JPH0986986A - Antibacterial, antifungal and seaweed proofing agent for mixing in cement and hydraulic cement composition using the agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial, antifungal and seaweed-proofing agent for mixing in cement having antibacterial, antifungal and seaweed-proofing activity for a long time by mixing powder of an inorganic compound having antibacterial, antifungal and seaweed-proofing activity with a powdery silicone resin. SOLUTION: This antibacterial, antifungal and seaweed-proofing agent for mixing in cement is produced by mixing at least powder of inorganic compound having antibacterial, antifungal and seaweed-proofing activity with a powdery silicone resin. The powder of inorganic compound is preferably frit powder containing a metal having oligodynamic action, and silver containing frit powder is especially preferable. Silver content of the silver-containing frit powder is preferably 0.1-5wt.% in terms of silver oxide. It is preferable that 0.5-20wt.% of a silicone resin be compounded with 1wt.% of the silver-containing frit powder. The antibacterial, antifungal and seaweed proofing agent is preferably added to a hydraulic cement at the ratio of 0.1-3wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial, antifungal and antialgal agent for cement admixture capable of imparting antibacterial, antifungal and antialgal properties to a hardened cementitious product and a hydraulic property using the same. It relates to a cement composition.

[0002]

2. Description of the Related Art There has been a long-standing demand for antibacterial, antifungal, and antialgal properties of hardened cementitious products, as represented by joints in bathrooms. Algae agents are being developed. These can be broadly classified into organic and inorganic.

[0003] Organic antibacterial, antifungal and antialgal agents include bacteria,
It is effective against mold and algae in the short term, but has poor long-term sustainability and is not fully satisfactory. Inorganic antibacterial, antifungal and antialgal agents include silver, copper and zinc. It utilizes the oligodynamic effect of metal ions,
Although effective for antibacterial and antialgal, it is not satisfactory because of poor antifungal effect. The oligodynamic effect here means that bacteria or microorganisms are adsorbed on the cell wall or condensed in the cell wall to inhibit their growth,
It is an effect that has an anti-algal effect. On the other hand, silicone resin has an indirect antibacterial, antifungal, and antialgal effect because it has an effect of making the surface of the cement-based cured product water-repellent and preventing neutralization, but the effect is small and satisfactory. It was not something.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems in the prior art, and an object of the present invention is to provide a cement admixture having antibacterial, antifungal and antialgal properties over a long period of time. An antibacterial, antifungal and antialgal agent for use and a hydraulic cement composition using the same.

[0005]

[Means for Solving the Problems] The antibacterial / mold / anti-algae agent for admixing cement according to claim 1 of the present invention specifically configured to achieve the above-mentioned problems is at least an antibacterial / mold / mold /
It is characterized in that an inorganic compound powder having an anti-algal action is mixed with a powdered silicone resin.
When a mixture comprising an inorganic compound powder having an antibacterial, antifungal and antialgal action and a silicone resin is added to a hydraulic cement, the antibacterial, antifungal and antialgal effects of the respective cements are dramatically improved by a synergistic effect.

According to a second aspect of the present invention, the inorganic compound powder having an antibacterial, antifungal, and antialgal action is a frit powder containing a metal having an oligodynamic effect. There is a feature.

Further, the antibacterial, antifungal and antialgal agent for admixing with cement according to claim 3 is characterized in that the frit powder containing a metal having an oligodynamic effect is a frit powder containing silver. .

Further, in the antibacterial / mildew / algae control agent for admixing cement according to claim 4, the content of silver in the frit powder containing silver is 0.1 to 5% by weight in terms of silver oxide. Is characterized in that.

Further, in the antibacterial, antifungal and antialgal agents for admixing with cement according to claim 5, the mixing ratio between the silver-containing frit powder and the silicone resin is such that the silver-containing frit powder is 1% by weight. Parts by weight of the silicone resin is 0.5 to 20 parts by weight.

The hydraulic cement composition according to claim 6 is obtained by mixing at least the antibacterial, antifungal and antialgal agent for cement admixture according to any one of claims 1 to 5 with a hydraulic cement. It is characterized by becoming.

The hydraulic cement composition according to claim 7 is characterized in that the antibacterial, fungicidal and antialgal agent for admixing with cement according to any one of claims 1 to 5 is added to the hydraulic cement in an amount of 0.1 to 0.1%.
It is characterized by being added by 1 to 3% by weight.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies, the present inventors have found that when a mixture comprising an inorganic compound powder having an antibacterial, antifungal and antialgal action and a silicone resin is added to a hydraulic cement, the antibacterial properties of the respective cements are increased. The present inventors have found that the fungicidal and anti-algae effects act synergistically to dramatically improve, and have completed the present invention. Hereinafter, embodiments of the present invention will be specifically described. However, the present invention is not limited by these embodiments.

[Constitution] The antibacterial, antifungal and antialgal agent for admixing cement according to the present invention is obtained by mixing an inorganic compound powder having at least antibacterial, antifungal and antialgal action with a silicone resin powder, and further mixing the same. The hydraulic cement composition used was
At least the antibacterial, antifungal and antialgal agents for admixing the cement and the hydraulic cement are mixed. As used herein, "mixing" means that one component is dispersed in another component and the other component is dispersed in one component.

The inorganic compound powder having an antibacterial, antifungal and antialgal action used in the present invention is not particularly limited. For example, silver, copper, zinc and other metals having an oligodynamic effect, particularly containing silver Frit powders Metals having an oligodynamic effect such as silver, copper, zinc, etc., especially calcium phosphate compound powder carrying silver cuprous oxide powder Mixed powder of cuprous oxide and a silver-containing substance Oligodynamics of silver, copper, zinc, etc. Metal powder having an effect, in particular, a compound powder in which silver is supported on ettringite, and the like can be mentioned. These compound powders can be used alone or as a mixed powder. The method for producing the inorganic compound powder having an antibacterial, antifungal and antialgal action is not particularly limited, either.
A conventionally known method can be used.

The antibacterial, antifungal and antialgal agents for admixing cement of the present invention contain a powdery silicone resin, and the hydraulic cement composition of the present invention contains a powdery silicone resin. As the silicone resin, for example, a silicone resin such as polysiloxane can be used, and is not particularly limited as long as it is water-soluble or dispersible in water. Further, these silicone resins may be used alone or as a mixture.

The hydraulic cement to which the antibacterial, antifungal and antialgal agents of the present invention are admixed is not particularly limited, and portland cement, mixed cement, alumina cement, plaster of Paris and the like can be used. In addition, various conventionally known additives such as a high-performance water reducing agent may be added to these hydraulic cements.

As described above, the antibacterial, antifungal and antialgal agents for admixing cement and the hydraulic cement composition using the same according to the present invention comprise an inorganic compound powder having at least antimicrobial, antifungal and antialgal effects and a silicone resin. And an inorganic compound powder having an antibacterial, antifungal and antialgal action, which does not inhibit the setting and hardening of hydraulic cement, From the viewpoint that the action is maintained over a long period of time, it is preferable to use a frit powder containing a metal having an oligodynamic effect,
Further, from the viewpoints of strong antibacterial, antifungal, and antialgal effects and high safety, it is particularly preferable to use a frit powder containing silver. The frit powder is obtained by quenching and pulverizing molten glass.

The case where a frit powder containing silver is used as an inorganic compound powder having an antibacterial, antifungal and antialgal action will be described in detail. Silver is allowed to exist as metallic silver, silver oxide, or other silver compounds in the frit powder. Therefore, as the frit powder containing silver, the components, compositions, and the like are not particularly limited as long as the frit powder contains silver in a known frit powder. The silver content in the frit powder containing silver is
0.1 to 5% by weight, preferably 0.3 to 3% by weight, in terms of silver oxide
% Is more preferred. This is because if the content is less than 0.1% by weight, a sufficient effect is hardly obtained, and if the content exceeds 5% by weight, a suitable effect cannot be obtained, and there is a possibility of discoloration. Further, the frit powder containing silver preferably has an average particle size of 5 to 20 μm from the viewpoint of miscibility with hydraulic cement.

Specific examples of the chemical composition of the frit powder containing silver include, for example, 30 to 40% by weight of SiO ₂ , 1 to ₃ % by weight of Al ₂ O ₃ , 7 to 10% by weight of CaO, B ₂ O ₃ ; 30 to 40% by weight, Na ₂ O; 13 to 2
0% by weight, P ₂ O ₆ ; 0.1-1% by weight, Ag ₂ O;
About 5% by weight.

The method of producing the frit powder containing silver is not particularly limited as described above.
For example, the Si is so adjusted that the final composition after melting is the above composition.
A source, an Al source, a Ca source, a B source ₂ , a Na source ₂ , a P source, and an Ag source are added, mixed, melted under a temperature condition of 1000 to 1200 ° C., and then quenched and pulverized in water. Also, a silver compound is added to a fritted glass that has been fritted in advance,
Again, a method of obtaining a silver-containing frit powder of the above composition by melting, quenching in water, and pulverizing under the above temperature conditions is an antibacterial silver
It is preferable because the antifungal and algal properties are exhibited most efficiently.

Further, the mixing ratio of the frit powder containing silver and the silicone resin is preferably 0.5 to 20 parts by weight of the silicone resin with respect to 1 part by weight of the frit powder. No effect. Furthermore,
Preferably, a mixture of the silver-containing frit powder and the powdered silicone resin is added in an amount of 0.1 to 3% by weight based on the hydraulic cement. This is because if it is less than 0.1% by weight, it is difficult to obtain a sufficient effect, and if it exceeds 3% by weight, a suitable effect cannot be obtained.

[Effects] In this embodiment, the antibacterial
Combination of an inorganic compound powder having a fungicidal and anti-algal action and a silicone resin is one that exhibits much better antibacterial, anti-fungal and anti-algal properties than using each alone,
The mechanism of the manifestation of this synergistic action / effect is considered as follows.

That is, since the silicone resin has water repellency, it is difficult for the microorganism itself and nutrients necessary for the growth of the microorganism to adhere to the surface of the cement-based hardened body, and further, the outflow of alkali from the inside of the cement-based hardened body is prevented. Therefore, an environment suitable for the growth of microorganisms cannot be obtained. But,
When the silicone resin is used alone, the propagation of the microorganism cannot be prevented because the silicone resin itself has no ability to kill microorganisms.

On the other hand, although inorganic compounds having an antibacterial, antifungal and antialgal action have the ability to kill microorganisms, they cannot supply nutrients necessary for growing microorganisms even when used alone. Since the elution amount of the silver component gradually decreases with time and the ability to kill microorganisms decreases, it is impossible to prevent the growth of microorganisms for a long period of time.

However, when an inorganic compound having an antibacterial, antifungal and antialgal action is coexisted with a silicone resin, when both coexist, the microorganisms themselves and nutrients necessary for the growth of the microorganisms become cement-based cured products. It is hard to adhere to, and even if microorganisms adhere, it is sterilized by the silver component, and furthermore, the water-repellent action of the silicone resin does not cause the killing component in the inorganic compound having antibacterial, antifungal and antialgal effects to disappear in a short time, Since it is considered to last for a long period of time, it is considered that it compensates for each other's disadvantages in the case of each of them alone and expresses a strong antibacterial, antifungal and antialgal effect.

[0026]

The present invention will be more specifically described below with reference to examples and comparative examples. However, the present invention is not limited at all by these examples. [Oligodynamic Preparation of frit powder containing a metal having an effect] SiO ₂ 40 wt%, the Al ₂ O ₃ 3% by weight, CaO and 8% by weight, the B ₂ O ₃ 35 wt%, Na
100 parts by weight of a frit containing 14% by weight of ₂ O
g ₃ PO ₄ was added at 3 parts by weight, mixed and melted at 1050 ° C.
The mixture was rapidly cooled by being put into water, and then pulverized by a ball mill to prepare a silver-containing frit powder (sample numbers 1 to 6) having an average particle size of 5 μm. The silver-containing frit powder contains 2.5% by weight of silver in terms of silver oxide.

Separately, C is added to 100 parts by weight of the frit.
10 parts by weight of uO were added and mixed and melted at 1050 ° C., and then a copper-containing frit powder (sample number 7) having an average particle size of 5 μm was prepared by the above-described method. The frit powder containing copper contains 9.1% by weight of copper in terms of copper oxide.

Further, separately, 10 parts by weight of ZnO was added to 100 parts by weight of the frit and mixed and melted at 1050 ° C.
Thereafter, a zinc-containing frit powder (sample number 8) having an average particle size of 5 μm was prepared in the same manner. This frit powder containing zinc contains 9.1% by weight of zinc in terms of zinc oxide.
It is contained.

(Example 1) The above silver-containing frit powder and a powdery silicone resin (Aqua seal 10 manufactured by Sumitomo Seika Co., Ltd.)
-P) was mixed with a V-type mixer in a weight ratio of 2: 1 to 1:20 to prepare an antibacterial / antifungal / algaeproofing agent for cement admixture (sample numbers 1 to 6). Further, an antibacterial, fungicidal, and antialgal agent for cement admixture having the composition shown in Table 1 was mixed using the copper-containing frit powder, the zinc-containing frit powder, and the powdered silicone resin in the same manner, and having the composition shown in Table 1. 7, 8) were produced.

(Example 2) The antibacterial, antifungal and antialgal agents for cement admixture obtained in Example 1 were mixed with ordinary Portland cement to obtain a hydraulic cement composition (sample) having the composition shown in Table 1. Nos. 1 to 8) were prepared.

Example 3 Using the hydraulic cement obtained in Example 2, a disk-shaped specimen (hardened cementitious body) having a diameter of 50 mm and a thickness of 3 mm was molded. The water / cement ratio is 50%. The molded body was cured for 28 days, and then adjusted to pH 7 in CO ₂ gas.
After being soaked in the warm water for 1 year, it was subjected to the following respective tests. "Antibacterial test" Each test specimen was 1.0 × 10 ⁶ cfu /
The cells were immersed in 10 ml of E. coli solution and the number of viable cells was measured 24 hours later. Table 1 shows the results. "Antifungal test" Each of the test pieces separately prepared was exposed to a bathroom for one year, and the occurrence of mold was visually observed. The judgment conditions are as follows. 0: No generation of mold is recognized. 1: Generation of mold is slightly observed. 2: Moderate generation of mold is observed. 3: The occurrence of mold on the entire surface is recognized. Table 1 shows the results. "Algae resistance test" Each of the separately prepared test specimens was exposed to a sunny place in a forest for one year, and the occurrence of algae was visually observed. The judgment conditions are as follows. 0: No generation of algae is observed. 1: Slight generation of algae is observed. 2: Moderate occurrence of algae is observed. 3: Generation of algae is observed on the entire surface. Table 1 shows the results.

(Example 4) As an inorganic compound powder having antibacterial, antifungal and antialgal actions, a powder of a silver-supported calcium phosphate-based compound pulverized to an average particle size of 5 μm, the silicone resin described in Example 1, Using Portland cement, an antibacterial, antifungal, and antialgal agent for cement admixture having the composition shown in Table 1 and a hydraulic cement composition (Sample No. 9) using the same were produced. The silver-supported calcium phosphate compound was prepared as follows.
800 ml of an aqueous solution containing 80 g of phosphoric acid and 40 ml of an aqueous solution containing 4 g of silver nitrate were mixed. Separately, an aqueous suspension containing 100 g of calcium hydroxide was prepared. The mixture was dropped into the calcium hydroxide suspension at a temperature of 40 ° C, and the resulting reaction mixture was aged at 40 ° C for 3 hours while stirring. The obtained reaction mixture was filtered to obtain a powder of a silver-supported calcium phosphate compound. The silver content in this powder was 1% by weight. Using the hydraulic cement composition thus obtained, an antibacterial test, a fungicide test and an algal test were carried out according to the method described in Example 3. The results are shown in Table 1.

(Example 5) As an inorganic compound powder having an antibacterial, antifungal and antialgal action, a powder obtained by pulverizing cuprous oxide (Cu ₂ O) to an average particle diameter of 1 μm and the silicone resin described in Example 1 were used. And ordinary Portland cement, Table 1
And an antibacterial, antifungal and antialgal agent for cement admixture having the composition shown in Table 1 and a hydraulic cement composition using the same (Sample No.
0) was prepared. Using the hydraulic cement composition thus obtained, an antibacterial test, a fungicide test and an algal test were carried out according to the method described in Example 3. The results are shown in Table 1.

(Example 6) As an inorganic compound powder having antibacterial, antifungal, and antialgal action, a compound in which silver is supported on ettringite is pulverized to an average particle size of 5 µm, and the silicone resin described in Example 1 is used. And an ordinary Portland cement were used to prepare an antibacterial / mildew / algicidal agent for cement admixture having the composition shown in Table 1, and a hydraulic cement composition (Sample No. 11) using the same. The silver-bearing ettringite was prepared as follows. 37 g of calcium hydroxide, 12.6 g of aluminum hydroxide and 68 g of anhydrous gypsum are suspended in 1 liter of distilled water,
The temperature was maintained at about 25 ° C and the mixture was stirred well. After stirring, the mixture was aged for 1 hour. Thereafter, 15 ml of an aqueous silver nitrate solution adjusted to a silver concentration of 0.1 g / ml was added, and the mixture was aged for 3 hours. After aging, the precipitate was filtered, and the precipitate was sufficiently washed with distilled water. The precipitate is then collected and
After drying at 50 ° C., the dried product was ground to an average particle size of 5 μm. The silver content in this powder was 1.4% by weight. Using this hydraulic cement composition, an antibacterial test, a fungicide test, and an algal test were carried out according to the method described in Example 3. The results are shown in Table 1.

Comparative Example 1 The method described in Example 3 was carried out using Portland cement (sample No. 12) which did not contain an inorganic compound having antibacterial, antifungal and antialgal activities and a silicone resin. Antibacterial test, antifungal test,
An alga resistance test was performed. The results are shown in Table 1.

Comparative Example 2 The above silver-containing frit powder as an inorganic compound powder having an antibacterial, antifungal and antialgal action,
Using a hydraulic cement composition comprising Portland cement (Sample No. 13), an antibacterial test, an antifungal test, and an algal test were carried out according to the method described in Example 3. The results are shown in Table 1.

(Comparative Example 3) A hydraulic cement composition comprising the silicone resin and Portland cement described in Example 1 without containing an inorganic compound powder having antibacterial, antifungal and antialgal activities (Sample No. 14) Was used to carry out an antibacterial test, an antifungal test, and an algal test in accordance with the method described in Example 3. The results are shown in Table 1.

Comparative Example 4 The above silver-containing frit powder as an inorganic compound powder having an antibacterial, antifungal and antialgal action,
Using a hydraulic cement composition (sample No. 15) composed of an acrylic resin and Portland cement, an antibacterial test, an antifungal test, and an algal test were performed according to the method described in Example 3. . The results are shown in Table 1.

[Comparative Results] As is clear from the results shown in Table 1, antibacterial, antifungal and antialgal agents for admixing cement produced in each Example and hydraulic cements using the same (Sample Nos. 1 to 11) Has antibacterial, antifungal, and antialgal properties that are clearly superior to Comparative Examples (Sample Nos. 12 to 15).

[Table 1]

[0040]

As described above, according to the present invention, the antibacterial / antifungal / algaeproofing agent for admixing cement according to the first aspect comprises at least an inorganic compound powder having an antibacterial / antifungal / antialgal action and a powdery form. Because it is mixed with silicone resin,
When added to hydraulic cement, each has its antibacterial, antifungal,
The anti-algal effect can be dramatically improved by these synergistic effects, and the anti-algal, anti-fungal and anti-algal properties can be maintained for a long period of time.

In the antibacterial, antifungal and antialgal agents for admixing with cement according to claim 2, the inorganic compound powder having an antibacterial, antifungal and antialgal effect comprises a frit powder containing a metal having an oligodynamic effect. As a result, a fine powder containing ionized metal having an oligodynamic effect can be obtained, and the ability to kill microorganisms by metal ions can be exerted for a long period of time.

In the antibacterial, antifungal and antialgal agents for admixing with cement according to claim 3, the frit powder containing a metal having an oligodynamic effect is a frit powder containing silver, whereby the oligodynamic effect is improved. Able to contain silver, which is a strong and safe metal with the ability to kill microorganisms among metals having
A finely divided powder containing ionized silver can be obtained, and the ability to kill microorganisms by silver ions can be exhibited for a long time.

In the antibacterial, antifungal and antialgal agents for admixing with cement according to claim 4, the silver content in the frit powder containing silver is 0.1 to 5% by weight in terms of silver oxide. As a result, antibacterial, antifungal and antialgal properties can be effectively exhibited with an appropriate silver content.

Further, in the antibacterial / fungicidal / algaeproofing agent for admixing with cement according to claim 5, the mixing ratio between the silver-containing frit powder and the silicone resin is set to 1 weight of the silver-containing frit powder. The silicone resin for the part
When the amount is 0.5 to 20 parts by weight, synergistic antibacterial, antifungal and antialgal properties can be effectively exerted by appropriately mixing the silver-containing frit powder and the silicone resin.

The hydraulic cement composition according to claim 6 is obtained by mixing at least the antibacterial, antifungal and antialgal agent for cement admixture according to any one of claims 1 to 5 with a hydraulic cement. Therefore, after hardening the cement,
It is possible to exert synergistic antibacterial, antifungal, and antialgal properties by an inorganic compound having antifungal and antialgal action and a silicone resin.

The hydraulic cement composition according to claim 7 is characterized in that the antibacterial / antifungal / algaeproofing agent for admixing with cement according to any one of claims 1 to 5 is added to the hydraulic cement in an amount of 0.1%.
Since 1 to 3% by weight is added, an appropriate amount of an antibacterial, antifungal, and antialgal agent added to the cement can effectively exhibit antibacterial, antifungal, and antialgal properties after the cement is cured. it can.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical location C09D 1/06 PCP C09D 1/06 PCP 5/14 PQM 5/14 PQM 5/16 PQJ 5/16 PQJ PQL PQL // C04B 103: 67

Claims (7)

[Claims] 1. An antibacterial / mold-proofing agent for cement admixture, characterized in that at least an inorganic compound powder having an antibacterial / mold-proofing / algae-proofing effect is mixed with a powdery silicone resin.
Algae repellent. 2. The antibacterial and fungicide for cement admixture according to claim 1, wherein the inorganic compound powder having an antibacterial, antifungal and antialgal action is a frit powder containing a metal having an oligodynamic effect. -Anti-algal agents. 3. The antibacterial, antifungal and antialgal agent for admixing cement according to claim 2, wherein the frit powder containing a metal having an oligodynamic effect is a frit powder containing silver. 4. The antibacterial and antifungal agent for cement admixture according to claim 3, wherein the silver content in the silver-containing frit powder is 0.1 to 5% by weight in terms of silver oxide. -Anti-algal agents. 5. The mixing ratio of the silver-containing frit powder to the silicone resin is such that the silicone resin is 0.5 to 20 parts by weight per 1 part by weight of the silver-containing frit powder.
5. The method according to claim 3, wherein the amount is by weight.
The antibacterial, antifungal and antialgal agents for admixing with cement according to any one of the above. 6. A hydraulic cement composition comprising at least the antibacterial, antifungal and antialgal agent for cement admixture according to claim 1 and a hydraulic cement. . 7. An antibacterial, fungicidal and antialgal agent for admixing cement according to any one of claims 1 to 5, wherein 0.1 to 3% by weight is added to the hydraulic cement. The hydraulic cement composition according to claim 6, wherein