JP2821968B2 - Mold-resistant waterproof coating - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for use in general buildings, hospitals, clean rooms, special buildings such as food factories, and underground waterfronts, etc. And a mold-resistant waterproofing material.

[0002]

2. Description of the Related Art Coating materials containing various organic fungicides for making the coating material mildew-proof are known. For example, an industrial germicidal composition in which 2-pyridylthio-1-oxide or a metal salt thereof is combined with 2- (4-thiazolyl) benzimidazole is known and is said to be applicable to paints and the like. 3-51684).

[0003]

The known antifungal coating waterproofing material exhibits some antifungal properties, but it is not effective against certain fungi under conditions favorable to the growth of fungi. Have been found by the present inventors. An object of the present invention is to provide a fungicide-resistant coated waterproofing material that is effective against a wider spectrum of bacterial species.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a zeolite particle carrying a metal ion having an antibacterial action, and one or more selected from a benzimidazole derivative and a bis (2-pyridylthio-1-oxide) metal salt. A mildewproof coating waterproofing material containing an organic mildewproofing agent. Generally, mold resistance is evaluated according to JIS Z2911.
The following five groups are used as molds for testing.

Group 1 (1) Aspergillus niger FE
RM S-1 (2) Aspergillus niger FERM S-2 (3) Aspergillus teleus FERM S-3 (4) Eurotium tonohirum FERM S-4 Group 2 (1) Penicillium citrinum FERM S-5 (2) Penicillium funiculosum FERM S -6 Third group (1) Resorps Stronifer FERM S-7 Fourth group (1) Cladosporium Cladosporioides
FERM S-8 (2) Aureobasidium pullulans FERM S-9 (3) Gliocladium virens FERM S-10 Group 5 (1) Ketomium globosum FERM S-11 (2) Fusarium proliferatum FERM S-12 ( 3) Milotesium Bercaria FERM S-13 As shown in the following examples, JIS Z291
The fungicidal properties of the coated waterproofing materials containing various antifungal agents were tested by enriching the nutrient sources of fungi more than 1, and all of the known fungicides for coating waterproofing materials showed sufficient fungicidal properties. Not found. When this was observed in more detail, Rhizopus stronifer of the third group out of the five groups was remarkably breeding on the waterproofing material, ketomium globosum of the fifth group was slightly breeding, and It was found that the bacteria of groups 1, 2 and 4 did not propagate. It is said that the Rhizopus stronifer in the third group is slightly weaker than the fungi in the first and second groups, but on the other hand, it is said to exhibit extremely vigorous growth on a substrate suitable for preference. It is surprising that the known fungicides for film waterproofing have little effect on Rhizopus stronifer in accelerated tests under eutrophication.

Accordingly, the present inventor has studied the application methods of various fungicides, and as a result, it has been found that the combination of specific fungicides is effective against the molds of the third and fifth groups, especially the third group which is a problem. Have been found to be effective, and the present invention has been completed. The zeolite particles carrying a metal ion having an antibacterial action used in the present invention are known per se, and are described, for example, in JP-A-62-243665 and JP-A-63-260810. As metal ions having antibacterial action,
Silver, copper, zinc, mercury, tin, lead, bismuth and cadmium, preferably silver, copper and zinc, or combinations thereof, especially silver ions.

The zeolite particles used in the present invention have a specific surface area of at least 150 m ² / g (based on anhydrous zeolite), and the zeolite constituent has a SiO ₂ / Al ₂ O ₃ molar ratio of 14 or less, particularly 11 or less. Are preferred. Either natural or synthetic zeolites can be used. For example, natural zeolites include analsime (analcime: SiO ₂
/ Al ₂ O ₃ = 3.6-5.6), Chabazit
_{e: SiO 2 / Al 2 O} 3 = 3.2 ~6.0 and 6.4 to 7.6
), Clinoptilolite (SiO ₂₎
/ Al ₂ O ₃ = 8.5-10.5), Erionit
_{e: SiO 2 / Al 2 O} 3 = 5.8 ~7.4), Fuojiyasaito _{(Faujastie: SiO 2 / Al 2} O 3 = 4.2 ~4.6
), Mordenite (mordenite: SiO ₂ / Al ₂ O ₃₎
= 8.34 to 10.0) Phillipsite (SiO)
₂ / Al ₂ O ₃ = 2.6 to 4.4). These typical natural zeolites are suitable for the present invention. Typical examples of of synthetic zeolite A- type zeolite _{(SiO 2 / Al 2 O 3} = 1.4 ~2.4), X- type zeolite _{(SiO 2 / Al 2 O 3} = 2~3), Y- type zeolite ( SiO ₂ / Al ₂ O ₃ = 3 to 6) and mordenite (SiO ₂ / Al ₂ O ₃ = 9 to 10), and these synthetic zeolites are suitable as the zeolite material of the present invention. Synthetic A-type zeolites, X-type zeolites, Y-type zeolites and synthetic or natural mordenites.

The average particle size of the zeolite particles is, for example, 100
Submicron, especially 0.5 to 10 microns are preferred.

Preferably, the metal ions are supported on the zeolite solid particles by an ion exchange reaction. Especially less than the ion exchange capacity of the zeolite solid particles, especially about 90
% Of the metal ions is preferably ion-exchanged. As a method for retaining metal ions, a case where various zeolites are converted to Ag-zeolites will be described as an example. Usually, a solution of a water-soluble silver salt such as silver nitrate is used at the time of Ag-zeolite conversion, but it is preferable to pay attention so that the concentration thereof is not excessive. For example, A
When converting the zeolite-or X-type (sodium-type) to Ag-zeolite using an ion exchange reaction,
If the silver ion concentration is high (for example, 1-2 M AgNO
At the time of ( ₃ ) use, silver ions are replaced with sodium ions in the solid phase by ion exchange, and at the same time, precipitate in the zeolite solid phase as silver oxide and the like. This has the disadvantage that the porosity of the zeolite is reduced and the specific surface area is significantly reduced. Even if the specific surface area does not decrease so much, the bactericidal activity is reduced by the presence of the silver oxide itself. In order to prevent the precipitation of excessive silver in the zeolite phase, it is preferable to maintain the concentration of the silver solution in a more diluted state, for example, 0.3 M AgNO ₃ or less. The safest concentration of AgNO ₃ is 0.
1 or less. When the AgNO ₃ solution having such a concentration is used, the specific surface area of the obtained Ag-zeolite is almost equal to that of the original zeolite, and the effect of the bactericidal power can be exerted under the optimum condition.

Next, when zeolite is converted to Cu-zeolite, a phenomenon similar to that of the above-mentioned Ag-zeolite occurs depending on the concentration of the copper salt used for ion exchange. For example, when converting A-type or X-type zeolite (sodium-type) to Cu-zeolite by ion exchange reaction, when 1M CuSO _{4 is} used, Cu ²⁺ is converted into solid phase Na.
⁺ , But at the same time, the Cu
_Since a basic precipitate such as ₃ (SO ₄ ) (OH) ₄ is deposited, the porosity of the zeolite is reduced, and the specific surface area is significantly reduced. In order to prevent such excess copper from being deposited on the zeolite phase, it is preferable to maintain the concentration of the water-soluble copper solution used in a more diluted state, for example, 0.05 M or less. When a CuSO ₄ solution having such a concentration is used, the specific surface area of the obtained Cu-zeolite is almost equal to that of the original zeolite, and there is an advantage that the bactericidal effect can be exhibited in an optimum state.

[0011] It has been stated that during the conversion to Ag-zeolite and Cu-zeolite, solids precipitate on the zeolite solid phase depending on the concentration of salts used for ion exchange. Such a phenomenon is not observed when the salt used is around 2 to 3M. Usually, the Zn-zeolite used in the present invention can be easily obtained by using salts having the above concentration.

When the above-mentioned ion exchange reaction for conversion to Ag-zeolite, Cu-zeolite and Zn-zeolite is carried out by a batch method, the zeolite material is immersed in a salt solution having the above-mentioned concentration. do it.
In order to increase the metal content in the zeolite material, the number of batch processes may be increased. On the other hand, when treating the zeolite material by a column method using a salt solution having the above-described concentration, filling the adsorption tower with the zeolite material,
If a salt solution is passed through this, the target metal can be easily
A zeolite is obtained.

The amount of metal in the above-mentioned metal-zeolite (based on anhydrous zeolite) is not more than 30% by weight for silver, and the preferred range is from 0.001 to 5% by weight. On the other hand, for copper and zinc, the amount of copper or zinc in the metal-zeolite (based on anhydrous zeolite) is 35% by weight or less, and the preferred range is 0.01 to 15% by weight. It is also possible to use silver copper and zinc ions in combination,
In this case, the total amount of metal ions may be 35% by weight or less based on the metal-zeolite (based on anhydrous zeolite), and the preferred range is about 0.001 to 15% by weight, depending on the composition ratio of the metal ions.

Before use, the germicidal zeolite is subjected to a drying treatment if necessary. Drying conditions are 100 to 50 under normal pressure or reduced pressure
It may be appropriately selected within the range of 0 ° C. Preferred drying conditions are 100-350 ° C under reduced pressure.

[0015] Such antibacterial zeolite particles are disclosed in
It may be coated as described in JP-A-62-243665. Thereby, the dispersion to the coating film waterproof material becomes good,
Further, the chemical stability in the coating film waterproof material is improved.

The benzimidazole fungicides used in the present invention are known per se. Preferably, it is selected from 2- (4-thiazolyl) -benzimidazole and 2-methoxycarbonylaminobenzimidazole , used alone or
May be any of two kinds in combination. The bis (2-pyridylthio-1-oxide) metal salt used in the present invention is also known per se, and is preferably a zinc salt.

The antimicrobial zeolite and these specific organic fungicides are preferably each 0.01 to 10% by weight, in particular 0.1 to 10% by weight.
２2% by weight (based on the total weight of the coating film waterproofing composition).

The coating waterproofing material itself is also known, and examples thereof include silicone, polyurethane, acrylic polymer, neoprene, butyl rubber, and chlorinated rubber. Preferably, silicone-based (including modified silicone-based) and epoxy-modified silicone-based coating waterproofing materials are used.

By adding and mixing the antibacterial zeolite particles according to the present invention and a specific organic fungicide to such a known waterproof coating material, the antifungal coating waterproof material of the present invention can be prepared. It can be used by conventional enforcement law.

The present invention is characterized in that the above antibacterial zeolite particles are used in combination with the above specific organic fungicide. If only one of them is used, the growth of the mold of the third group cannot be effectively prevented under favorable conditions. The combined use surprisingly prevented the growth of the mold of the third group. In addition, a situation may occur in which it is rather difficult to prevent the growth of the mold of the fifth group, but even in such a case, the combined use of the antibacterial zeolite particles according to the present invention and the specific organic fungicide results in complete fungicide resistance. be able to.

[0021]

Examples Composition of Agent A (parts by weight) Epoxy resin; Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd.) 100.0 Calcium carbonate; 40.0 Titanium oxide; 20.0 Dibutyltin dilaurate; 2.0 Vinyltrimethoxysilane; 2.0 Antibacterial zeolite (Type A) Zeolite, average particle size 2μ, 2.2% by weight of silver, 9.5% by weight of zinc) 0.6% by weight based on the total amount of the mixture of agent A and agent B The above amount of calcium carbonate, titanium oxide, antibacterial zeolite, and a part of epoxy resin are high-speed When the dispersion was completed by kneading with a stirrer, the remaining epoxy resin was blended to form a paste. Next, a tin compound and vinyltrimethoxysilane were added and sufficiently stirred, and the pressure was reduced to produce a uniform paste. To adjust the viscosity, toluene (20% by weight based on the total weight) was then added.

Agent B composition (parts by weight) Modified silicone resin; Kaneka MS polymer (manufactured by Kaneka Corporation) 100.0 Calcium carbonate; 50.0 N-β (aminoethyl) -γ-aminopropyltrimethoxysilane; 2.0 Amine compound 2,4,6- (trisdimethylaminomethyl) phenol 2.5 vinyltrimethoxysilane 2.0 2- (4-thiazolyl) -benzimidazole 0.1% by weight based on the total amount of the mixture of agent A and agent B The above amounts of calcium carbonate and vinyl Trimethoxysilane, 2- (4-thiazolyl) -benzimidazole, and a part of the modified silicone resin are stiffened with a high-speed stirrer, and when the dispersion of the filler is completed, all the remaining modified silicone resin is compounded to form a paste. Had made. Then about 100
The mixture was stirred under reduced pressure while heating at 30 ° C for 30 minutes. Finally, aminosilane and an amine compound were added to produce a uniform paste.
To adjust the viscosity, toluene (20% by weight based on the total weight) was added.

The agent A and the agent B were mixed at a weight ratio of 1: 1 to prepare a waterproof coating material. This was cured at 20 ° C. and 65% RH for 14 days to obtain a 40 × 40 × 3 mm sheet, which was used in the following tests.

For comparison, a sample containing only one of the antibacterial zeolite and 2- (4-thiazolyl) -benzimidazole and a sample containing neither of them were prepared.

(2) Mold Generation Acceleration Test Mold resistance was tested by the following method.

Bacteria used: Aspergillus niger of group 1 Penicillium citrinum of group 2 Rhizopus stronifer of group 3 Cladosporium cladosporioides of group 4 Ketomium globosum of group 5 Medium: inorganic salts having the following composition Medium was used.

[0027] Monopotassium phosphate 0.7 g Dipotassium phosphate 0.7 g Ammonium nitrate 1.0 g Magnesium sulfate 0.7 g Sodium chloride 0.005 g Ferrous sulfate 0.002 g Zinc sulfate 0.002 g Manganese sulfate 0.001 g Agar 15.0 g Purified water 1000 ml Nutrient solution : A nutrient solution having the following composition was prepared.

Monopotassium phosphate 0.7 g Dipotassium phosphate 0.7 g Ammonium nitrate 1.0 g Magnesium sulfate 0.7 g Sodium chloride 0.005 g Ferrous sulfate 0.002 g Zinc sulfate 0.002 g Manganese sulfate 0.001 g Glucose 3.0 g Purified water 1000 ml Test method: The above medium was dispensed in 20 ml portions into a sterile petri dish, and after solidification, a coating film waterproof material sample was placed on the top.

Five platinum loops of each of the above five mold spores were taken and suspended in a 0.005% aqueous solution of dioctyl sodium sulfosuccinate. Each suspension was rubbed with gauze and mixed to prepare a mixed spore suspension. This solution was centrifuged, and the nutrient solution was added to the residue from which the supernatant was removed to prepare a mixed spore suspension nutrient solution. This solution was sprayed onto the surface of the sample and the medium at a ratio of 0.9 ml per 40 × 40 mm surface area and cultured.

Culture conditions: temperature 28 ± 2 ° C. Relative humidity 95% or more Culture period: 4 weeks The results are shown in Table 1.

[0031]

Table 1 Example 1 Antibacterial zeolite benzimidazole 2 weeks 4 weeks 1 − − ++ +++ 2 0.6 − ++ +++ 3 − 0.1 ++++ ++++ 40 0.6 0.1 + + −: No mold was observed.

+: Mold generated on the sample surface is 10% or less of the surface area.

++: Mold generated on the sample surface is 10 to 30% of the surface area.

+++: Mold generated on the sample surface is 30 to 70% of the surface area.

+++++: Mold generated on the sample surface is 70 to 100% of the surface area.

Under the above conditions for promoting the generation of mold, the case where only the antibacterial zeolite was added (Example 2) showed almost no anti-mold property. Observation of the grown mold revealed that most of them were Rhizopus stronifer in the third group, and ketomium globosum in the fifth group was slightly observed. In the case of adding only the benzimidazole-based fungicide (Example 3), there was no fungicide at all.

However, when the benzimidazole-based fungicide which did not show any fungicide was used in combination with the antibacterial zeolite particles (Example 4), remarkable fungicide was achieved. That is, excellent effects not expected from the results of Examples 2 and 3 were achieved in Example 4.

For confirmation, the bacteria of Groups 3 and 5 were not used in the test, and Aspergillus niger of Group 1 and
Using the penicillium floclosum of the group and all three species of the fourth group, a mold development promotion test was carried out in the same manner as described above, but the fungi were found to develop for both 2 weeks and 4 weeks even with the benzimidazole fungicide alone. The result was not recognized (-). In other words, benzimidazole-based fungicides alone are sufficiently effective against bacteria other than the third and fifth groups. However, the present invention is effective for preventing mold in the third group (and the fifth group) under conditions favorable for mold generation.

The same results were obtained in Examples in which bis (2-pyridylthio-1-oxide) zinc was used in the same amount in place of 2- (4-thiazolyl) -benzimidazole.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shin Terauchi 2-19-1, Tobita-Ki, Chofu-shi, Tokyo Kashima Construction R & D Co., Ltd. (72) Inventor Yoshikazu Takei 2- 19-1, Tokita-Tokita, Chofu-shi, Tokyo Kashima Construction Research Institute, Inc. (72) Inventor Masaharu Sasaki 2-1-19 Tobita, Chofu, Tokyo Kashima Construction Research Institute Inc. (72) Inventor, Tadahiro Shimazu 1-2-7 Moto-Akasaka, Minato-ku, Tokyo Kashima Construction (72) Inventor Takeo Tanimoto 8-17 Kurakuen Sanbancho, Nishinomiya City, Hyogo Prefecture (72) Inventor Ryuhei Matsuo 1-4-3-607 Tomobuchicho, Miyakojima-ku, Osaka-shi, Osaka ( 72) Inventor Junji Tsurumoto Inside 4-5-9 Higashi Gotanda, Shinagawa-ku, Tokyo, Japan (72) Inventor Junzo Makino 4-5-9 Semeda, Higashi-Gotanda, Shinagawa-ku, Tokyo (72) Inventor Yasushi Hayashi 2-2-2-2 Nakanoshima, Kita-ku, Osaka-shi, Osaka Nichimen Co., Ltd. (72) Inventor Aritsune 2-2-2 Nakanoshima, Kita-ku, Osaka, Osaka Nichimen stock In-company (58) Field surveyed (Int.Cl. ⁶ , DB name) C09D 5/14 C09D 5/00

Claims (4)

(57) [Claims] A zeolite particle carrying a metal ion having an antibacterial action, and one or more organic fungicides selected from benzimidazole derivatives and bis (2-pyridylthio-1-oxide) metal salts. A mildew-proof coating waterproofing material. 2. The antifungal coating waterproofing material according to claim 1, comprising 0.01 to 10% by weight (based on the total weight of the coating waterproofing material) of each of the antibacterial zeolite particles and the organic fungicide. . 3. The waterproof material according to claim 1, wherein the metal ions are silver ions. 4. A method according to claim 1, wherein the benzimidazole derivative is 2- (4-
The fungicide according to any one of claims 1 to 3, wherein the thiazolyl) -benzimidazole and / or 2-methoxycarbonylaminobenzimidazole is used, and the bis (2-pyridylthio-1-oxide) metal salt is a zinc salt. Water-resistant waterproof coating.