JPH10176163A - Antimildew sealant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sealant which can retain antimildew effects for a long term, does not discolor even under severe conditions such as under exposure to ultraviolet rays, and is excellent in durability by causing a triazole-base antimildew compd. to be carried between layers of a layered silicate. SOLUTION: A known layered silicate, natural or synthetic, may be used. An example is montmorillonite. Pref. it has an average particle size of 0.1-7μm, a narrow particle size distribution, uniform particle sizes, and a cation exchange capacity of 0.1meq/g or higher. The lower limit of the amt. of the triazole-base antimildew compd. carried by the layered silicate is 0.1% of the silicate. The conditions for preparing this sealant are not specifically limited and can be suitably varied depending on the types of the antimildew compd. and the silicate and the amt. of the compd. carried. For example, the pH of a solvent used is 0.1-13; the stirring time is 0.5-72hr; the stirring temp. is in the range of from normal temp. to about 40-60 deg.C; and the stirring speed is 10-1,000rpm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fungicidal sealing material composition having a fungicidal agent and a sealing substrate. It demonstrates. The composition of the present invention is useful as a sealing material composition that can be applied to various materials such as metals, plastics, and ceramics that require antifungal properties.

[0002]

2. Description of the Related Art A sealing material is used for filling a gap to enhance waterproofness or airtightness. In general, at the time of construction, the gap is often filled with a sealing material without completely removing mold present in the gap, and water or water vapor in the air that comes into contact with the sealing surface stays. For this reason, there is a problem in that, as time passes after filling with the sealing material, coloring contamination and deterioration often occur on the sealing surface due to generation of mold, as seen in the case of tile joints.

In order to prevent the occurrence of such molds, it has been proposed to include an inorganic or organic fungicide in the sealing material. Conventionally, as an inorganic fungicide, a metal ion having antibacterial properties such as silver, copper, and zinc supported on activated carbon, apatite, zeolite and the like is known.

On the other hand, organic antibacterial and antifungal agents include quaternary ammonium salt compounds represented by benzalkonium chloride, sulfur-containing benzimidazole compounds represented by 2,4-thiazolylbenzimidazole, Bisthiocyanate compounds represented by methylenebisthiocyanate, quinolinol compounds represented by 8-quinolinol, alcohol compounds represented by ethanol,
Antifungal agents such as aldehyde compounds represented by formalin, phenol compounds represented by cresol, and carboxylic acid compounds represented by sorbic acid are known.

[0005] However, although the above-mentioned inorganic fungicides are excellent in heat resistance and chemical resistance, they have a problem that they are inferior to fungi as compared with antibacterial effects against bacteria, and organically. Although the antifungal agent is highly effective against fungi, it tends to recrystallize inside the sealing material after application, and is easily released to the outside over time (bleed-out phenomenon). What is missing is the reality. In addition, organic compounds have poor chemical resistance and relatively high solubility in various solvents, so they elute during use, have low persistence of fungicidal effects, and have a low effect on the human body. However, its use is limited because some compounds have problems. Furthermore, many organic antifungal agents are deteriorated by ultraviolet rays, which may cause discoloration.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a fungicidal sealing material composition containing a fungicide and a sealing substrate, and by using this composition, the fungicide effect is maintained for a long time. It is an object of the present invention to provide a sealing material composition which is capable of forming a sealing with excellent durability and which does not discolor even under a severe environment such as ultraviolet irradiation.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that it is extremely effective to contain a specific inorganic fungicide. The invention has been completed. That is, the present invention
A fungicidal sealing material composition comprising a fungicidal agent having a triazole-based fungicidal organic substance supported between layers of a layered silicate and a sealing substrate.

Hereinafter, the present invention will be described in detail. □ Sealing base material The sealing base material in the present invention is a component serving as a main agent for forming a sealing, and any of those conventionally used can be used. Preferred sealing substrates include organic, inorganic, and organic-inorganic mixed materials, and, for example, organic materials include synthetic resin emulsions and resin-based materials such as reaction-curing resins.
Examples of the inorganic material include a cement material.

Preferred resin materials include, for example, silicone-based sealing materials, polysulfide-based sealing materials,
Polyurethane sealant, SBR sealant,
There are a butyl rubber sealing material, an acrylic sealing material, and the like.

[0010] Cement is an inorganic substance which shows curability when mixed with water, and is mainly composed of calcium silicate, calcium aluminate, calcium sulfate or calcium oxide. As preferred cement materials, dolomite plaster, slaked lime, plaster, plaster,
Magnesia cement, hydraulic lime, roman cement,
There are natural cement, Portland cement, alumina cement, lime mixed cement, mixed Portland cement, water glass cement, dental cement and the like. These cements can be used as cement paste mixed with water, or can be used as cement mortar or concrete by mixing with aggregates such as cement sand. And a substrate that can be used as a joint material.

When the sealing substrate is solid at room temperature or has a high viscosity, a solvent or a dispersant for lowering these viscosities can be appropriately compounded to facilitate filling. . Solvents or dispersants
It may be either hydrophilic or lipophilic.

□ Fungicide The fungicide of the present invention comprises a fungicidal layered silicate in which a triazole-based fungicidal organic compound is supported between layers of the layered silicate.黴 Fungicidal organic compound The fungicidal organic compound in the present invention is a triazole-based fungicidal organic compound, and preferred specific examples include the following compounds (wherein <> indicates a common name). That is, α-
[2- (4-chlorophenyl) ethyl] -α- (1,1
-Dimethylethyl) -1H-1,2,4-triazol-1-yl-ethanol <debuconazole>, 1- (4
-Chlorophenoxy) 3,3-dimethyl-1- (1H-
1,2,4-triazo-1-yl-2-butanone <triadimefon>, β- (4-chlorophenoxy) -α
-(1,1-dimethyl-ethyl) -1H-1,2,4-
Triazole-1-ethanol <triadimenol> and <hexaconazole>. In the present invention,
Only one kind may be used as the fungicidal organic compound.
More than one type may be used in combination.

Layered silicate The layered silicate in the present invention is conventionally known, and can be used without particular limitation as long as it is a silicate in which crystal layer units are stacked on each other to form a layered structure. Any of a natural product and a synthetic product may be used.

Preferred layered silicates include clay minerals, and specific examples thereof include the following. That is, smectites such as montmorillonite, beidellite, hectorite, saponite, etc., mica such as muscovite, phlogopite and biotite, brittle mica such as margarite and clintite, and green mud such as sudoite. Kaolins such as stones, kaolinite, halloysite, etc.
It is a serpentine family such as antigorite. Other preferred layered silicates include: That is, there are layered sodium silicates such as magadiite, kenyaite, kanemite, macatite, and ironerite, layered calcium silicates such as tobermorite, and synthetic mica in which anions such as hydroxyl ions are substituted with fluorine ions. Preferred are smectite group phyllosilicates, bimeculite group phyllosilicates, synthetic mica, and layer silicates in which some or all of the hydroxyl ions in these phyllosilicates are substituted with fluorine ions.

The particle size, water content, ion exchange capacity, color and the like of the layered silicate in the present invention are not particularly limited. When used for kneading into plastics, rubber or fibers, powder having an average particle size of 10 μm or less is preferable, more preferably a powder having an average particle size of 0.1 to 7 μm, and further, the particle size distribution is narrow, More preferably, the particles have a uniform particle size. Further, in order to exhibit a sufficient fungicidal effect when a fungicidal layered silicate is used, the cation exchange capacity is 0.1 m.
It is preferably at least eq / g. One of these layered silicates may be used alone, but two or more of them may be used in combination for controlling the sustained release.

In the layered silicate, some or all of the ion-exchangeable metal ions may be replaced by other ions. The ion to be exchanged is not particularly limited as long as it is an ion-exchangeable ion, but is preferably a hydrogen ion, a lithium ion, a sodium ion, a calcium ion or the like.

The preferred lower limit of the amount of the triazole-based antifungal organic compound supported on the antifungal layered silicate of the present invention is based on 100 (hereinafter simply abbreviated as “parts”) of the antifungal layered silicate of the present invention. 0.1 part, more preferably 1 part
Parts, particularly preferably 5 parts. If the amount is too small, the antifungal effect is reduced. The upper limit of the supported amount is determined by the type of the layered silicate and the antifungal organic compound, but the antifungal layered silicate that is unnecessarily supported in a large amount is mixed with the sealing base material or at the time of execution. Since there is a possibility that discoloration may occur or control of sustained release may become difficult, it is preferable to set a suitable upper limit of the amount supported by a preliminary test.

The method of loading the triazole-based antifungal organic compound on the layered silicate is not particularly limited. Basically, it suffices to contact the antifungal organic compound with the layered silicate.
It can be introduced regardless of whether the antifungal organic compound is in a solid phase, a liquid phase, or a gas phase. For example, in the case where the fungicidal organic compound is in a liquid phase, the fungicidal organic compound is mixed with the layered silicate and stirred, and then dried and pulverized, or the fungicidal organic compound is highly soluble. The solution dissolved in the solvent and the layered silicate are mixed and stirred, followed by filtration and washing, followed by drying and pulverization to obtain a fungicidal layered silicate having the layered silicate loaded with a fungicidal organic compound. be able to.
In addition, you may dry and grind as it is without washing.

The conditions for preparing the above-mentioned mildew-resistant layered silicate are not particularly limited, and can be appropriately changed depending on the kind of the mildewproof organic compound and the layered silicate to be used, and the amount of the mildewproof organic compound carried. Specifically, for example, the pH of the solvent is 0.1 to 13, the stirring time is 0.5 to 72 hours, the stirring temperature is from room temperature to, for example, about 40 ° C. to 60 ° C., and the stirring speed is 10
It may be up to 1000 times / minute.

Other components Components conventionally used as sealant components, such as coloring agents, moisture proofing agents, waterproofing agents, alkali aggregate reaction controlling agents,
An antifoaming agent, a bulking agent, a flocculant and the like can be used arbitrarily as long as the fungicide of the present invention is not impaired.

In the sealing material composition of the present invention, silver,
An inorganic antibacterial agent in which a metal ion exhibiting antibacterial properties such as copper and zinc is carried on activated carbon, apatite, zeolite, zirconium phosphate, titanium phosphate or the like can be used in combination.

The mixing ratio of the fungicide is preferably 0.05 to 30 parts, more preferably 0.3 to 10 parts, per 100 parts of the sealing substrate.
Department. If the amount is less than 0.05 part, the antifungal effect may not be sufficiently exerted. On the other hand, if the amount is more than 30 parts, the effective component for forming the sealing is reduced, so that a high quality sealing is formed. May be difficult.

Production Method The fungicidal sealing material composition of the present invention is obtained by mixing, mixing or mixing the above fungicide with a sealing substrate and other desired components at an appropriate temperature or pressure according to the properties of the components used. It can be easily prepared by a kneading method, and specific operations thereof may be performed by a conventional method. The fungicide-resistant sealing material composition thus obtained has little deterioration during mixing of the fungicide with the sealing substrate and during storage or use thereafter, and has long-term fungicidal properties.

Use The fungicidal sealing material composition of the present invention has fungicidal properties,
It is effective in fields where a long-lasting antifungal effect and formation of a seal without discoloration are required, such as exterior walls, baths, pools, toilets, washrooms, windows, roads, piers, aquariums, and silos, and tiles. It is particularly effective as a jointing material for the like.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to examples.

[0026]

The present invention will be described below in more detail with reference to examples. (Reference Example 1) Preparation of Ca-type layered silicate To 1.0 liter of 0.1 mol / l CaCl ₂ aqueous solution, 100.0 g of Na-type fluorine-substituted synthetic moth, which is a layered silicate, was added.
The suspension was stirred for a time (300 rpm) to replace the ion-exchangeable sodium ions of the layered silicate with calcium ions. After the suspension was filtered, the filtrate was washed with ion-exchanged water. After confirming that the Na ion in the washing solution was 1 ppm or less, the washing was completed, then dried at 100 ° C. and crushed lightly. A Ca-type layered silicate having an average particle size of 5 μm was obtained.

Reference Example 2 Preparation of Fungicide A α- [2- (4
-Chlorophenyl) ethyl] -α- (1,1-dimethyl-1H-1,2,4-triazol-1-yl-ethanol (hereinafter debuconazole) to 7.5 g of the Ca-type layered silicate obtained in Reference Example 1. Add 42.5g, mix thoroughly in a mortar,
Heat at 120 ° C. for 2 hours, then cool to room temperature. The obtained product was washed with pure water, vacuum-dried at 100 ° C., and then lightly pulverized to obtain a white fungicide A.

Reference Example 3 Preparation of Fungicide B In 500 ml of a 50% methanol / water solution, 7.5 g of 2- (4-thiazolyl) benzimidazole (hereinafter referred to as TBZ), which is a fungicidal organic compound other than the triazole type, is used. A solution was prepared, and 42.5 g of the Ca-type layered silicate obtained in Reference Example 1 was added thereto.
added. Thereafter, a white fungicide B was obtained in the same manner as in Reference Example 2.

(Example 1) Preparation of antifungal sealing material composition The antifungal agent A obtained in Reference Example 2 was added to a silicone sealing material (manufactured by Cemedine Co., Ltd.) as shown in Table 1 below.
These were uniformly mixed to obtain a fungicidal sealing material composition.

(Comparative Examples 1 to 3) Preparation of antifungal sealing material composition The antifungal agent B, debuconazole and TBZ obtained in Reference Example 3 were
The same kind of sealing base material as that used in Example 1 was added as shown in Table 1 below and uniformly mixed to obtain a fungicidal sealing material composition.

[0031]

[Table 1]

Evaluation of durability of antifungal property A test piece was prepared as follows using the antifungal sealing material composition prepared in Example 1 and Comparative Examples 1 to 3, and the antifungal property was maintained. Was evaluated as follows. (Preparation of test piece) 5 cm ×
A metal mold of 5 cm × 0.5 cm was filled and air-dried for one day. A 1 cm square piece was cut from the filler immediately after the formation of the sealing, and used as a test piece immediately after the production (after 0 day). afterwards,
It was left in a room at 20 ° C., and after 10 days and 20 days had elapsed, 1 cm squares were cut from the filling, and used as test specimens after 10 days and after 20 days, respectively. The surface of each of the three types of test specimens obtained as described above was wiped clean, and the time-dependent change in the antifungal property was evaluated as follows. (Anti-mold test) Using black koji mold (Aspergills niger) as a mold, place a test piece on a potato dextrose agar medium coated with mold spores (contact the outer surface of the filler at the time of sealing formation with the agar medium). T), the antifungal property was evaluated by measuring the width of inhibition zone formation after culturing at 25 ° C. for 2 weeks. Table 2 shows the growth inhibition zones measured as described above.

[0033]

[Table 2]

Note) "-" indicates that no growth inhibition zone is observed (the same applies hereinafter).

Evaluation of chemical resistance A certain antifungal sealing material composition has a hole of 1 mm diameter at the center of the bottom surface, 2 cm × 2 cm × 20 cm (depth).
Were prepared, and a sealing was formed in each of the plastic containers as follows. That is, the mold-resistant sealing material composition was added to the plastic container in a thickness of 0.3 cm so as to cover the bottom hole.
And air-dried for one day. A 1 cm square piece was cut from the filler immediately after the formation of the sealing, and used as a test piece immediately after the production (after 0 day). 75 ml of 0.1N hydrochloric acid was placed in the two plastic containers having the sealing formed as described above.
After that, it was left in a room at 20 ° C., and after 4 days and 7 days, 1 cm square was cut out from the filling to obtain a test piece after 4 days and a test piece after 7 days. 3 obtained as above
The surface of each test piece of the seed was wiped cleanly, and the time-dependent change of the antifungal property was evaluated in the same manner as in the above "Evaluation of the durability of antifungal property". Table 3 shows the results of the antifungal test and the overall evaluation.
When dilute hydrochloric acid was added to the plastic container, there was no leakage from the bottom of the container, and the sealing was good.

Evaluation of Weather Resistance Using the compositions prepared in Example 1 and Comparative Examples 1 to 3, a 1 cm square test piece was prepared in the same manner as that used for the evaluation of the durability of the antifungal property. The test pieces were prepared and the weather resistance of each test piece was evaluated using a weather resistance tester (UVCON manufactured by ATLAS). The test conditions of the weather resistance tester are as follows: one cycle is 8 hours, a 4-hour process of irradiating ultraviolet rays of 350 nm or less at 60 ° C., and a 4-hour process of leaving at 40 ° C. in an atmosphere of 95% or more humidity. Become. Using a color difference meter (color difference meter SZ- # 80 manufactured by Nippon Denshoku Industries Co., Ltd.), the color (L ₁ , a ₁ , b ₁ ) after 0 cycles of the weather resistance test and the color (L ₂ , a ₂ , b ₂ ) were measured, and the color difference (ΔE) was calculated by the following equation [1] using these measured values.
Table 3 below shows the evaluation of the chemical resistance, the results of the weather resistance test, and the overall evaluation obtained as described above. Delta] E = ^{_{[((L 1 -L 2) 2}} + (a 1 - 2) 2 + (b 1 -b 2) 2) ] ^1/2 [1]

[0037]

[Table 3]

(Display of Overall Evaluation) A: Excellent as an overall evaluation. ×: Inferior in overall evaluation.

The following can be seen from the test results in Tables 2 and 3. Table 2: Example 1 and Comparative Example 1 both maintain the antifungal property even after 0 to 20 days, but Comparative Examples 2 and 3
After 10 days, the antifungal property has already been reduced. -Table 3: Example 1 and Comparative Example 1 were hardly affected by contact with dilute hydrochloric acid for 0 to 7 days and maintained their antifungal properties. However, Comparative Example 2 and Comparative Example 3 Already after 4 days, the antifungal property has been significantly reduced. -Table 3: Example 1 has excellent weather resistance, but Comparative Example 1 shows remarkable discoloration after the weather resistance test and is inferior in weather resistance. From the above results, Example 1 using the fungicidal sealing material composition of the present invention showed longer durability of the fungicide and chemical resistance than Comparative Examples 2 and 3 in which the fungicidal organic compound was directly blended. It is remarkably excellent in weatherability, and is excellent in weather resistance as compared with Comparative Example 1 in which a fungicidal organic compound which is not a triazole-based fungicidal organic compound is supported. From Tables 2 and 3, it can be seen that the mold-resistant sealing material composition of the present invention is extremely excellent in terms of durability, chemical resistance and weather resistance as a whole.

[0040]

EFFECT OF THE INVENTION The fungicidal sealing material composition of the present invention comprises:
Compared to a conventional sealing material composition directly containing an antifungal organic compound, the antifungal effect is excellent in persistence of the antifungal effect and also high in water resistance and chemical resistance, so that it is formed by the composition of the present invention. The sealing can maintain the antifungal property for a long period of time even if it is exposed to water, an acid or alkaline atmosphere. Also,
The fungicidal sealing material composition of the present invention does not discolor even under a severe environment such as ultraviolet irradiation, and can form a sealing excellent in durability. Due to these properties, the fungicidal sealing material composition of the present invention can be used in fields where long-term fungicidal effect and non-discolorable sealing are required, such as outer walls, baths, pools, toilets, toilets, windows, roads, It is effective in piers, water tanks, silos, etc., and is particularly effective as a joint material such as tiles.

Continuation of front page (72) Inventor Hideki Kato 1 at Funamicho, Minato-ku, Nagoya-shi, Aichi 1 Nagoya R & D Co., Ltd.

Claims (1)

[Claims] 1. A fungicidal sealing material composition comprising a fungicide having a triazole-based fungicidal organic substance supported between layers of a layered silicate and a sealing substrate.