JPH1025435A - Antimicrobial coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial coating composition which has excellent resistance to weathering and shows an antimicrobial effect sustainable for a long time, by incorporating thereto a antimicrobial composition comprising two specific types of antimicrobial agents both of which contain at least one metal ion selected from among silver, copper and zinc ions. SOLUTION: An antimicrobial composition is prepared which comprises (A) a first antimicrobial agent comprising a porous silica gel having, on its surface, an aluminosilicate film containing at least one metal ion selected from among silver, copper and zinc ions, and (B) a second antimicrobial agent comprising, as a main component, crystalline silicon dioxide containing at least one metal ion selected from among silver, copper and zinc ions. This antimicrobial coating composition is obtained by dispersing and incorporating the antimicrobial composition into a coating composition. This resulting antimicrobial coating composition exhibits desirable antimicrobial and bactericidal activity and has an ability to kill bacteria almost completely, and also has excellent protective ability against mold. Further, since the antimicrobial composition has good dispersibility into a coating, a homogeneous antimicrobial coating composition can be produced with ease.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial coating composition containing a novel antibacterial composition.

[0002]

2. Description of the Related Art Silver having a bactericidal action on the surface of silica gel,
An antibacterial composition characterized by having an antibacterial coating of an aluminosilicate containing an antibacterial metal ion such as copper, zinc, mercury, tin, lead, bismuth, cadmium and chromium is known. Since the antibacterial composition is not only excellent in antibacterial performance against general bacteria but also remarkably excellent in antibacterial performance against fungi, the development of applications using the antibacterial composition is actively conducted. However, in the case of the amorphous antibacterial composition based on silica gel containing the above antibacterial metal ions, when this is mixed with the coating composition, there is a problem of undesired coloring depending on the type of the polymer, and the aging of the molded article. There is a problem of discoloration that causes the discoloration. Therefore, the development of a new material having excellent weather resistance and long-lasting effects has been desired.

[0003]

SUMMARY OF THE INVENTION The present invention provides an antimicrobial coating composition containing a novel antimicrobial agent composition. That is, the present invention provides a first antimicrobial agent having a film of an aluminosilicate containing at least one ion of a metal selected from the group consisting of silver, copper and zinc on the surface of porous silica gel, and silver, copper And an antimicrobial coating composition comprising an antimicrobial composition containing a second antimicrobial agent based on crystalline silicon dioxide containing at least one ion of a metal selected from the group consisting of zinc and zinc.

The first antimicrobial agent is amorphous, and the second
Antimicrobial agents are crystalline. The main component of the first antibacterial agent used in the antibacterial composition of the present invention is silica, preferably 70% by weight or more as SiO ₂ and alumina (A).
l ₂ O ₃ ) of up to 15% by weight, preferably at least 0.1% of silver, preferably at least 0.3% of zinc,
And optionally containing antibacterial 1-3 valent metal ions. The first antimicrobial agent has a pore volume (PV)
Is preferably at least 0.2 cm ³ / g,
More than 0.3 cm ³ / g is more preferable. The pore volume is more preferably 0.3cm ³ /g~1.5cm ³ / g
And most preferably from 0.7 cm ³ / g to
It is in the range of 1.0 cm ³ / g. Specific surface area (SSA)
At least 65m is preferably ² / g or more of taking into account the reactivity of the material, more preferably 90m ² / g or more, and most preferably having a specific surface area in the range of 350～600M ² / g. However, SSA is the value measured by BET of N ₂ gas adsorption method, PV is the measured value by mercury porosimetry, these values being referred to herein is a value measured by the respective methods described above. Further, in the first antibacterial agent, the average pore diameter (PD) is preferably as large as possible, preferably at least 50 angstroms or more, and more preferably 200 angstroms or more.

Further, the bulk specific gravity at the time of vibration filling 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 0.7 g / cm ^3.
0 g / cm ³ , most preferably 0.50 to 0.6
0 g / cm ³ . Since the bulk specific gravity slightly varies depending on the particle diameter, it is necessary to measure the average particle diameter as 1 to 10 microns. In addition, the above description does not mean that it is necessary to be in the above-mentioned bulk specific gravity range in all of the particle size range of 1 to 10 microns, and it is sufficient that the above-mentioned bulk specific gravity range is in any of the above-mentioned particle size ranges. The purpose of this is. The bulk specific gravity serves as a scale for evaluating the degree of firing, and it can be considered that the higher the bulk specific gravity, the more advanced the firing.

The crystalline form of crystalline silicon dioxide, which is the main component of the second antibacterial agent used in the antibacterial composition of the present invention, is not particularly limited, but is preferably cubic.
c) or cristobalite
e) having the crystalline form of The crystallization ratio is not particularly limited, but preferably has a crystallization ratio of 50% or more, more preferably 70-100%. The result of the X-ray diffraction revealed that the second antibacterial agent was composed mainly of the crystal structure of silicon dioxide. The crystalline silicon dioxide preferably contains at least 70% by weight, more preferably at least 75% by weight, most preferably at least 79% by weight. In addition, preferably less than 15% by weight, more preferably less than 11% by weight, most preferably 8% by weight.
It may contain aluminum oxide (Al ₂ O ₃ ) in an amount of up to wt%. The second antimicrobial agent is preferably from 0.4 to 1.
4, more preferably a bulk specific gravity in the range of 0.45 to 1.3. The second antibacterial agent is porous and has a large specific surface area (SSA). Preferably, 0.3 cm
^It has a pore volume (PV) of ³ / g or more, more preferably 0.4 to 1.0 cm ³ / g, and preferably 5 m ² / g.
As described above, it preferably has a specific surface area in the range of 25 to 600 m ² / g, most preferably 350 to 600 m ² / g.

[0007] Both the first antibacterial agent and the second antibacterial agent have a preferable metal ion content depending on the type of metal ion contained. When the metal ions contained in the first antibacterial agent are silver ions, the preferred content is 0.1 to 20% by weight of the weight of the first antibacterial agent, and the contained metal ions are copper and zinc. When it is at least one kind of metal ion selected from the group consisting of, the preferable content is 0.3 to the weight of the first antibacterial agent.
It is 16% by weight. Further, when the contained metal ion is at least one kind of silver ion and a metal ion selected from the group consisting of copper and zinc, the amount of silver ion is 0.1 to 0.1 weight of the first antibacterial agent. Preferably, the amount of at least one ion of a metal selected from the group consisting of copper and zinc is 0.3 to 13% by weight of the weight of the first antibacterial agent.

Similarly, when the metal ion contained in the second antibacterial agent is silver ion, its preferred content is 0.1 to 20% by weight of the weight of the second antibacterial agent. When the ions are at least one ion of a metal selected from the group consisting of copper and zinc, the preferred content is 0.3 to 16% by weight of the second antimicrobial agent. Further, when the contained metal ion is silver ion and at least one kind of metal ion selected from the group consisting of copper and zinc, the amount of silver ion is 0.1 to 0.1 weight of the second antibacterial agent. Preferably, the amount of the at least one metal ion selected from the group consisting of copper and zinc is 0.3 to 13% by weight of the second antibacterial agent. The amount of each metal ion in the present specification is based on the weight of the antibacterial composition in an anhydrous state,
The anhydrous state refers to a state where there is no water bound to the antibacterial composition and no water attached to the surface.

In the antibacterial coating composition of the present invention, the first
The mixing ratio of the antibacterial agent and the second antibacterial agent is arbitrary, and can be selected according to desired antibacterial performance and weather resistance. Generally, the content of the second antimicrobial agent is preferably higher, and the preferred mixing ratio of the first antimicrobial agent to the second antimicrobial agent is 7: 1 to 1: 7, more preferably 2: 1. :
The range is from 1 to 1: 7. In order to prevent discoloration of the paint and to further improve the weather resistance, the content of the second antibacterial agent is preferably equal to or more than the content of the first antibacterial agent. Both the first antibacterial agent and the second antibacterial agent used in the antibacterial coating composition of the present invention have a large specific surface area and are extremely porous. The shape of the antimicrobial composition used in the present invention may be arbitrary, and particularly preferably in the form of fine powder. The antibacterial composition used in the present invention has an advantage of exhibiting a remarkable bactericidal activity not only against general bacteria but also against molds (fungi).

The inorganic antimicrobial agent used in the antimicrobial coating composition of the present invention has higher safety, better dispersibility in the coating composition, and lower evaporation loss than the organic antimicrobial agent. It has the characteristic that there is little. In addition, products containing inorganic antibacterial agents have excellent bactericidal activity against bacteria and fungi,
It has been found that the antifungal effect is maintained for a long time. Moreover, the antibacterial coating composition of the present invention has excellent weather resistance and good physical properties.

A feature of the antimicrobial coating composition of the present invention resides in the use of the novel antimicrobial composition. Therefore, all coating resins and coating formulations containing the same are provided,
The composition containing the antibacterial composition corresponds to the antibacterial coating composition of the present invention. Generally, the coating compositions of the present invention include a film-forming resin. The film-forming resin refers to a resin capable of forming a continuous film, which may be either a solvent-based or an aqueous-based resin, may be arbitrarily crosslinked, and may be a thermoplastic or thermosetting resin. You may.

The coating composition of the present invention preferably contains the antimicrobial composition in an amount of 0.02 to 30% by weight based on the solids weight of the coating composition. When the content is in the range of 0.05 to 20% by weight, weather resistance and physical properties are further improved, so that it is more preferable. When the amount of the antibacterial composition is small, the bactericidal effect tends to be insufficient, and in particular, the antifungal effect tends to be insufficient. On the other hand, even when the amount of the antibacterial composition is more than the above range, the bactericidal and antifungal effects are almost unchanged, and the physical properties of the coating composition may be adversely affected to deteriorate the original performance.

The antibacterial coating composition of the present invention can be produced by mixing the antibacterial composition and a film-forming resin. The shape and particle size of the antibacterial composition used in the present invention are not particularly limited, but are preferably in the form of powder to fine particles. In order to uniformly disperse in the paints, depending on the kind of the paint, fine powder of the antibacterial composition, for example, 10 μm
An antibacterial and antifungal coating composition can be prepared using the following fine powder, more preferably a fine powder of 3 μm or less. In addition, the antibacterial particles, depending on the properties of the coating product,
It can be added to paints in a hydrated or anhydrous state. The germicidal solid particles have good dispersibility in paints, and it is easy to prepare a homogeneous antibacterial and antifungal paint composition. Further, an organic or inorganic dispersant can be used in combination for the purpose of increasing the degree of dispersion of the solid particles of the antibacterial composition in paints and making the particles more homogeneous.

A specific method for preparing the first antibacterial agent used in the antibacterial composition of the present invention is known, and the first antibacterial agent is prepared by using porous silica gel with an alkali solution and an aluminate solution. Chemical treatment to form a non-antibacterial layer made of aluminosilicate ion-bonded to the surface of silica gel (micropores and macropores), and then perform ion exchange using antibacterial metal ions to perform the antibacterial The layer can be converted into an antimicrobial layer, and the resulting antimicrobial composition can be produced by heat treatment. Specifically, the antibacterial composition of the present invention comprises: 1) treating silica gel with an alkali solution and an aluminate solution, and forming an aluminosilicate layer containing an ion-exchangeable metal substantially on the active surface of the pores of the silica gel matrix. 2) Then, the solution is 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 bactericidal metal ions to the aluminosilicate layer, 3) The obtained antibacterial composition is treated with 350-800
It can be manufactured by heat-treating at a temperature of ° C.

The silica gel used as a starting material of the antibacterial composition of the present invention may be any of powder, particles, crushed or molded into pellets, tablets and the like. Raw material silica gel (SiO ₂ ) x · (H ₂ O) y [where x is
And y represent the coefficients of SiO ₂ and H ₂ O, respectively.
Has an innumerable number of internal pores. Considering reactivity, a porous active substance having a large pore diameter and a large specific surface area is preferable. Silica gel is commercially available in the form of granules, spheres, crushed products, powders, molded products (pellets, tablets) and the like, and any shape can be used.

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 _{xM 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, K, or 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 antibacterial layer made of aluminosilicate, which is fixed by ionic bonding on the surface of the silica gel matrix obtained by the above method, are determined by the physical properties of the silica gel material, the amount used, the alkali concentration, the alumina It can be adjusted arbitrarily 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 above-mentioned non-antibacterial layer is formed by using a solution containing at least one metal ion selected from the group consisting of silver, copper and zinc as an antibacterial to bactericidal metal ion. An antimicrobial agent 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 agent, but usually a heat treatment at 350 to 800 ° C. is carried out for a predetermined time. Thereby, the first antibacterial agent used in the present invention can be obtained. When the antibacterial agent is in a powder form, the sintering density does not increase in a treatment in a temperature range of 350 ° C. or lower, and in a treatment in a temperature range of 800 ° C. or higher, the antibacterial activity tends to gradually decrease as the temperature increases. 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 agent 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. The heat treatment is preferably performed in a temperature range of 380 to 550 ° C. because the properties are slightly low. Further, even if the antibacterial composition is a pellet, a tablet, a sphere, or a massive (coagulated) body, the aforementioned 3
The first antibacterial agent can be obtained by selecting and performing an appropriate temperature range in the heat treatment region of 50 to 800 ° C.

In the first antibacterial agent, a required amount of antibacterial metal ion is contained alone or in a complex state (Ag ⁺ , Ag ⁺ -Z).
n ^2+, Ag ⁺ -Cu ^2+, although present in Ag ⁺ -Zn ²⁺ -Cu ^2+, etc.), non-antimicrobial metal ions 1-3 valent therein, for example, monovalent Alkali metal ion, divalent nickel or alkaline earth metal ion, trivalent rare earth element [lanthanoid element; Ln ³⁺ ; elements of atomic symbols 58 to 71 and atomic numbers 21 (Sc), 39 (Y), 57 ( La) plus 17 elements) and perkonium (perconyl state ZrO
²⁺ ) may be present, of course. In addition, ammonium ions such as NH ₄ ⁺ , C
^{_{7 H 15 N 2 +, C}} 8 H 16 N +, Me 4 N + (TMA: tetramethylammonium ^{_{ion), Et 4 N + (TEA}} : tetraethylammonium ^{_{ion), Pr 4 N + (TPA}} : tetrapropylammonium ion ) May be present.

The second antibacterial agent used in the present invention is produced by heat-treating the first antibacterial agent before the heat treatment described above in two stages. As the first stage heat treatment,
In order to remove most of the water contained in the antibacterial agent, 2
The heat treatment is performed in a temperature range of 50 ° C. to 500 ° C. under normal pressure or reduced pressure. Next, high-temperature baking is performed as a second heat treatment to convert the amorphous antibacterial agent into a crystalline antibacterial substance. The firing temperature and time in this case vary depending on the type and composition of the starting material. Usually, firing is performed for a predetermined time (1 to 3 hours) in a temperature range of 800 ° C. to 1300 ° C. to change the crystal structure of silicon dioxide. A crystalline antimicrobial agent for use in the present invention, which is the main parent, is prepared. Here, "to remove most of the water contained in the antibacterial agent" means, specifically, to remove water adhering to the surface. The second stage heat treatment temperature is preferably in the range of 800C to 1300C. 800 ° C
At the following temperatures, crystallization is insufficient, and when an antibacterial polymer composition is prepared using such a fired body, its weather resistance becomes insufficient. On the other hand, in the heat treatment at 1300 ° C. or more,
Crystallization is performed without any problem, and when the antibacterial polymer composition is prepared using such a fired body, the weather resistance is extremely excellent. However, since the antibacterial activity of the antibacterial agent obtained by the heat treatment at or above the upper limit value tends to gradually decrease with an increase in temperature, in order to suppress a decrease in the antibacterial activity of the agent itself,
The heat treatment is preferably performed at 1300 ° C. or lower. A preferred temperature range for the heat treatment is from 800C to 1200C.

The first used as a raw material for the second antibacterial agent
The specific surface area of the antimicrobial agent is large, for example, 350 to 600 m
² / g, which is extremely porous. In addition, since these components are inorganic, they have high heat resistance. When a raw material having such physical properties is heat-treated and crystallized, there is no loss of individual inorganic components in the firing step, and there is an advantage that the chemical composition of the fired body is kept constant. By using such a raw material, the reduction of the SSA and porosity of the fired body is kept moderate, so that the pulverization of the fired body becomes easy.
This has the effect of increasing the antibacterial to bactericidal rate of the finally obtained antibacterial powder against bacteria.

Although it has already been described that ammonium ions may be present in the first antibacterial agent, when the second antibacterial agent is prepared from the first antibacterial agent containing the same, the following is required. In some cases, it is preferable because it produces an effect. For example, NH
When the silica gel containing ₄ ⁺ using an amorphous antimicrobial agent as a host as a raw material, the decomposition gas is generated because accompanied by fine foaming when crystallized by performing this high temperature firing,
Holding the finally obtained antibacterial agent powder more porous,
This has the effect of suppressing the decrease in SSA, and as a result, maintaining the bulk specific gravity and SSA in preferred ranges. Those having such properties have the advantage of increasing the antibacterial to sterilizing rate in order to maintain good contact with bacteria. Further, for example, a second antibacterial agent is changed from a first antibacterial agent containing perconyl ion (ZrO ²⁺ ), a rare earth element series lanthanum ion (La ³⁺ ), and a divalent metal calcium ion (Ca ²⁺ ). When prepared, the presence of Zr ²⁺ , La ³⁺ or Ca ²⁺ has the advantage of improving the heat resistance, weather resistance and discoloration resistance of the finally obtained antimicrobial agent. Further, an antibacterial metal ion (Ag) to be contained in the crystalline antibacterial agent used in the present application.
⁺ , Zn ²⁺ , Cu ²⁺ ) and antibacterial metal ions (La ³⁺
And ZrO ²⁺ ) also have the effect of further increasing the antimicrobial activity due to the difference in binding energy.

The second antibacterial agent is coagulated and is in the form of a glass or ceramic. It is preferable that the second antibacterial agent is coarsely or finely pulverized to have a predetermined particle size. The bulk specific gravity (apparent density) of the pulverized crystalline antibacterial agent varies depending on the physical properties, composition, processing temperature and the like of the raw material, but is usually 0.4 to 1.
It is preferable to prepare the dispersion in the range of 4 in order to obtain a homogenous substance having good antibacterial performance and good dispersibility by combining the antibacterial agent and the polymer.

The particle size of the antibacterial composition suitably used in the antibacterial coating composition according to the present invention is not limited at all, but there is a preferable range depending on the use. For example, generally, antibacterial composition particles having a size of 30 to 100 mesh are used, but in order to achieve a more uniform dispersion in a paint, particles having a smaller particle size, for example, 200 to 300 mesh particles or more are used. It is preferable to use fine particles of several microns to tens of microns. The particle size of the antimicrobial agent can be adjusted by selecting a pulverizer. For example, a fine powder can be obtained by using a JET pulverizer.

The antimicrobial coating composition of the present invention may contain other commonly used components such as the following. For example, polymerization media, stabilizers, weathering (light) compounding agents, antioxidants, activators, polishes, blowing agents, flame retardants, modifiers, brighteners, organic or inorganic pigments, inorganic or organic fillers And various plasticizers and lubricants can be added as needed. Further, it may contain an organic solvent or water.

The effects of the present invention are summarized as follows. (1) The antibacterial coating composition of the present invention comprises: coil and S. Preferred antibacterial against bacteria such as Aureus
It exerts a bactericidal action and not only does not see any growth of the bacteria, but also kills these bacteria almost completely. (2) The antibacterial mixture composed of the first antibacterial agent and the second antibacterial agent based on silica gel used in the antibacterial coating composition of the present invention is compared with a known antibacterial antibacterial zeolite. Since the antibacterial and antifungal properties are very excellent, the coating composition of the present invention containing the antibacterial and antifungal properties also has excellent antibacterial and antifungal properties. (3) The novel antimicrobial coating composition comprising the amorphous first antimicrobial agent and the crystalline second antimicrobial agent of the present invention is an antimicrobial paint composition.
The antifungal effect lasts for a long time. (4) The dispersibility of the antibacterial composition used in the present invention in paints is extremely good, and a homogeneous antibacterial paint composition can be produced extremely easily and economically.

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the scope of the present invention in any way. Evaluation Test Method of Antibacterial Activity In order to evaluate the antibacterial effect and the antifungal effect of the samples of the examples, an evaluation test of an antibacterial activity by a drop method (drop method) and a mold resistance test were performed. (1) Mold resistance evaluation test A mold resistance test of a subject was performed according to JIS Z2911.

The fungus resistance test method (JIS Z2911 compliant) using strain Aspergillus niger IFO-4407 Penicillium funiculosum IFO -6345 Chaetomium globosum IFO-6347 Gliocladium virens IFO-6355 Aureobasidium pulluans IFO-6353 Cladosporium sp ( mixed inoculation of 6 strains)

Preparation of Spore Suspension After the above strain is cultured on a potato dextrose agar slant medium until sufficient spores are formed, the spores are sterilized by 0.005%.
It was suspended in dioctyl sodium sulfosuccinate solution to obtain a single spore suspension. An equal amount of each single spore suspension was mixed to prepare a mixed spore suspension. Medium composition: KH ₂ PO ₄ (0.7 g), K ₂ HPO ₄ (0.
_{7g), MgSO 4 · 7H 2} O (0.7g), NH 4 NO 3
(1.0 g), NaCl (0.005 g), FeSO _{4
· 7H 2 O (0.002g),} ZnSO 4 · 7H 2 O
_{(0.002g), MnSO 4 · 7H} 2 O (0.002
g), agar (15 g), glucose, sodium glutamate, and pure water (1000 ml). The above glucose and sodium glutamate were prepared at 2% and 1%, respectively, in the medium. Evaluation of Test Results The evaluation of test results was performed in the following five stages. However, the following%
Indicates a percentage of the surface area.

−−−−−−−−−−−−−−−−−−−−−−−−−−−− Evaluation symbol Remarks −−−−−−−−−−−−−−−−−− 0 No bacterial growth at all 1 Slight bacterial growth (10% or less) 2 Slight bacterial growth (10-30%) 3 Intermediate bacterial growth (30 〜60%) 4 Growth of intense bacteria (60 to 100%) --------------------------

(2) Evaluation test of antibacterial activity by drop method Escherichia coli IFO-12732 (Escherichia coli): Staphylococcus aureus IFO-12732 (Staphylococcus aureus) Preparation of bacterial bacterial solution 18% at 37 ° C. on a normal agar medium The test cells cultured for 1 hour were suspended in a phosphate buffer (1/15 M, pH = 7.2) and suspended in
0 ⁸ cells / ml suspension build of was used in the test and diluted timely this. Test operation by drop method 1 ml of bacterial solution was dropped on each surface (one side) of a test sample (50 x 50 mm) washed with alcohol cotton, and stored at 25 ° C. The number of bacteria was measured by a pour plate method using a culture medium for measuring the number of bacteria of the liquid sample. The viable cell count was measured after a lapse of a predetermined time. In the above culture, M
Weller Hinton 2 (BBL) medium was used.

Reference Example 1 This example shows a production example of a first antibacterial agent containing silver and zinc as antibacterial metals used in the present invention. In this example, FD gel [silica gel of Fuji Deavison Co., Ltd .; SSA = 450 m ² / g;
Pore volume (PV) = 0.80 cm ³ / g; Pore diameter (PD) = 70 Å; particle size 40 mesh pass] to 430 g, and sodium aluminate 190 g
And 1700 ml of water were added, and at pH = 12.3, about 6
The intermediate composition was synthesized at 0 ° C. for 10 hours with intermittent stirring. After completion of the synthesis reaction, the mixture was filtered, and the solid phase was washed with warm water. After washing, the solid phase is kept at 100 ° C-1
Dried at 10 ° C. The resulting intermediate composition had Na = 4.3.
The composition had a composition of 1% and Al = 5.00% (both on an anhydrous basis). 0.17 M AgNO ₃ -0.40 M Zn (NO ₃ ) based on 120 g of the intermediate composition obtained above.
Was added ₂ mixed solution 240 ml, it was held to ion exchange reaction over 5 hours the reaction temperature at 60 ° C. under continuous stirring. At this time, the pH of the aqueous phase at the time of ion exchange was almost 3.9.
5 was maintained. After the completion of ion exchange, the mixture was filtered and the solid phase was washed with water. Washing was carried out using Ag ⁺
Was carried out until the presence of no. Finally, the washed product was dried at 100 to 110 ° C. Dry product is SiO
₂ = 83.38% and Al ₂ O ₃ = 7.56%. The antibacterial metal content in the dried product was Ag = 2.9.
1%, Zn = 2.81% (both on an anhydrous basis),
SSA = 329 m < ² > / g; V. = 0.73 cm ³ / g
Met. The dried product of the antibacterial agent was made to have an average particle size (Dav) of 3.2 μm by pulverization, and was used for trial production of an antibacterial and antifungal coating composition.

Reference Example 2 In this reference example, a method for producing the second crystalline antibacterial agent used in the present invention will be described. Starting materials for preparing the antibacterial agents of Samples 1 to 7 are the antibacterial agents based on silica gel obtained in Reference Example 1. It also contained a small amount of monovalent alkali metal (Na ⁺ ) as a non-antibacterial metal ion. Using the above powdery starting material, it was preheated at 350 ° C. for 1 hour as shown in Table 1 to remove most of the water. Next, as described in the high-temperature baking, the baking was performed in a temperature range of 800 ° C. to 1200 ° C. for 1 or 2 hours to obtain a fired body of a crystalline antibacterial agent. The obtained massive fired body was coarsened using a crusher, and then JET-pulverized to a fine powder. Samples 1 to 7, which are the second antibacterial agents of the present invention, had SiO ₂ = 83.38% and Al ₂ O ₃ =
It contains 7.56% and its antimicrobial metal contains 3.6 or 3.7% silver and 2.0% zinc.
The average particle size (Dav) of the antimicrobial agent finely divided in this example
Is in the range of 2.9 to 8.3 μm as described in Table 1, and the bulk specific gravity (apparent density) of such powder is 0.40 to 0.40.
1.00 (d ₁ ) and within the range of 0.46 to 1.10 (d ₂ ). However, d ₁ and d ₂ indicate the bulk specific gravity at the time of light filling and at the time of vibration filling, respectively, and the specific measuring method is as follows. Bulk specific gravity (d ₁ ) 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. Bulk specific gravity (d ₂ ) at the time of vibration filling: The powder was put into a 200 ml measuring cylinder while vibrating, and after the powder settled, the vibration was further repeated, and finally the volume and weight of the powder were measured and calculated.

[0035]

[Table 1]

Example 1 In this example, the antibacterial performance of the coating composition was evaluated by the drop method. 100 g of an acrylic resin emulsion paint composed of 70% by weight of an acrylic resin emulsion having a solid content of 43%, 10% by weight of titanium dioxide, 10% by weight of hydroxyethyl cellulose, 8% by weight of Demol EP (manufactured by Kao Soap Co., Ltd.), and water Collected in cans. On the other hand, the first amorphous antibacterial agent (Ag = 2.91%; Zn =
2.81%; SiO ₂ = 84.39%; Al ₂ O ₃ = 7.
46%; Dav (average particle size) = 3.2 μm) and a second crystalline antimicrobial agent (Ag = 3.6%; Al ₂ O ₃ = 7.56)
%; SiO ₂ = 83.38%; Al ₂ O ₃ = 7.56%;
(Dav = 3.7 μm) was added and mixed so as to be 1.5% and 2% by weight of the anhydride based on the entire coating composition. The paints obtained in this example are designated as P-1 and P-2, respectively. In addition, the sample P-BL without an antibacterial composition added for a blank test was also experimentally produced. The number of bacteria is 1 as a typical example of spoilage bacteria.
0 ⁵ / ml B. subtilis diluted in (Bacillus subtilis), Pse
udomonas aeruginosa (Pseudomonas aeruginosa) and E. coli (Escherichia coli)
Of the respective mixed suspensions were inoculated into the paint prepared in the manner described above, and the resulting mixtures were stirred and homogenized.
The cans containing the paint were sealed and cultured at 25 ° C. for one week, and the viable cell count was measured. Table 1 shows the results of this example. In the trial paints P-1 and P-2, no growth of putrefactive bacteria was observed at all, and it was confirmed that the fungi were almost completely killed. P-BL was a paint for a blank test without the addition of an antibacterial agent, in which the growth of bacteria was recognized, and the kill rate was 0.

Example 2 A fungicidal and antibacterial paint P- of the present invention produced in trial in Example 1.
A mold resistance test was carried out using No. 1 and P-2 in the following manner. That is, using a coating composition of P-1 and P-2, a slate plate (50 × 50
m / m), the slate was dried for one week to prepare a test piece. Then, a mold resistance test was conducted using the slate plate according to the method described in JIS.
Performed in accordance with Z2911. Test sample Sample S-1: P-1 paint Sample S-2: P-2 paint Test operation JIS method: The test sample was placed in a petri dish, and the mixed spore suspension was spread thereon until the surface became wet. 2. These petri dishes were cultured at a temperature of 29 ° C. and a humidity of 85 ° C. or higher for 4 weeks, and the state of growth of hyphae formed on the surface of the test sample after the culture was visually observed.

[0038]

[Table 2]

The results of the mold resistance test are shown in Table 2,
The antibacterial coating composition of the present invention shows no mold growth as seen in the test pieces S-1 and S-2, and the antifungal and antibacterial coating composition of the present invention is a known inorganic type. It was confirmed that it had an overwhelmingly excellent antibacterial effect as compared with the antibacterial agent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09D 133/04 PGB C09D 133/04 PGB

Claims (8)

[Claims] 1. A first antibacterial agent having a film of an aluminosilicate containing at least one ion of a metal selected from the group consisting of silver, copper and zinc on the surface of porous silica gel, and silver, copper and An antibacterial coating composition comprising an antibacterial composition containing a second antibacterial agent containing crystalline silicon dioxide as a main component containing at least one ion of a metal selected from the group consisting of zinc. 2. The metal ion contained in the first antibacterial agent is silver ion, and its amount is 0.1 to 2 parts by weight of the first antibacterial agent.
The antibacterial coating composition according to claim 1, which is 0% by weight. 3. The metal ion contained in the first antibacterial agent is at least one of metal ions selected from copper and zinc.
The antimicrobial coating composition of claim 1, wherein the antimicrobial coating composition is a seed, the amount of which is 0.3 to 16% by weight of the first antimicrobial agent. 4. The method according to claim 1, wherein the first antimicrobial agent is 0.1% by weight of the first antimicrobial agent.
2. The composition of claim 1, comprising 1 to 15% by weight of silver ions and 0.3 to 13% by weight of the first antimicrobial agent of at least one ion of a metal selected from the group consisting of copper and zinc. Antimicrobial coating composition. 5. The metal ion contained in the second antibacterial agent is silver ion, and its amount is 0.1 to 2 parts by weight of the second antibacterial agent.
The antibacterial coating composition according to any one of claims 1 to 4, which is 0% by weight. 6. The metal ion contained in the second antibacterial agent is at least one of metal ions selected from copper and zinc.
The antimicrobial coating composition according to any one of claims 1 to 4, wherein the antimicrobial coating composition is a seed, the amount of which is 0.3 to 16% by weight of the weight of the second antimicrobial agent. 7. The method according to claim 7, wherein the second antimicrobial agent is 0.5% by weight of the second antimicrobial agent.
5. The composition of claim 1, comprising 1 to 15% by weight of silver ions and 0.3 to 13% by weight of the second antimicrobial agent of at least one ion of a metal selected from the group consisting of copper and zinc. The antibacterial coating composition according to any one of the above. 8. The antibacterial coating composition according to claim 1, wherein the total amount of the first antibacterial agent and the second antibacterial agent is 0.02 to 30% by weight based on the solid content of the antibacterial coating composition. Item 8. The antibacterial coating composition according to Item.