JPH0699174B2 - A joint material composition having antifungal and antibacterial properties - Google Patents

Description

TECHNICAL FIELD The present invention relates to a joint material composition having antifungal and antibacterial properties. More specifically, the present invention relates to a novel joint material composition having antifungal and antibacterial properties, which has a preferable action against general bacteria and fungi (fungi).

BACKGROUND ART As is well known, jointing materials are widely used in tile construction and the like. Joint filling is usually carried out after a certain curing period after attaching the coil, but as the joint material used for this, cement-based materials mainly composed of inorganic materials are mainly used, and sometimes organic materials are mainly used. Also used are synthetic polymer materials (sealing agents for construction, etc.). The former on-site mix type jointing materials include white cement, cement such as Portland cement,
Fine aggregates such as river sand and silica sand, admixtures such as methyl cellulose and ethyl cellulose, and in some cases, alkali-resistant pigments are usually added and used for the preparation. In addition, the above-mentioned fine bone agent, admixture and pigment are added to cement, and a water-proofing agent and organic antifungal agent are added and mixed in advance to this mixture. So-called ready-made blended joint materials to be provided are also commercially available. Examples of commercially available ready-made joint preparations include Inameji (Ina Ceramics Co., Ltd.), Medifit (light ceramics), Tyrone for joints (Onoda Construction Materials), NS joint cement (Nippon Kasei) and the like. As an organic visual material made of the above-mentioned synthetic polymer material, for example, an acrylic resin emulsion-based interior joint material is commercially available. Examples of this type include, for example, porpoise-S-
31 is mentioned.

In recent years, it has been strongly demanded that each of the above-mentioned organic or inorganic joint materials has antibacterial properties and especially antifungal properties. However, the existing organic antifungal agents added to the joint material for the purpose of satisfying such requirements have insufficient antifungal effect, and particularly lack the long-term sustainability of the antifungal effect. After the clogging of the joint, evaporation and elution loss of the organic fungicide itself is considerably larger than that of the joint material with the passage of time, so that there is a problem in the long-term sustainability of the fungicide prevention effect. Further, addition of an antibacterial zeolite to a joint material as an inorganic antibacterial agent has been proposed, but there are still problems to be improved in terms of mildew resistance and weather (light) resistance (Japanese Patent Laid-Open No. 243665/1987). ).

Problems to be Solved by the Invention By improving the drawbacks of the existing inorganic or organic joint fillers, and imparting excellent antifungal and antibacterial properties to the joint fillers, it has preferable physical properties to exert the effect for a long time. It is a main object of the present invention to provide a stable joint material composition.

Means for Solving the Problems The present inventors mixed an antibacterial composition containing silica gel, which has a film of an aluminosilicate containing a metal ion having a bactericidal action on the surface of silica gel as a matrix, into a joint filler to conduct an antibacterial test. When a weather resistance test was conducted, extremely satisfactory results were obtained. The present invention has been completed against the background of such facts.

INDUSTRIAL APPLICABILITY The present invention has a novel antibacterial composition characterized by having a film of aluminosilicate holding metal ions having a bactericidal action on the surface of silica gel and antifungal and antibacterial properties including a known joint material composition. A joint material composition is provided.

The antibacterial composition used in the present invention will be described. First, the silica gel as a raw material used for preparing the antibacterial composition will be described.

As is well known, silica gel has SiO ₂ as a main component and has the general formula (S
It is an amorphous porous material represented by iO ₂ ) _x (H ₂ O) _y .
The above x and y represent the polymerization numbers of SiO ₂ and H ₂ O, respectively. Silica gel is desiccant, adsorbent, catalyst carrier, paper,
As a filler for rubber and plastics,
It has been found to be more versatile than it used to be. Silica gel is commercially available in various sizes in the form of granules, spheres, and crushed products, but most of them have a SiO ₂ content of 99.5% or more, and impurities such as trace amounts of Na ₂ O and Fe ₂ O. ₃ , MgO, CaO, A
l ₂ O ₃ etc. are included. Although the physical properties of commercially available silica gel vary depending on the manufacturer, its pH is in the range of 4 to 8, the true specific gravity is 2.2, the pore volume is 0.3 to 0.8 cm ³ / g, and the specific surface area is 10
0 to 800 m ² / g (by BET method; the same applies unless otherwise specified in the present specification) and pore size 20 to 200
Is a product with a physical property value of Å currently on the market in Japan? Examples of domestic silica gel sellers / manufacturers include Fuji Davison Co., Ltd., Asahi Glass Co., Ltd., Mizusawa Chemical Co., Ltd., Toyota Kako Co., Ltd. An example of a trader is Grace (Grace Chem. Co.). In the latter case, silica gel (pH of suspension = 5 to 7) having various particle sizes (eg 10 to 30 µm; 0.5 to 1 mm; 1 to 3 mm) and different physical properties is produced. For example, pore volume 0.3-1.8 cm ³ / g, specific surface area 20-750 m ²
Silica gels with pore sizes of / g, large, medium and small are commercially available. W seen in the GWP XWP series
The pore size of ide porous silca gel is very large, 250-1500
It spans Å.

The silica gel used as the material of the present invention may be in the form of powder, particles, or a molded form, but in consideration of the case where chemical treatment of silica gel is carried out by the method described below, fine-form silica gel is preferred. . Furthermore, it is desirable that the pores are innumerably developed inside and that the pore diameter and the specific surface area are large. For example the pore volume as silica gel material of the present invention is preferably at least ^{0.3cm 3 / g, 0.4cm 3 /} g or more of the more preferred.
Further, the pore size of silica gel is preferably as large as possible, preferably at least 50 Å or more, and more preferably 70 Å or more. Furthermore, regarding the specific surface area, at least 100 m ² / g is preferable, and further 200 m ² / g
The above is more suitable.

The reason why the silica gel material having the above-mentioned characteristics is preferable is based on the following. That is, silica gel having the above-mentioned physical properties is very porous, and the surface of the pores thereof is extremely active. The chemical treatment of such silica gel is carried out by the method described below to form an aluminosilicate film on the active surface of the pores, and then, when the sterilizing metal is stably held by ion exchange, the chemistry involved in the reaction There is an advantage that chemical species and metal ions are rapidly diffused so that the chemical reaction proceeds smoothly on the surface of the silica gel pores. In addition, the bactericidal metal in the antibacterial composition of the present invention, as described above, is almost uniformly distributed in a preferred state on the surface of the silica gel pores, and dissociation of dissociated bactericidal metal ions in the pores is It is carried out quickly, and the growth of the fungi is suppressed and the fungi are killed in a state where the contact area between the bactericidal metal ions and the fungi is large.

The metal ion having a bactericidal action may be a metal ion having substantially antibacterial properties and bactericidal properties, and the type thereof is not particularly limited.

Typically, silver, copper, zinc, mercury, tin, lead, bismuth,
There are cadmium and chromium, and these metals can be used alone or in combination.

In the present invention, the aluminosilicate refers to one represented by the following general formula.

Where x and y are the coefficients of the metal oxide and silicon dioxide, M is an ion-exchangeable metal, n is the valence of M,
z represents the number of water molecules. M is usually a monovalent metal such as Li, Na, K, or may be NH ₄ ⁺ . Furthermore, it may be partially or completely replaced by a divalent metal such as Mg, Ca, Sr.Ba, Mn, Ni, Co or Fe.

The film made of the aluminosilicate described above may be crystalline (zeolite) or amorphous, or both may be present together. The thickness and composition of the aluminosilicate film can be adjusted by the physical properties and amount of the silica gel raw material used, the alkali concentration, the amount of aluminate added, the reaction temperature, the reaction time, and the like. In either case of crystalline or amorphous, the SiO ₂ / Al ₂ O ₃ molar ratio is preferably in the range of 1.4-40. Typically, an A-type zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 1.4 to 2.4, an X-type zeolite having the above ratios of 2 to 3 and a Y type zeolite of 3 to 6, or SiO ₂ / Al ₂
Amorphous aluminosilicates with a molar ratio of O ₃ of mainly 1.4 to 30, or a mixture of the abovementioned crystalline and amorphous aluminosilicates are used.

Next, a method for producing the antibacterial composition according to the present invention will be described.

The antibacterial composition according to the present invention is obtained by chemically treating porous silica gel with an alkali solution and an aluminate solution.

As the alkaline solution, for example, a solution of an alkali metal hydroxide such as NaOH, KOH, or LiOH is used, and the treatment is carried out while keeping the aqueous phase alkaline, for example, pH in the range of 9.5 to 11. On the other hand, as the latter aluminate solution, for example, an alkali metal aluminate solution such as NaAlO ₂ , KAlO ₂ or LiAlO ₂ is used, and the chemical treatment of silica gel using the alkali solution and the aluminate solution is performed. It is performed at room temperature or under heating. By such a chemical treatment, SiO ₂ existing on the surface of the pores of silica gel reacts to form an aluminosilicate film containing an ion-exchangeable metal on the active surface of the pores. The antimicrobial composition of the present invention has a pore volume of at least 0.3 cm ³ / g and a specific surface area of at least 100 m ² / g, which is preferable antibacterial to promote the sterilization rate against fungi ~ It is also necessary to exert the bactericidal power.

The silica gel that has been subjected to the chemical treatment is washed with water to remove excess alkali and metal components existing in the solid phase.
For the water washing, either a batch method or a currum method may be applied. Next, ion exchange is carried out to hold the antibacterial to sterilizing metal ions in the film. That is, a metal ion having a bactericidal action, preferably silver, copper, zinc, mercury,
It is treated with a neutral or slightly acidic solution of a salt containing one or more metal ions selected from the group consisting of tin, lead, bismuth, cadmium and chromium. As the liquid for example _{AgNO 3, Cu (NO 3)} 2, nitrates such as _{AgNO 3 -Zn (NO 3) 2} , sulfates such as _{ZnSO 4, SnSO 4, CuSO 4} -SnSO 4, AgCl
_{O 4, Cu (ClO 4)} 2, Zn (ClO 4) 2, Cd perchlorate such as _{(ClO 4) 2, ZnCl 2} , ZnCl 2 hydrochloride as -CdCl _2, Ag- acetate,
Organic acid salts such as Zn-acetate, Cu-tartrate, Cd-citrate are used. Furthermore, a single or a plurality of germicidal metals can be ion-exchanged in the aluminosilicate coating M
Then, at room temperature or under heating, ion exchange is carried out to carry out the step of stably supporting a predetermined amount of sterilizing metal in the film by ionic bonding to prepare an antibacterial composition having silica as a matrix of the present invention. . There may be coexistence of other non-antibacterial metal ions in the bactericidal salt-containing liquid used for the above ion exchange. The substitution rate of the sterilizable metal with the ion-exchangeable metal M in the film can be adjusted by the concentration and composition of the salt solution containing the sterilizing metal, the reaction temperature and the time during the ion exchange, and the like. By adjusting the preparation conditions of the aluminosilicate film and the ion exchange conditions of bactericidal metal ions,
The total amount of sterilizing metal, for example 0.003-0.5 mmol / 100m
It is also possible to keep it at ² (based on the surface area of 100 m ² of the anhydrous antibacterial composition). By adjusting the liquidity at the time of ion exchange as described above, antibacterial to bactericidal aluminosilicate film formed on the active surface of the silica gel pores of silver, copper, zinc and other bactericidal metal ions Due to the generation of products based on hydrolysis such as oxides and basic salts, the formed antibacterial film is contaminated and becomes impure, resulting in the original antibacterial-bactericidal ability of the antibacterial composition. It is possible to prevent the tendency to decrease. Instead of the above-mentioned ion exchange of the bactericidal metal ion-containing liquid, ion exchange may be carried out using an organic solvent such as alcohols and esters, or using a mixed system of solvent and water. For example, when substituting the sterilizing metal ion Sn ^2+, which is susceptible to hydrolysis, by ion exchange with the ion-exchangeable metal M in the film, SnO can be obtained by using an alcohol solvent such as methyl alcohol or ethyl alcohol. Since it is possible to prevent SnO ₂ , a basic tin compound, etc. from depositing on the film, it is possible to prevent the phenomenon that the antibacterial activity of the film is lowered. Next, the silica gel that has been subjected to the above chemical treatment is washed with water until the sterilizing metal ions are no longer observed in the liquid, and then dried at 100 to 110 ° C to finally prepare the sterilizing composition of the present invention. . When it is necessary to further reduce the water content depending on the use of the composition, drying under reduced pressure may be performed, or the heating temperature may be increased to 200 to 350 ° C. to remove water.

The total amount of bactericidal metal in the obtained antibacterial composition, in order to exert a preferable antibacterial ~ bactericidal activity against bacteria and fungi, and also to show an algae-preventing effect, may be 0.003 mmol / 100 m ² or more. Preferably, more preferably 0.005 mmol / 10
It is 0 m ² or more [based on the surface area of 100 m ² of the anhydrous antibacterial composition], and usually in the range of 0.03 to 0.5 mmol / 100 m ² .

When two or more bactericidal metals are used, the total amount thereof is preferably within the above range.

The antibacterial composition used in the present invention is prepared by the above-mentioned method, but when it is added to the joint material, there is no limitation on the particle size thereof. However, since the average particle size of commercially available cement-based joint materials is often about 10 μm, the particle size of the composition may be adjusted using a crusher according to this.
By taking such means, it is possible to easily mix and homogenize the joint material and the antibacterial composition. Next, the antibacterial composition exhibits an antifungal and antibacterial effect which is preferably contained in the range of 0.1 to 25% by weight with respect to the entire anti-fungal joint material composition of the present invention on the anhydrous basis. Desirable to do. Further, in order to maintain the above effect for a long period of time, the content of 1% by weight or more is more desirable. On the other hand, if the content exceeds the upper limit of 25% by weight, the mechanical strength of the joint material tends to deteriorate with the addition of the added amount.

The known joint material composition as referred to in the present invention includes all joint material compositions that are currently known.

As the inorganic material, there is a joint material composition containing a cement material as a main component, for example, white cement, cement such as Portland cement, cement mortar, lime cement mortar, a mixture of fine aggregate and an admixture, and if necessary, Ingredients such as inorganic pigments and other waterproofing agents may be added. The joint material composition of the present invention can be obtained by adding a predetermined amount of the above-mentioned antibacterial composition particles or granular products to such a known joint agent composition and mixing and homogenizing the mixture. The joint material composition of the present invention can be put to practical use by adding 25 to 50% of water and mixing them.
As an expedient method, the antibacterial composition used in the present invention may be added to a commercially available cement-based joint material in a necessary amount and wet-mixed before use. For example, an organic joint material such as one mainly composed of an acrylic resin-based polymer emulsion can be used, and the above-mentioned antibacterial composition is added so as to have a content within the above-mentioned range and uniformly dispersed. Let it be used.

Action The antibacterial composition, antifungal, and antibacterial joint material composition according to the present invention have the following actions.

The silica gel used as the matrix of the antibacterial composition is porous and its pore surface is active. Therefore, when forming an aluminosilicate film or performing ion exchange, chemical species and metal ions are rapidly diffused, and the chemical reaction rapidly proceeds on the silica gel surface.

Since the pore size of the antibacterial composition having the silica gel of the present invention as a base is larger than that of the known aluminosilicate antibacterial agent, the bactericidal metal ion based on the dissociation of the composition is It diffuses in the pores and easily comes into contact with fungi. On the other hand, an antibacterial composition having a known aluminosilicate as a matrix, for example, in an antibacterial zeolite, since its pore size is small, it takes time to diffuse dissociated bactericidal metal ions, and in some cases, with fungi. In some cases, it was impossible to contact them. Therefore, even if the apparent specific surface area is increased by using the porous aluminosilicate particles, the area where the germicidal metal and the bacteria can contact is not substantially increased, and the antibacterial performance is also increased as expected. I didn't.
In other words, even if the sterilizing metal was present on the surface of the mother body, there was a dead space that could not come into contact with the bacteria.

The antibacterial composition according to the present invention does not have such a situation, and all bactericidal metals present on the surface of the mother can contact the bacteria and act effectively.

Further, in the present invention, since the matrix silica gel is coated with aluminosilicate substituted with a sterilizing metal, the amount of useless sterilizing metal present inside, which does not come into contact with bacteria, is drastically reduced. .

Due to the above two factors, the effective utilization rate of the sterilizing metal, that is, the movement of the metal present on the surface against the used metal is significantly improved, and it is possible to obtain excellent antifungal and antibacterial performance with a small amount of use. it can.

Further, the antibacterial composition used by being mixed with the joint material of the present application not only has antibacterial to bactericidal action but also retains the original hygroscopic property of silica gel. The antibacterial composition of the present application is a kind of electrolyte and has an excellent ability to retain bactericidal metal, which dissociates in a hygroscopic state to easily release bactericidal metal ions. The metal ions have the effect of easily diffusing in the pores and contacting the fungi to kill them.

Therefore, when the antifungal and antifungal joint material composition of the present application is prepared by mixing the antibacterial composition with the joint material, the discoloration of the joint material composition observed upon light irradiation due to the presence of a large amount of metal, It has become possible to obtain a joint material composition having a higher antibacterial activity, which is more excellent in weather resistance by reducing changes in physical properties such as coloring.

Reference examples for the preparation of antibacterial compositions for use herein are described below.

Reference Example-1 This example relates to a preparation example of the antibacterial composition of the present invention in which silica gel is used as a matrix and silver and zinc are combined as a sterilizing metal.

Silica gel [Toyota Corporation's spherical silica gel (specific surface area,
450m ² / g; Pore diameter, 60A; Pore volume, 0.75ml / g; Particle diameter, 40m
esh pass)] 2.5 l of demineralized water was added to about 1.3 kg, and then the mixture was stirred at 400 to 450 rpm to form a homogeneous slurry liquid. On the other hand, 0.5N sodium hydroxide solution was gradually added to finally make the pH of the slurry liquid 9.5 to 10.
It was adjusted to 0. For the above slurry liquid
About 2.6 l of sodium aluminate aqueous solution with a concentration of 0.27 mol / l
Was added, the slurry liquid was heated at 20 ° -23 ° C. for about 15 hours,
The aluminosilicate film was formed on the surface of the silica gel pores by stirring at 450 to 500 rpm. Then, filtration was performed, and the obtained solid phase was washed with water to remove excess alkali and unreacted sodium aluminate existing in the solid phase. In this case, the pH of the liquid upon washing with water was maintained at about 9.
As AgNO ₃ -Zn (NO _{3) 2} mixture (AgNO ₃ and Zn (NO _{3) 2} with respect to the washing ends already solid phase, respectively, water-diluted solution containing 0.6M and 0.2 M; pH = 4.1) was added and the resulting mixture was kept at 20 ° -21 ° C. and continuously stirred at 450-500 rpm for about 15 hours. The above-mentioned ion exchange reaction is carried out to prepare an antibacterial composition containing bactericidal silver and zinc, which is then rinsed with water to remove excess silver and zinc present in the solid phase. It was The washed product was dried at 100 ° to 110 ° C to prepare an antibacterial composition containing the silica gel of the present invention as a matrix and silver and zinc as bactericidal metals.

The specific surface area of the antibacterial composition prototyped in Reference Example-1 is
319 m ² / g (measured by N ₂ gas adsorption of BET), pore volume was 0.67 cm ³ / g, and the quantitative values of silver and zinc were 3.79% and 0.83% (anhydrous basis), respectively. It was The amount of silver and zinc per 100 m ² of surface area of the antibacterial composition (anhydrous basis) obtained in Reference Example-1 were 0.11 mmol and 0.04 mmol, respectively.

As an antibacterial activity evaluation test of the inorganic and organic joint filler compositions according to the present invention, a mold resistance evaluation test and a change over time in the number of bacteria by the shake flask method were carried out.

Mold Resistance Evaluation Test The mold resistance test was conducted according to the test method of ASTM G-21 using a test piece prototyped by the method described below. The composition of the medium is KH ₂ PO ₄ (0.7 g), K ₂ HPO ₄ (0.7 g), MgSO ₄
7H ₂ O (0.7g), NH ₄ NO ₃ (1.0g), NaCl (0.005g), FeSO
_{4 · 7H 2 O (0.002g)} , ZnSO 4 · 7H 2 O (0.002g), MnSO 4 · 7H 2 O
A medium consisting of (0.001 g), agar (15 g), and 1000 ml of pure water was used. As a test bacterium, Aspergillus ni
ger (ATCC9642), Penicillium funiculsum (ATCC964
4), Chaetomium globosum (ATCC6205), Trichoderma
T-1 (ATCC-9645), and Aureobasidium pullulans
(ATCC9348) was used, and these bacteria were mixed and inoculated.

The culture was carried out at a relative humidity of 85 to 95% for 30 days, and the test results were evaluated in the following 5 stages.

Evaluation test of antibacterial activity by shake flask method Using a fungus (Aspergillus niger) as an evaluation test of antibacterial activity of the joint material composition of the present invention and the joint material composition of the comparative example, the change over time in the number of bacteria by the shake flask method The measurement was performed. The measurement outline is described below.

(I) Preparation of Aspergillus niger bacterium solution-Conidia of the test bacterium, which had been cultivated for 7 days at 25 ° C using a potato dextrose agar slant medium, were suspended in physiological saline containing sterile 0.05% polysorbate 80 to give 10 ⁷ cells / A suspension (ml) was prepared, and this was diluted at appropriate times and used for the test.

(Ii) Shake flask method-Two specimens (about 10 x 10 mm; thickness about 3 mm) are placed in a 200 ml constant volume flask containing 70 ml of phosphate buffer, and a test bacterial suspension is further added to ~ 10 ⁵ cells. / m
I tried to be l. The resulting mixture is then 25 ± 5 ℃
The cells were shaken at 37 ° C. and acted for a predetermined time, and the viable cell count was measured over time. When measuring the viable cell count, the medium described below was used, 0.1 ml of the liquid was dispersed therein, and the number of viable solids was measured after 48 hours at 30 ° C.

(Iii) Strain used-Aspergillus niger IFO-31125 (iv) Medium-fungus (Aspergillus niger); Sabouraud De
xtrose Agar (BBL); Example-1 This example relates to the preparation of a joint material composition having antifungal and antibacterial properties, and the antibacterial activity test thereof.

In this example, a molded article of the inorganic joint material composition of the present invention was prototyped, and a mold resistance test was conducted by using the molded article.

Commercially available joint material mixture consisting of Portland cement, river sand, and methylcellulose admixture (average particle size = 11μ
m), the antibacterial composition obtained in Reference Example-1 (surface area 319 m ² / g, pore area 0.67 cm ³ / g, Ag = 0.11 mmol / 100 m ² , Zn = 0.04 mmol / 100 m ² ) Finely pulverized product (average particle size 10 μm) as its anhydride is 1.0% with respect to the entire joint material composition having antifungal and antibacterial properties, and
It was added to be 2.0%. The above mixture is V-
Blended to homogeneity using a mixer. Next, about 35% of water was added to the mixture, which was subsequently mixed, and then pressed into a plate-shaped molded body of 50 × 50 mm (thickness of about 3 mm). The obtained molded product was air-dried, and a mold resistance evaluation test was conducted by using the same, and the results shown in Table 2 were obtained.

Indicated on the specimen (50 × 50 mm; thickness about 3 mm) of the joint material composition containing 1.0% and 2.0% of the indicated antibacterial composition (finely pulverized product of the composition obtained in Reference Example-1) As did
The evaluation value was 0, and no generation of mold was observed.
On the other hand, comparative sample 1-BL containing no antibacterial composition
(50 × 50mm; thickness about 3mm) The evaluation value was 2, and bacterial growth was observed over 10 to 30% of the total surface area of the subject. It is apparent from the above-mentioned test that the anti-mold and anti-bacterial joint material composition of the present invention exhibits excellent anti-mold property.

Example-2 This example relates to the preparation of a joint material composition having antifungal and antibacterial properties and the antibacterial activity test thereof.

In this example, a molded body of the organic joint material composition of the present invention was manufactured as a prototype, and the mold resistance test was carried out using the molded body.

As the antibacterial composition, the antibacterial composition obtained in Reference Example-1 (surface area 319 m ² / g, pore volume 0.67 cm ³ / g, Ag = 0.11)
Millions / 100 m ² , Zn = 0.04 mmol / 100 m ² ) of a finely pulverized product having an average particle size of 10 μm is 1.5% as shown in Table 3 with respect to the entire organic joint filler composition having antifungal and antibacterial properties.
And 4.0% content was added. In this case, an acrylic resin emulsion (interior joint material) was used as the organic joint material. This was mixed with the above-mentioned antibacterial composition to form a paste-like mixture, and then about 35 kg
/ cm ² · G pressure-molded joint material molding (50 x 50 mm;
The thickness is about 3 mm). A mold resistance test was carried out by the method described above using the above test piece.

The test results are shown in Table 3. An organic joint material composition comprising an antibacterial composition retaining silver and zinc as a bactericidal metal used in the present invention, As can be seen from the test pieces 2-1 and 2-2, the evaluation values of the mold resistance test were all 0, and no mold growth was observed, indicating excellent antibacterial activity. The test piece 2-BL containing no Naho antibacterial agent showed mold growth, and the evaluation value was 1
It was in the middle of ~ 2.

Example 3 This example relates to preparation of an inorganic joint filler composition having antifungal and antibacterial properties, and a test of antibacterial activity using the same. As an antibacterial activity test, the change of fungus with time was measured.

Portland cement (75% by weight), river sand (15% by weight)
And the antibacterial composition (surface area 319 m ² / g, pore volume 0.67) obtained in Reference Example-1 with respect to the inorganic joint material composition (average particle diameter 11 μm) consisting of and methyl cellulose admixture (10% by weight) cm ³ / g, Ag = 0.11 mmol / 100 m ² , Zn = 0.04
Millimeter / 100m ² ) finely pulverized product (average particle size 10 μm)
As an anhydride thereof, it was added so as to be 1.0% with respect to the entire joint material composition having antifungal and antibacterial properties. About 35% of water was added to the above mixture, and after mixing, it was molded into a plate-shaped molded body of 50 × 50 mm (thickness: about 3 mm). The molded body is further cut into small test pieces 3
-1 (about 10 x 10 mm; thickness about 3 mm) and then air dried.
A comparative small test piece 3-BL containing no Naho antibacterial agent was molded in the same manner as above and then air-dried.

An evaluation test of antibacterial activity was conducted by the above-mentioned shake flask method using the above-mentioned small test piece. In the test, the fungus Aspergillus niger was used and the time-dependent change in the number of bacteria was measured by the shake flask method.

Comparative Example-1 This example relates to preparation of a comparative inorganic joint material and a test of antibacterial activity using the same. As the antibacterial activity test, the change of fungus with time was measured.

Portland cement (75% by weight), river sand (15% by weight)
Antibacterial zeolite (NaAgZnZ; Ag = 3.97%; Zn = 1.27% (however, as an anhydride content) to an inorganic joint filler composition (average particle diameter 11 μm) consisting of and methylcellulose admixture (10% by weight) ); An average particle diameter of 3.4 μm; Z = matrix of A-type zeolite) as a fine powder of an antibacterial zeolite as an anhydride thereof.
It was added to 0%. About 3 for the above mixture
50 × 50mm (thickness about 3mm) after adding 5% water and mixing
Was molded into a plate-shaped molded body. The above molded body was further cut into small test piece comparison-1 (about 10 × 10 mm; thickness about 3 m
m) and then air dried.

An evaluation test of antibacterial activity was conducted by the above-mentioned shake flask method using the above-mentioned small test piece.

The test results are shown in Table 4. When the specimen (3-1) formed by molding the joint material of the present invention is used, Aspergillus niger
The viable cell count was 1.2 × 10 ⁴ cells / ml after 6 hours, which corresponds to a mortality rate of 98.6%. After 12 hours, the viable cell count was 6.9 × 10 ² cells / ml and the mortality rate was 99.
Equivalent to 9%. After 24 hours, the fungus is completely dead. On the other hand, when using a specimen (Comparison-1) obtained by molding a joint material composition containing a known antibacterial zeolite, the mortality of Aspergillus niger at 6 hours and 12 hours was 93.0% and It was 99.5%, and the bacterium remained even after 24 hours, and was not completely killed. The change over time in the number of bacteria when a blank test sample (3-BL) containing no Naho antibacterial agent is used is as shown.

The antibacterial metal contents of silver and zinc in the joint materials of Sample 3-1 and Comparative-1 are almost the same, but rather the latter is slightly higher. However, as shown in Table 4, more excellent antibacterial activity was obtained when 3-1 sample was used as compared with Comparative-1.

The difference in the antibacterial activity when using both specimens is the difference in the basic structure between the antibacterial composition containing silica gel as the matrix and the antibacterial agent containing zeolite as the matrix, the difference in the distribution state of the bactericidal metal in the antibacterial agents, and the sterilization. It is considered to be based on the difference in the diffusion rate of metal ions in the pores and the difference in the contact rate between bactericidal metal ions and bacteria.

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Claims (4)

[Claims] 1. An antibacterial composition comprising an aluminosilicate film having a metal ion having a bactericidal action and having a bactericidal action on the surface of silica gel, and an antifungal and antibacterial property including a known joint material composition. Joint material composition. 2. The antibacterial composition comprises one or more metal ions having a bactericidal action selected from the group of metal ions of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium and chromium. The joint material composition having antifungal and antibacterial properties according to claim 1, which holds metal ions. 3. The antifungal agent according to claim 1, wherein the antibacterial composition has a pore volume of at least 0.3 cm ³ / g and a specific surface area of at least 100 m ² / g. And a joint material composition having antibacterial properties. 4. An antibacterial composition, based on its anhydrous basis, with respect to the entire joint material composition having antifungal and antibacterial properties,
The joint material composition having antifungal and antibacterial properties according to any one of claims 1 to 3, which is contained in an amount of 0.1 to 25% by weight.