activity tends to gradually decrease as the temperature increases. is there. The optimum temperature and the required time for the heat treatment vary depending on the shape and composition of the antibacterial composition. For example, since the heat resistance of an antibacterial composition based on silica gel using silver and zinc as antibacterial metals is high, the heat treatment is suitably performed in a temperature range of 400 to 800 ° C, and a composition using only silver. Is slightly lower in heat resistance, so that the heat treatment is suitably performed in a temperature range of 380 to 550 ° C. Also, the antibacterial composition is a pellet,
The antibacterial composition of the present invention can be obtained by selecting an appropriate temperature range from the above-mentioned heat treatment region of 350 to 800 ° C. even if it is a tablet, a sphere or a block (coagulated) body. Can be.

The antibacterial composition of the present invention is suitably used as an antibacterial agent in various uses, and has an excellent effect particularly as a water treatment agent. The main features of the antibacterial composition of the present invention are listed below. 1) The antibacterial composition (shape: crushed product, granular product, molded product) obtained by the method of the present invention has slightly different heat resistance depending on the type and composition thereof. If heat treatment is performed in an appropriate temperature range, an antibacterial composition having a structurally stable antibacterial activity similar to that before heat treatment can be obtained. 2) When the antibacterial substance is a powder, by sintering or sintering it after molding it,
The mechanical strength and water resistance of the finally obtained antibacterial composition can be increased, and a water treatment agent suitable for an aqueous system can be obtained. Even when the antibacterial substance is in the form of a lump to a molded body, the heat treatment of the present invention can further increase the sintering density and provide a high strength agent suitable for water treatment.

3) By performing the heat treatment, the physical properties of the surface of the pores of the antibacterial composition containing silica gel as a matrix are further improved, and the antibacterial metal ions such as Ag ⁺ , Zn ^2+, and Cu ²⁺ are compared with the matrix. Is extremely suppressed, and when used as a water treatment agent, a long-term effect is expected. 4) By performing the heat treatment, the diffusion rate of the antibacterial Ag ⁺ , Zn ²⁺ and Cu ²⁺ in the pores of the antibacterial composition becomes appropriate, and the ions are gradually released out of the system. It can be used for a long period of time, such as strength, algae prevention and slimming prevention. Further, Ag ⁺ generated by dissociation from the mother,
Antimicrobial metal ions such as Cu ²⁺ or Zn ²⁺ are rapidly diffused in the pores and diffused with a large contact area between the antimicrobial metal ions and fungi, so ideally for suppressing or killing fungal growth. Done in

5) Since the pore size of the present antibacterial composition is extremely large as compared with the known antibacterial agents, even in an aqueous system containing a large amount of chloride ions, hardly soluble or insoluble precipitates (such as AgCl)
Thus, there is an advantage that the pores are not blocked, so that antibacterial to sterilization can be performed smoothly and the antibacterial effect is maintained for a long time. Further, the water treated with the antibacterial composition of the present invention is characterized in that no growth of various bacteria is observed for at least 48 hours or more. Such an effect is an effect that cannot be seen with current known antibacterial agents, and is a matter to be noted. 6) When the antibacterial composition of the present invention is used as a water treatment agent, it has high water resistance and abrasion resistance, and is not limited to general bacteria,
It exerts a favorable antibacterial effect on fungi such as molds.
In addition, there is an advantage that effects such as algae prevention, slimming prevention, and odor prevention are also exhibited.

7) An aqueous treating agent obtained by calcining an antibacterial composition comprising silica gel as a matrix and an antibacterial metal mainly composed of copper can be used in an aqueous system having a high salt concentration, for example, in seawater. Under the influence of CuCl ₂ , C
It has an effect of suppressing the growth of various bacteria (mainly, bacteria of the genus Vibrio) in seawater without precipitation of uCl or the like. This is a feature not found in known inorganic antibacterial agents. 8) The mechanical strength (hardness) is threateningly large and the water resistance is excellent. As shown in the examples described below, in the water resistance test, the phenomena of breakage, cracking, abrasion, and pulverization of the antibacterial composition of the present invention are not visually recognized. 9) All are poorly soluble in water, and the antibacterial metal ions released from the base of the antibacterial composition are sustained release (ppm to ppb order), based on which antibacterial, antialgal, deodorant, anti-slimming, There is an advantage that the blackening prevention effect lasts for a long time.

10) Since the antibacterial composition of the present invention is based on active silica gel, it is also effective in adsorbing deodorant components. Further, when the polymer molded article is immersed in water containing the antibacterial composition and held for a long period of time, there is an advantage that no slime is generated. 11) Copper antimicrobial composition of the present invention having that mainly antimicrobial metal is usually the water well, high salinity water, be used, for example seawater, under the influence of chloride ion, CuCl ₂ No precipitation of copper salts such as CuCl and the like is observed, and an excellent effect is exhibited. In addition, when this product is used in seawater systems, it exerts an antibacterial effect on bacteria such as Vibrio spp., Escherichia coli, and Staphylococcus aureus, which are mainly present in seawater, and suppresses the growth of these bacteria, Or has the effect of completely killing. This is a feature not found in known inorganic antibacterial agents. 12) The antibacterial composition containing silver as the main antibacterial metal can be used for the precipitation layer of various types of water and the filtration layer of water filters and water purifiers.
It is easy to keep [Ag ⁺ ] in the effluent from these filtration layers to 50 ppb or less (Ag ⁺ regulation in drinking water of EPA is 50 ppb or less), and exhibits excellent effects for antibacterial to sterilization purposes in water. I do.

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are merely examples of the present invention, and do not limit the technical scope of the present invention. Reference Example 1 In this reference example, prior to the preparation of the antibacterial composition, the silica gel material was treated with an alkali and an aluminate solution to form an aluminosilicate layer containing an ion-exchangeable metal on the active silica gel matrix. This is an example of a method of forming an antibacterial intermediate composition by forming it on the surface of a pore. Silica gel (trade name: CARIACT-30, 5 to 10 mesh beads) manufactured by Fuji Silysia Ltd. was used as a starting silica gel material. After about 25 kg of the silica gel as an anhydride was added to the reaction vessel, 60 liters of water was added, and the aqueous phase was circulated to prepare a silica gel bead mixture. Then a thin NaOH solution is added and the aqueous solution p
H was kept at 9.6. 3.9 kg of solid NaOH and A
l (OH) ₃ was dissolved in 5.2 kg of water by heating, and water was further added to add a total volume of about 45 liters (pH = 12.9) of N.
An aAlO ₂ solution was prepared. After adding the obtained NaAlO ₂ solution to the reaction vessel under stirring, the aqueous phase of the reaction vessel was heated under circulation, kept at 58 to 60 ° C., and then reacted at the same temperature range for 72 hours. Then, an intermediate composition (an intermediate composition having an aluminosilicate layer on the base surface of silica gel) was synthesized. After completion of the reaction, the solid phase was separated by a SUS filter (filter cloth: Saran), and then washed with warm water (about 60 ° C.). Washing was performed until the pH of the filtrate became 10 or less. After the completion of washing, the above intermediate composition was dried at 110 to 120 ° C. using a dryer. Through the above steps, about 26 kg of a dried product of the intermediate composition was obtained. The moisture content of the dried beads is 5.55%, Na = 4.74%,
Al = 5.39% (anhydrous basis).

Example 2 This example relates to a preparation example of an antibacterial composition containing copper as an antibacterial metal and containing silica gel as a matrix, using the intermediate composition prepared in Reference Example 1. In this example, an antibacterial composition was prepared by heat-treating the obtained antibacterial composition after the intermediate composition prepared in Reference Example 1 was subjected to antibacterial treatment by using both the carram method and the batch method. Was done.

An ion exchange column made of transparent vinyl chloride [I.
D. 104 × 150 m / m (effective length)], the intermediate composition beads prepared in Reference Example 1 [Na = 4.74]
%, Al = 5.39% (anhydrous basis)] was charged to each column in an amount of about 5.5 kg. The towers were back-washed with water and the intermediate composition beads were homogenously packed into a carram. After connecting the two units in series, 130 liters of a 0.30 M Cu (NO ₃ ) ₂ solution (pH = 3.30; load solution) kept at room temperature was flowed at a flow rate of 5 liters / hour (linear velocity 1.1 cm / min.). ). This treatment was performed until the copper ion concentration in the water-flowing liquid and the liquid (Eluate) flowing out from the bottom of the carrum became almost the same, and the ion exchange system reached dynamic equilibrium. After passing the solution, take out both phases in the ion exchange column,
On the other hand, a small amount of the above-mentioned 0.30 M Cu (NO ₃ ) ₂ solution was added, and the aqueous phase was slowly circulated at room temperature for 24 hours to reach equilibrium (batch method). After separating the two phases, the bead-like antibacterial composition having the copper in the solid phase was washed with water to remove excess Cu ²⁺ from the solid phase. After completion of the water washing, the solid phase was dried at 100 to 110 ° C. to prepare beads of an antibacterial composition containing copper. The yield of the dried beads obtained in this example was about 11.5 kg, and Cu = 5.9% and Na = 0.2% (anhydrous basis) in the beads.

Next, about 500 g of a dried product of the antibacterial composition beads prepared through the above-described steps was collected, and heat-treated at 490 ° C. for 3 hours to contain the copper of the present invention as an antibacterial metal. An antimicrobial composition was prepared. The antibacterial composition prepared in Example 2 (KCu-1-1;
Composition and physical properties of the product fired for 3 hours): Cu = 5.9%; Na =
0.2%; Al = 5.39%; SiO ₂ = 82.2%
(Anhydrous basis); SSA = 94 m ² / g; V = 0.9
3 cm ³ / g; D. = 285 angstroms (anhydrous basis)

Compressive Strength (Hardness) Measurement and Water Resistance Test The compressive strength (hardness) of the antibacterial composition (beads fired at 490 ° C. for 3 hours) obtained in Example-2 was measured by using a Kiya hardness meter. It was implemented. At the time of hardness measurement, a population (about 200 g) of the antibacterial composition was prepared, from which 10 beads were randomly sampled and the hardness was measured (Table 1). The average hardness was 14.8 kg / bead as indicated. In the above hardness measurement, the average value was calculated as 20 kg / bead when the hardness measured value was 20 kg / bead or more. Table 1 shows that the mechanical strength of the antibacterial composition prepared according to the present invention is threateningly high.

Next, the antibacterial composition prepared in Example 2 (beads fired at 490 ° C. for 3 hours) was subjected to a water immersion test in water.
This was performed by soaking for 2 hours. The beads immersed in water for 72 hours were randomly extracted and the hardness was measured after removing the surface moisture. As shown in Table 1, 11.3 kg / bead was obtained as an average hardness value of the wet beads. These values indicate that the antibacterial composition obtained in the present invention has extremely high water resistance and is excellent. In addition, no phenomenon such as breakage of beads or powdering due to abrasion was observed at all during the water-resistant immersion for 72 hours. Further, the beads after the water resistance test were dried at 100 ° C. for 3 hours, and the hardness of the obtained beads was measured. As shown in Table 1, 15.2 kg / bead was obtained as an average hardness value (compressive strength) of the dried beads. From these tests, it was shown that the antibacterial composition of the present invention has physical properties suitable for use in aqueous systems and can withstand long-term use.

[0030]

[Table 1]

Antibacterial activity test The antibacterial activity test of the antibacterial composition obtained in Example 2 was conducted by the shake flask method under the following conditions. Antimicrobial activity assay: shake flask method (S. F. Law) total liquid volume during the test: 100 cm ³ constant liquid temperature: about 25 ° C. test bacteria: Escherichia coli (Escherichia coli); strain IFO-12734 Staphylococcus aureus ( Staphylococcus aureus); strain IFO-12732 Initial number of bacteria: E. coli 8.3 × 10 ⁵ cells / ml Staphylococcus aureus 7.3 × 10 ⁵ cells / ml Medium: Mueller Hinton 2 (BBL) Test results are shown in Tables 2 and 3. 3 is shown. These results indicate that, in an aqueous system, antimicrobial metal ions are dissociated from the parent of the antimicrobial composition, and a small amount of Cu ²⁺ is continuously released, based on which a favorable antimicrobial activity against general bacteria is exhibited. It is shown that.

[0032]

[Table 2]

[0033]

[Table 3]

Anti-algae test The antibacterial composition (KCu-1) prepared in Example 2 was added to 500 ml of well water (Nanagi-cho, Kikuchi-gun, Kumamoto).
20 g of -1) was added and stored in a polyethylene bottle. On the other hand, 500 ml of well water was collected for a blank test and stored in a polyethylene bottle. Both bottles were stored for 3 months under intermittent agitation and the presence or absence of algae growth was observed. Algae formation was not observed at all in the solution containing the antibacterial composition of the present invention, while a large number of algae were observed in the blank test solution in about one month. This test also shows that the antibacterial composition has an excellent antialgal effect.

Example 3 An antibacterial intermediate composition (bead 5) prepared in Reference Example 1
-10 mesh; Na = 4.74%; Al = 5.39
%) Is collected in a reaction vessel, and about 20 liters of water is added thereto.
It was kept at 0 ° C. Then, a dilute nitric acid solution was gradually injected while circulating the aqueous phase of the reaction vessel, and the pH of the aqueous phase was finally adjusted to 4.4 ± 0.1. After performing solid-liquid separation, an AgNO ₃ solution (0.1
9.9 liters (4 mol / l) were added, and then the ion exchange reaction for 36 hours was carried out batchwise with circulation of the aqueous phase, keeping the liquid temperature at 60 ° C. As a result, the above-mentioned intermediate composition (non-antibacterial) mainly composed of silica gel having the alumina silicate layer was made antibacterial and converted to an antibacterial composition containing silver as an antibacterial metal. The antimicrobial composition beads prepared through the above reaction are 50 to 6
Washed with warm water at 0 ° C. Washing was performed until no excess Ag ⁺ was found in the filtrate. Next, the beads that had been washed with water were dried at 100 to 110 ° C. to obtain antibacterial composition beads having a water content of 4.5%. Heat treatment at 500 ° C. for 2 hours 3
Running for 0 minutes, the antimicrobial composition using silver as the antimicrobial metal of the present invention was finally prepared. Yield of antibacterial composition (B-1-A) prepared in Example 3: 4.6 kg Composition and physical properties of antibacterial composition prepared in Example 3: A
g = 3.4%; Na = 3.6%; Al = 5.39%; S
iO ₂ = 81.3% (on anhydrous basis); SSA = 91 m ² /
g; V. = 0.96 cm ³ / g; D. = 290
Angstrom (anhydrous basis)

Measurement of Compressive Strength (Hardness) and Water Resistance Test (Example 3) The antibacterial composition obtained in Example 3 (500 ° C. for 2 hours
The compression strength (hardness) of the 0-minute fired beads (B-1-A) was measured according to Example 2. At the time of hardness measurement, a population (about 250 g) of the antibacterial composition was prepared, and three sets of small populations were prepared therefrom. In this case, the small population consisted of 10 beads randomly selected. In measuring the compressive strength (hardness), the minimum and maximum values of the hardness were deleted as shown. Example 3 as described in Table 4
The average hardness (Hm) of the antibacterial composition (B-1-A) is 1
At 2.0 kg / bead, beads having excellent mechanical strength were obtained. Further, a water resistance test of the antibacterial composition (B-1-A) obtained in Example 3 was performed according to Example 2. In the water resistance test, the B-1-A beads were immersed in water for one week, and then the hardness of the wet beads was measured after removing water adhering to the surface. Table 4 B-1-1
This is exactly the same as the case of A (500 ° C. for 2 hours 30 minutes).

As shown in Table 5, the average hardness (Hm) of the wet beads after one week of immersion in water was 10.
9 kg / bead, and Hm = 12.0 k in Table 4
It is clear from the comparison of g / beads that the water resistance is extremely large and the mechanical strength is hardly deteriorated even when the agent is immersed in water. No deterioration, breakage, or powdering of the beads during the water resistance test was observed at all. From the above test, it was found that the antibacterial composition obtained in Example 3 had properties suitable for use in aqueous systems. Further, the average hardness of the dried beads after immersion is Hm = 11.5 kg / bead as shown. It is clear from these tests that the B-1-A beads of the present invention have preferable physical properties as an aqueous treatment agent.

[0038]

[Table 4]

[0039]

[Table 5]

Anti-algae test Antibacterial composition (B-1-A) prepared in Example 3 against 500 ml of well water (Nanagi-cho, Kikuchi-gun, Kumamoto)
Was added and stored in a clear bottle. On the other hand, for the blank test, the well water was stored in a 500 ml transparent bottle. Both bottles were stored for 3 months under intermittent shaking, and the occurrence of algae was observed. No generation of algae was observed at all in well water containing B-1-A of the present agent, while generation of a large number of algae was clearly confirmed in the blank test solution after one and a half months. It is clear that the antimicrobial composition exhibits an excellent anti-algal effect than this test.

Example 4 The non-bacterial intermediate composition (bead 5) prepared in Reference Example 1
-10 mesh; Na = 3.6%; Al = 5.39%)
About 5 kg was collected in a reaction vessel, and 20 liters of water was added thereto. Then, the aqueous phase was heated while maintaining circulation.
It was kept at 0 ° C. Next, the aqueous phase of the reaction vessel (60
C.), the pH of the aqueous phase was finally adjusted to 4.4 ± 0.1 by slowly injecting the dilute nitric acid solution. For the solid phase obtained after performing solid-liquid separation, A
gNO ₃ -Zn (NO _{3) 2} mixture [AgNO _3, 0.2
1 kg + Zn (NO ₃ ) ₂ .6H ₂ O, 0.88 kg + H ₂
O → 9.9 liters (pH = 4.35)]
Next, the liquid temperature was maintained at around 60 ° C., and the ion exchange reaction for 36 hours was carried out while maintaining the circulation of the aqueous phase (batch method).

In this case, if necessary, the pH of the aqueous phase was maintained at 3.7 to 4.6 by occasionally adding dilute nitric acid. According to the above-mentioned method, the intermediate composition based on silica gel having the alumina silicate layer was made antibacterial, and was converted into a composite antibacterial composition containing silver and zinc as antibacterial metals. The antimicrobial composition beads prepared through the above reaction are 5
Washed with hot water at 0-60 ° C. Wash with excess Ag
Performed until no more ⁺ was found in the filtrate. Next, after completion of washing with water, the beads were dried at 100 to 110 ° C to obtain beads of an antibacterial composition having a water content of 5.28%.
The dried beads were subjected to heat treatment at 650 ° C. for 2 days.
The operation was carried out for 40 minutes to finally prepare the antibacterial composition comprising silver and zinc of the present invention. Yield of antibacterial composition (B-2-AZ) prepared in Example 4: 4.7 kg Composition and physical properties of antibacterial composition prepared in Example 4: Ag = 3.1%; Zn = 3.6%; Na = 1.0%; A
l = 5.39%; SiO ₂ = 80.7% (on anhydrous basis);
SSA = 93 m ² / g; V. = 0.98cm ³ /
g; D. = 280 angstroms (anhydrous basis)

Measurement of Compressive Strength (Hardness) and Water Resistance Test (Example 4) The antimicrobial composition obtained in Example 4 (650 ° C. for 2 hours 4 hours)
The measurement of the compressive strength (hardness) of the 0-minute fired product (B-2-AZ) was performed according to the above-described example. Preparation of a population or a small population of the antibacterial composition at the time of hardness measurement is exactly the same as in the above example. As shown in Table 6, the average hardness (Hm) of the antibacterial composition (baked at 650 ° C. for 2 hours and 40 minutes; B-2-AZ) prepared in this example was 9.2 kg / bead. It can be seen that the sample still has a preferable hardness.
Further, the above water-immersed product (wet beads immersed in water for one week) also has an Hm of 10.0 kg / bead as indicated, indicating extremely high water resistance. No pulverization phenomenon was observed. Further, the beads which have been immersed in water are heated at 100 to 110 ° C.
Hm of the dried beads dried at 9.5 kg / bead. From these tests, it is clear that the antimicrobial composition beads prepared in Example 4 of the present invention have preferable physical properties suitable for treatment of aqueous systems.

[0044]

[Table 6]

Example of Measurement of Antibacterial Activity of Antibacterial Composition The antibacterial composition in the form of beads prepared according to Examples 3 and 4 will be described. The antibacterial activity was measured by the following shake flask method. Test method for antibacterial activity: Shake flask method (SF method) Total liquid volume during test: 200 ml (constant) Liquid temperature: about 25 ° C Test bacteria: Escherichia coli: strain IFO-12734 Bacillus subtilis: strain IFO-13719 Pseudomonas aeruginosa: strain IFO-12689 MRSA (Methycillin-resistant staphylococcus aureus): strain KB-1005 Initial bacterial count: E. coli: 6.7 × 10 ⁵ cells / ml Bacillus subtilis: 7.9 × 10 ⁵ cells / ml Pseudomonas aeruginosa: 3.8 × 10 ⁵ cells / ml MRSA: 8.6 × 10 ⁵ cells / ml Medium used: Mueller Hinton 2 (BBL)

As shown in Table 7, the results of the antibacterial activity test on Escherichia coli were as follows: B-2-AZ (65
Example 4) shows that the baked beads at 0 ° C. for 2 hours and 40 minutes exhibit excellent antibacterial activity against the above bacteria, and the bacteria are killed in a very short time. S-1 was prepared according to Example 3. Regardless of the antimicrobial composition beads having a relatively low antimicrobial metal Ag content (Ag = 0.66%), the number of bacteria is 3
It has disappeared in 0 minutes.

Next, the test results for Bacillus subtilis are shown in Table 8. B-1-A (500 ° C. for 2 hours 30 minutes fired beads; Example 3), B-2-AZ (65
Baked beads at 0 ° C. for 2 hours and 40 minutes;
It has excellent antibacterial activity against cillus subtilis. Further, Table 9 shows the results of an antibacterial activity test on Pseudomonas aeruginosa, in which B-2-AZ (65
The fired beads at 0 ° C. for 2 hours and 40 minutes; Example 4) kills the above bacteria in a short time. MRSA (Methycillin-
Table 1 for resistant staphylococcus aureus)
0, the antimicrobial compositions (B-1-A and B
-2-AZ) shows preferable antibacterial activity. Table 7
The parenthesized values shown in Tables 10 to 10 indicate the amount of the antibacterial composition beads collected in a total volume of 200 ml (constant). In each of the above tables, the time-dependent change in the number of bacteria when no antibacterial composition beads were added is described for a blank test (control value). The antimicrobial metal ions in the antimicrobial composition are rapidly diffused in the pores of the silica gel matrix, and come into contact with fungi to achieve the preferred antimicrobial activity.
The germicidal effect is evident from the antibacterial activity test described above.

[0048]

[Table 7]

[0049]

[Table 8]

[0050]

[Table 9]

[0051]

[Table 10]

Example 5 This example relates to an example of preparing a molded antibacterial composition. In this agent, silica gel composed of relatively fine particles is used as a raw material, and this is treated with an alkali and aluminate solution to form an aluminosilicate layer containing ion-exchangeable metal ions (Na ⁺ ) as a base material of the silica gel. An inorganic antimicrobial intermediate composition was formed on the active pore surface, which was then antimicrobial and converted to a particulate antimicrobial composition. The composition was molded in the presence of an organic binder, molded into a sphere, and finally baked to prepare the antimicrobial composition of the present invention.

Preparation of Intermediate Composition As a starting material, a commercial product of Toyoda Kako Co., Ltd. (50 mesh pass; true specific gravity 2.2: SSA 450 m ² / g; pore diameter: about 60 Å: pore volume: about 0.8 Milliliter / g) was used. The silica gel was added to about 5.
After adding 5 kg to the reaction vessel, about 15 liters of water was added and stirred to prepare a silica gel slurry mixture. The pH of the aqueous phase was then adjusted to 9.7 by injecting a dilute NaOH solution. NaOH, 0.93k
g of water 0.8 liters and Al (OH) _3, 1.
The mixture with 2 kg was heated and dissolved, and water was added to the solution to make a total volume of 10.9 liters. A NaAlO ₂ solution (pH = 1)
2.9) was prepared. The obtained Na was added to the reactor under stirring.
After 10.9 liters of the AlO ₂ solution was injected, the temperature of the reaction vessel was raised with stirring and maintained at about 60 ° C., and then the reaction was carried out at the same temperature for 7 hours, so that the silica gel matrix surface The synthesis of an intermediate composition with a fixed aluminosilicate layer was performed. After completion of the reaction, the solid phase was taken out to a stainless steel filter (filter cloth: Saran) and washed with warm water. Washing was performed until the pH of the filtrate became 10 or less. Then, the intermediate composition is 110-120.
Dried at ℃. Through the above steps, 5.3 kg of a dried product of the intermediate composition (fine particles, 50 mesh pass) was obtained, and the composition was Na = 4.48% and Al = 4.30% (anhydrous basis).

Antibacterialization of Intermediate Composition As an anhydride of the intermediate composition obtained in the above synthesis [fine particles; 50 mesh pass; Na = 4.48%, Al = 4.30% (anhydrous basis)] 4. 9 kg is collected in the reaction tank,
After adding about 20 liters of water thereto, the temperature of the reaction vessel was raised and maintained at about 60 ° C. Then, the reaction vessel was kept under stirring, and dilute nitric acid was gradually injected to adjust the pH of the aqueous phase to around 4.4 finally. AgNO ₃ , 0.31
kg and _{Zn (NO 3) 2 · 6H} 2 O, and 1.3kg was dissolved in water, the total volume and 10 liters, AgNO ₃ -Zn
(NO ₃ ) ₂ mixture was prepared. After this was added to the solid phase obtained after solid-liquid separation, the liquid temperature was maintained at 60 ° C., and an ion exchange reaction was carried out for about 3 hours with stirring (batch method). . During the ion exchange, the pH of the aqueous phase was maintained at 3 to 4. By this method, the intermediate composition in the form of non-antibacterial fine particles was converted into an antibacterial composition having silver and zinc as antibacterial metals.
The fine-particle antibacterial composition prepared through the above steps was washed with warm water of about 60 ° C. Wash with excess Ag
^This was done until no more ⁺ was found in the filtrate. Then
The water-washed antibacterial composition was dried at 100 to 110 ° C. Yield of the particulate (50 mesh pass) antibacterial composition obtained in this example: about 4.8 kg (anhydrous)

Molding and heat treatment About 2 kg of the fine-particle antibacterial composition (50 mesh pass) prepared through the above-mentioned steps was collected and used as an organic binder. C. A liquid containing 1% (methylcellulose) was added and mixed, and then molded into a spherical body using a marmellaizer. Next, the spherical molded body is dried at about 100 ° C. and then sintered through a heat treatment at 645-650 ° C. for 2 hours to obtain a spherical antibacterial composition comprising silver and zinc as the antibacterial metal of the present invention. Thing was obtained. The antibacterial composition obtained in Example 5 (B-3-AZ; 645 to 650 ° C-2)
H) Composition Ag = 3.4%; Zn = 2.1%; Na =
1.5%; SiO ₂ = 83.6% (anhydrous basis); SSA
= 434 m ² / g; V. = 0.75cm ³ / g; P.
D. = 56 angstroms

Table 11 shows the relationship between the heat treatment and the antibacterial activity of the antibacterial composition (50-mesh pass product) obtained in the step of antibacterializing the intermediate composition of Example 5. The antibacterial composition obtained in this example has a stable structure (result of X-ray diffraction) at a heat treatment of 500 to 800 ° C., and exhibits excellent antibacterial activity against E. coli and A. niger. It is clear from Table 11. Next, the antibacterial composition (B-
3-AZ; beads) were measured in the same manner as in the above-mentioned Example. The antibacterial composition (a product fired at 645 to 650 ° C .; beads) obtained in this example was sieved to prepare a population of beads having a diameter of 2.0 to 3.4 m / m. Hardness was measured randomly (Table 12). In this case, the maximum and minimum values have been removed as indicated. 9.8 kg / average hardness Hs
Beads were obtained. From this test, it can be seen that the antibacterial composition (B-3-AZ) obtained in the present invention has excellent hardness and is suitable as an aqueous water treatment agent.

[0057]

[Table 11]

[0058]

[Table 12]

Example 6 The antibacterial composition (KCu-1-) prepared in Example 2 was used for 10 liters of seawater (seawater near Ojimisaki, Omuta-shi).
1: 490 ° C. for 3 hours fired beads).
After stirring for a predetermined time, 200 ml of a seawater sample was collected, and copper ions in the seawater were quantified, and bacteria present in the sample seawater were measured by a quantitative culture method.
Table 13 shows the results. Sample S-0 contains KCu in seawater.
-1-1 represents an additive-free product. S-6-12 and S
-6-24 shows a seawater sample obtained by adding about 6 g of KCu-1-1 beads to 10 liters of seawater and stirring the mixture, and after 12 hours and 24 hours, respectively. S
12-12 and S-12-24 are KCu-1-1.
About 12 g of beads were added to 10 liters of seawater and stirred, and seawater samples collected at the lapse of 12 hours and 24 hours, respectively, are shown. S-24-12 and S-24
-24 indicates a seawater sample obtained by adding about 24 g of KCu-1-1 beads to 10 liters of seawater and stirring the mixture, and after 12 hours and 24 hours, respectively. Cu ²⁺ in the collected seawater sample was as shown in Table 13,
It is in the range of 1 to 3.7 ppm, and in this range, the germs in the seawater are significantly reduced as compared with the sample S-0.
It has been clearly shown that KCu-1-1 beads have an antibacterial effect against various bacteria existing in seawater.

[0060]

[Table 13]

Example 7 The apparent densities of the finely pulverized products of the antibacterial compositions of Examples 2 to 5 were measured. Table 14 shows the results. In Table, d ₁ represents the apparent density when packed lightly, d ₂ represents the apparent density when the vibration filling. Each measuring method is as follows. d ₁ (apparent density when lightly filled): Powder was placed in a 200 ml measuring cylinder, lightly vibrated, and after the powder settled, the volume and weight of the powder were measured and calculated. d 2 _(apparent density when the vibration filling): is vibrated in 200 ml graduated cylinder while putting powder after the powder settled, further repeated vibrations, capacity and weight of the final powder was calculated by measuring . The dried product (molded product) of Example 5 (B-3-AZ) dried at 110 to 120 ° C. was pulverized into fine powder (Dav = 2.54 μm), and d ₁ = 0.21 and d ₂ = Was 0.29. On the other hand, when the molded body fired at 645 to 650 ° C. for 2 hours was made into a fine powder (Dav = 2.88 μm), d ₁ = 0.34 and d ₂ = 0.50. From the comparison of these values, it is clear that the sintering degree increases through the firing step of the present invention, the bonding force between the powders increases, and the mechanical strength of the molded body increases.

[0062]

[Table 14]

──────────────────────────────────────────────────の Continued on the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) A01N 59/16 A01N 25/08 A01N 59/20 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (7)

(57) [Claims] (1) Silica gel is used as the main base material, and
Consists of silver, copper and zinc ionically bonded to silica gel
Holds at least one antibacterial metal ion selected from the group
Is a sintered body of particles having an antibacterial aluminosilicate layer
A pore volume of at least 0.2 cm ³ / g
Both have a specific surface area of ^70m 2 / g, and the SiO ₂ containing
The content is 65-90% by weight and does not include an inorganic binder.
Antibacterial composition. 2. The antimicrobial composition according to claim 1, wherein the average pore size is at least 50 Å. 3. The antibacterial composition according to claim 1, wherein the antibacterial metal ion is silver ion, and the silver content is at least 0.2% of the anhydrous antibacterial composition. 4. The antimicrobial composition according to claim 1, wherein the antimicrobial metal ion is a copper ion and the copper content is at least 0.5% of the anhydrous antimicrobial composition. 5. The antimicrobial composition according to claim 1, wherein the antimicrobial metal ion is a zinc ion, and the zinc content is at least 3% of the anhydrous antimicrobial composition. 6. The antibacterial composition according to claim 1, which is a water treatment agent. 7. A step of: 1) treating silica gel with an alkali solution and an aluminate solution to substantially fix an aluminosilicate layer containing an ion-exchangeable metal on the active surface of the pores of the silica gel matrix; 2) Silver, copper and zinc are treated with a salt solution containing at least one metal ion selected from the group consisting of zinc to form bactericidal metal ions in the aluminosilicate layer,
A step of forming an antimicrobial layer, and 3) using the obtained antimicrobial composition with an organic binder.
The method for producing an antibacterial composition according to claim 1, comprising a step of performing a heat treatment at 350 to 800 ° C.