JPH06227912A - Mildew-proofing sealing material composition - Google Patents

Abstract

PURPOSE:To obtain a mildew-proofing sealing material effective for suppressing the growth of mold on a sealing material for a long period and preventing the surface contamination and deterioration of performance caused by the growth of mold. CONSTITUTION:A sealing material composed mainly of a modified silicone is compounded with a mildew-proofing agent consisting of bis(2-pyridylthiol-1- oxide) zinc salt and at least one kind of compound selected from benzimidazole compound, isothiazoline compound, pyridine compound, N-haloalkylthio compound, phthalimide compound, triazine compound and iodine compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention contains a bis (2-pyridylthiol-1-oxide) zinc salt and an antifungal agent having a low water solubility, and is used inside and outside a building, particularly around water. The present invention relates to an antibacterial sealant composition.

[0002]

2. Description of the Related Art In recent years, sealing materials have been widely used for the purpose of filling watertightness and airtightness by filling the joints and gaps of various building members. Among them, a sealing material containing a modified silicone as a main component is excellent in weather resistance and paintability and is used as a jointing agent for interiors and exteriors of buildings (JP-A-2-306907). A sealing material containing polydiorganosiloxane as a main component has excellent weather resistance, durability and dimensional stability, and is used in bathrooms, washrooms and the like.

However, it is known that when the sealing material is used for a long period of time, mold is generated on the surface thereof. As a cause of this, it is considered that the surface of the sealing material is in a state in which mold is likely to be generated due to the supply of nutrients from the dust adhering to the surface and the supply of water by the water absorbing action of the sealing itself. .

[0004] Alternaria (A) is a typical fungus of molds that propagate in sealing materials used in buildings and the like.
genus Lternaria, Cladosporium (Clad
genus osporium, Ulocl
genus adium, Exophial
a) Bacteria such as genus have been detected.

The generation of such molds contaminates the surface of the sealing material and spoils its aesthetic appearance, so that the sealing material must be reconstructed. In addition, the mold that propagates on the surface of the sealing material does not stay on the surface, but the mycelium of the mold penetrates into the interior, causing peeling and cracking of the sealing material, resulting in damage to buildings and water damage. There was a problem of bringing it.

Therefore, there is a strong demand for a technique capable of protecting the sealing material from mold deterioration over a long period of time.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and an object thereof is to suppress the generation of mold on the sealing material for a long period of time, and to prevent surface contamination and deterioration of performance by mold. It is to provide an antibacterial sealing material that prevents the above.

[0008]

The present invention will be described below. The sealing material used in the present invention comprises a modified silicone as a main component, to which a curing catalyst, a plasticizer, a filler, etc. are mixed.

The fungicide used in the present invention is preferably one which prevents the growth and reproduction of mold without impairing the characteristics of the sealing material, and is preferably bis (2-pyridylthio-).
1-oxide) zinc salt (hereinafter referred to as antifungal agent A) and the following compound (hereinafter referred to as antifungal agent B).

The antifungal agent B is at least one selected from the group consisting of benzimidazole compounds, isothiazoline compounds, pyridine compounds, N-haloalkylthio compounds, phthalimide compounds, triazine compounds and iodo compounds. There are more than one species.

Examples of the above-mentioned benzimidazole compound include 2- (4-thiazolyl) benzimidazole and the like.

Examples of the above isothiazoline compounds include 2-n-octyl-4-isothiazolin-3-one and 1,2-benzisothiazolin-3-one.

Examples of the pyridine compound include:
Tetrachloro-4-methylsulfonylpyridine and the like can be mentioned.

Examples of the N-haloalkylthio compound include N, N-dimethyl-N '-(fluorodimethylthio) -N'-phenylsulfanide.

Examples of the phthalimide compound include N- (trichloromethylthio) phthalimide.

Examples of the above triazine compounds include hexahydro-1,3,5-triethyl-S-triazine.

Examples of the iodo-based compound include diiodomethyl-p-trisulphone.

The above-mentioned antifungal agent may be added to the silicone polymer at the time of kneading with a curing catalyst or the like.
It is preferable to make the antifungal agent as fine powder as possible or to dissolve it in an appropriate solvent and mix it.

If the compounding amount of the above-mentioned antifungal agent is small, the antifungal effect is not exhibited, and if it is too large, the tensile strength of the sealing material is lowered or becomes brittle, and therefore 0.01 to 10% by weight based on the modified silicone polymer. Is preferable, and more preferably 0.1 to 5% by weight.

The antifungal agent is, for example, antifungal agent A.
If the amount of either of the antifungal agent B and the antifungal agent B is increased, the antifungal performance is deteriorated. Therefore, the mixing ratio of the antifungal agent A and the antifungal agent B is 1: 9 to 9: 1 by weight. Preferably
It is more preferably 1: 1. Particularly, when the mixing ratio is 1: 1, the excellent control effect and durability are exhibited.

To the sealing material composition of the present invention, for example, a coloring agent, an antioxidant, a reaction modifier, an antistatic agent, a polymer other than the modified silicone, and a fungicide other than the above are added, if necessary. May be done.

Next, the present invention 2 will be described. Invention 2
The sealing material used in (1) contains polydiorganosiloxane as a main component, and a curing catalyst, a plasticizer, a filler, and the like added thereto.

As the antifungal agent used in the present invention 2,
It is preferable to prevent the generation and reproduction of mold without impairing the characteristics of the sealing material, and it is composed of a mixture of the antifungal agent A and the following compound (hereinafter referred to as antifungal agent C).

The antifungal agent C is selected from the group consisting of benzimidazole compounds, isothiazoline compounds, pyridine compounds, N-haloalkylthio compounds, phthalimide compounds, triazine compounds, phenol compounds and iodo compounds. At least one selected from the above is included.

As the above-mentioned benzimidazole compound, isothiazoline compound, pyridine compound, N-haloalkylthio compound, phthalimide compound, triazine compound and iodo compound, the same compounds as those used in the present invention can be used. Can be mentioned.

Further, as the above-mentioned phenolic compound,
For example, p-chloro-m-cresol and the like can be mentioned.

The above-mentioned antifungal agent may be added to the polydiorganosiloxane polymer by adding it at the time of kneading with a curing catalyst or the like. The antifungal agent is previously made into a fine powder as much as possible or is dissolved in an appropriate solvent and mixed. Preferably.

The content of the above-mentioned antifungal agent is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the polydiorganosiloxane polymer.

The mixing ratio of the fungicide A and the fungicide C is preferably in the range of 1: 9 to 9: 1 by weight, more preferably 1: 1.

The antibacterial sealant composition of the present invention 2 contains a colorant, an antioxidant, a reaction modifier, if necessary.
Antistatic agents, other polymers, antifungal agents other than the above, and the like may be added.

[0031]

EXAMPLES Examples of the present invention will be described below. (Example 1) [Preparation of antibacterial sealing material] As a fungicide, bis (2-pyridylthio-1-oxide) zinc salt (Olin
"ZINC OMADAINE" manufactured by N. Co., Ltd. and a benzimidazole compound [component: 2- (4-isothiazolyl)]
-Benzimidazole, Sanai Oil Co., Ltd. "San-Isol 100") equivalent mixture was used, and 0.1% by weight of the above antifungal agent was added to 1000 ml of modified silicone (Sekisui Chemical Co., Ltd. "modified silicone"). Roll kneading was performed to prepare an antibacterial sealing material.

[Evaluation of Performance of Antibacterial Sealing Material] With respect to the above antibacterial sealing material, each test of 1) mold resistance test, 2) durability test and 3) field test was carried out to evaluate its antifungal performance. . 1) Mold resistance test (a) Preparation of test piece From the above antibacterial sealing material, thickness 500 μm, diameter 3
A cm disk was molded and air dried to give a test piece. (B) Preparation of agar medium In a plastic petri dish, 1 part by weight of non-sar LN-1 (manufactured by NOF Corporation), 1 part by weight of non-sar TN-1 (manufactured by NOF CORPORATION), 1 part by weight of peptone (manufactured by DIFCO),
An agar medium was prepared by mixing 1.5 parts by weight of agar and 100 parts by weight of water. (C) Preparation of mixed spore suspension A mixed solution consisting of 1 part by weight of each of non-sar LN-1 and non-sar TN-1 and 1000 parts by weight of water was sterilized under pressure and cooled, and then eight mixed solutions were prepared. , A for each mixture
lternaria, alternata, Clado
sporiumcladosporioides, Ul
Any one of the bacteria O. cladium atra, Exophiala and jeanselmei was dispersed, and equal amounts of the solutions obtained from the bacteria were mixed to prepare a mixed spore suspension. (D) Test method for mold resistance test The test piece prepared in (a) was placed on an agar medium, and 1 ml of the mixed spore suspension was sprayed on the test piece, and then the thermostatic bath (2
After culturing at 8 ° C and relative humidity of 95 to 100%, the mold growth conditions were determined on the 7th day, 14th day, 21st day and 28th day according to the following criteria, and the results are displayed. Shown in 1. (Criteria for Judgment) 3: No mold growth was observed on the test piece. 2: Mold growth is recognized on the test piece, but the growth area does not exceed 1/3 of the whole. 1: Mold growth was recognized on the test piece, and the growth area exceeded 1/3 of the whole.

2) Durability test A test piece prepared in (a) was irradiated on a sunshine weatherometer for 100 hours, and the same test as (4) was conducted as a test piece for a durability test. ) Was determined according to the same criteria as the mold resistance test, and the results are shown in Table 1.
It was shown to.

3) On-site test After peeling off the mold-contaminated sealing material part of the outer wall of the household where mold is generated, the antibacterial sealant prepared above is applied to the peeled part for 3 months. , Every 6 months, 12 months and 24 months, the mold generation was observed and judged according to the following criteria, and the results are shown in Table 1. (Judgment Criteria)-: No mold is found. +: A slight amount of mold was observed. ++: Mold is considerably generated.

[0035]

[Table 1]

(Examples 2 to 63, Comparative Examples 1 to 25) Table 2
-An antibacterial sealing material was prepared in the same manner as in Example 1 except that the antifungal agent A and the antifungal agent B shown in Table 7 were mixed in the proportions shown in the table. The same performance evaluation as in Example 1 was performed on this sealing material, and the results are shown in Tables 2 to 8.
It was shown to.

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

[Table 6]

[0042]

[Table 7]

[0043]

[Table 8]

(Examples 64-144, Comparative Examples 26-5)
3) As a silicone sealant, "Silicon Sealant" manufactured by Sekisui Chemical Co., Ltd. was used, except that the antifungal agent A and the antifungal agent B shown in Tables 8 to 16 were blended in the ratios shown in the above tables. An antibacterial sealing material was prepared in the same manner as in Example 1. A mold resistance test and a durability test were performed on this antibacterial sealing material in the same manner as in Example 1, and the results are shown in Tables 9 to 18. In the field test, after removing the mold-contaminated sealing material in the bathroom at home, the antibacterial sealing material was applied, and the mold generation status was checked every 3 months, 6 months, 12 months and 24 months. Observe and judge according to the same judgment criteria as in Example 1,
The results are shown in Tables 9-18.

[0045]

[Table 9]

[0046]

[Table 10]

[0047]

[Table 11]

[0048]

[Table 12]

[0049]

[Table 13]

[0050]

[Table 14]

[0051]

[Table 15]

[0052]

[Table 16]

[0053]

[Table 17]

[0054]

[Table 18]

In Tables 2 to 18, the following substances were used as the antifungal agent B. -Benzimidazole-based compound: 2- (4-isothiazolyl) -benzimidazole ("San-Isol 100" manufactured by San-ai Oil Co., Ltd.)-Isothiazoline-based compound: 2-n-octyl-4-isothiazolin-3-one (Rohm and Haas. "SKANE M-8" sold by Japan Co., Ltd. ・ Pyridine compound: tetrachloro-4-methylsulfonylpyridine ("Densil sold by ICI Japan Co., Ltd."
S100 ") N-haloalkylthio compound: N, N-dimethyl-
N ′-(fluorodimethylthio) -N′-phenylsulfanide (manufactured by Bayer “Preventol A
4 ")-phthalimide compound: N- (trichloromethylthio) phthalimide (" Prevento "manufactured by Bayer)
l A3 ")-Triazine-based compound: hexahydro-1,3,5-triethyl-S-triazine (“ Sanba ”manufactured by San-ai Petroleum Co., Ltd.
c ")-Iodo compound: diiodomethyl-p-tolylsulfone (" AMICAL48 "manufactured by San-Apro) -Phenolic compound: p-chloro-m-cresol (" PCMX "manufactured by Mitsubishi Gas Chemical Co., Inc.)

[0056]

The antibacterial sealant composition of the present invention comprises:
A sealing material containing modified silicone and polydiorganosiloxane as a main component is added with bis (2-pyridylthio-1-
(Oxide) zinc salt and various organic antifungal agents have a synergistic effect of antifungal performance. With a small addition amount, it suppresses the occurrence of mildew for a long period of time, and the appearance and contamination of sealing materials It is possible to prevent deterioration. Second
The antibacterial sealing material composition of the present invention can be suitably used particularly as a sealing material around water such as in a bathroom.

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Claims (2)

[Claims] 1. A sealing material containing a modified silicone as a main component, and a bis (2-pyridylthiol-
1-oxide) zinc salt, benzimidazole compound, isothiazoline compound, pyridine compound, N-
Haloalkylthio compounds, phthalimide compounds,
An antibacterial sealant composition comprising at least one selected from the group consisting of triazine compounds and iodine compounds. 2. A sealing material containing polydiorganosiloxane as a main component, a bis (2-pyridylthiol-1-oxide) zinc salt as a fungicide, a benzimidazole compound, an isothiazoline compound, and a pyridine compound. Compound, N-haloalkylthio-based compound, phthalimide-based compound, triazine-based compound, phenol-based compound, and at least one selected from the group consisting of iodo-based compounds are blended, antibacterial sealing material composition characterized by the above-mentioned .