KR100710557B1 - Novel sterilizing composition and use thereof - Google Patents

Abstract

The present invention relates to a bactericidal composition comprising IPBC (3-Iodo-2-propynylbutylcar bamate) represented by the following Chemical Formula 1 and BCM (2-Benzimidazolylcarbamine acid methylester) represented by the following Chemical Formula 2 and its use. The bactericidal composition of the present invention can suppress mold development more effectively and broadly in a small amount, and the fireproof coating, water paint, or papering paste prepared using the bactericidal composition of the present invention has excellent mold growth prevention effect. It can be used very effectively.

IC≡CCH ₂ OOCNHC ₄ H ₉

IPBC, BCM, Bactericidal Composition, Mold, Fire Retardant

Description

Novel sterilizing composition and use thereof

The present invention relates to a bactericidal composition comprising IPBC (3-Iodo-2-propynylbutylcar bamate) represented by the following Chemical Formula 1 and BCM (2-Benzimidazolylcarbamine acid methylester) represented by the following Chemical Formula 2 and its use.

IPBC is a widely used disinfectant for many applications, including wood preservatives and paint preservatives. In particular, the compound may be mixed with other germicidal components in addition to being used alone, and may be applied to various fields. For example, PCT International Publication No. WO 96/028972 discloses fungicidal compositions comprising 2- (thiocyanomethylthio) benzothiazole (TCMTB), IPBC, nonionic surfactants and enhancers, and The composition is applied to emulsify the leather in the form of emulsion or to provide the fungal resistance to the organic coating. However, IPBC has a relatively poor sterilizing effect against blue mold, has a weak heat resistance and tends to be ineffective at high temperature, and yellowing is easily caused by light.

On the other hand, BCM is a fungicide used in a variety of paints, plastics, leather and the like. The compound is one of benzimidazole derivatives, and it is generally known that benzimidazole derivatives have fungicidal activity. In this regard, National Patent No. 243539 to Bayer discloses an active formulation containing one or more azole derivatives and one or more benzimidazole derivatives. However, BCM has a weak sterilizing effect against black mold, so the effect is weak when used alone where the black mold is the main cause.

The most common causative agents found in environments where mold is a problem are the black molds and blue molds described above. Therefore, in the case of using the sterilizer alone, in order to exhibit better sterilization characteristics, the throughput is increased, thereby causing a problem of worker safety or a cost increase, and a problem of physical properties in the treated product. May cause. Therefore, there is a demand for the development of more improved fungicides.

Therefore, the inventors have conducted extensive research, and as a result, the two kinds of compounds mentioned above compensate for the shortcomings in the mutual sterilization ability to expand the sterilization spectrum, and not only show the arithmetic sum of the effects but also the synergy effect. The present invention was completed based on this.

Accordingly, it is an object of the present invention to provide a bactericidal composition which can suppress the occurrence of fungi in an effective and wide range in a smaller amount by complementing and inducing synergistic disadvantages of the bactericidal effect possessed by IPBC and BCM. .                         

It is another object of the present invention to provide a bactericidal composition which can significantly reduce the yellowing problem and persistence problem caused by IPBC by reducing the amount of IPBC used.

Still another object of the present invention is to provide a mold prevention fireproof coating, an aqueous paint or a paste for the production using the sterilizing composition.

The sterilizing composition of the present invention for achieving the above object is characterized in that it comprises 7 to 17% by weight of IPBC represented by the formula (1) and 83 to 93% by weight of BCM represented by the formula (2):

Formula 1

IC≡CCH ₂ OOCNHC ₄ H ₉

Formula 2

Hereinafter, the present invention will be described in more detail.

According to the present invention, the sterilizing composition in which IPBC represented by Chemical Formula 1 and BCM represented by Chemical Formula 2 is mixed is prepared by mixing a powder of IPBC and a powder of BCM. At the time of the mixing, a method using a simple mechanical manual mixing and mechanism, agitation, and the like may be used, and are not necessarily limited to a specific mixing method. In the present invention, the sterilizing composition in which IPBC and BCM are mixed shows a sterilizing effect remarkably superior to the arithmetic combination of the sterilizing effects obtained when each component is used alone. That is, by using two kinds of fungicides having different sterilization mechanisms and sterilization spectra, it is possible to suppress the occurrence of mold more effectively and broadly in a small amount, and to reduce the frequency of occurrence of resistant bacterial strains compared to the single use. You can get the effect.

The composition of the present invention is prepared by mixing with 7 to 17% by weight of IPBC and 83 to 93% by weight of BCM, when the content of IPBC is less than 7% by weight has a problem that the effect on the black mold is reduced, 17 weight If the percentage is exceeded, there is a problem that the cost rises without any further increase as the amount of IPBC is increased.

The sterilizing composition prepared as described above is applied to various applications in the form of a powder mixed or dispersed in water as needed, in particular, since it has excellent sterilizing ability against mold, it can be widely used for the purpose of controlling various fungi. have.

Fire-resistant cladding, which is used to prevent premature collapse of steel structures due to the fire of a building, contains a lot of organic matter that is easy to cause mold. It can be prepared by adding the sterilizing composition of the present invention to the raw material component of such a fireproof coating. At this time, the content of the sterilizing composition in the refractory coating material is preferably used in the range of 0.05 to 0.2% by weight, when less than 0.05% by weight, the sterilization power is lowered, and when it exceeds 0.2% by weight, the cost is increased without increasing the sterilization effect. The problem arises.

The bactericidal composition of the present invention can be added to the aqueous paint in a dispersed form to be applied to the production of an aqueous paint for preventing mold growth. At this time, the antimicrobial composition is preferably added in an amount of 0.5 to 2.0% by weight in the aqueous paint. Preferably, the antimicrobial composition is added in the form of dispersed in water, 7 to 10% by weight of the bactericidal composition (IPBC and BCM) of the present invention in the form of dispersed in water by adding to surfactant, viscosity regulator, and water After formulation is prepared, it is introduced into an aqueous paint. If the content of the antimicrobial composition is less than 0.5% by weight, the bactericidal power is lowered. If the content of the antimicrobial composition exceeds 2.0% by weight, a yellowing problem occurs when the light is exposed. The surfactant is preferably selected from the group consisting of Tween 80 and Tween 81, and more preferably Tween 80. In addition, the viscosity modifier is preferably selected from the group consisting of Vangel B (Vangel B) and xanthan gum, more preferably used together with Vangel B (Vangel B) and xanthan gum. The content of the surfactant and the viscosity modifier is used in an appropriate amount in consideration of the kind, use, etc. of the aqueous paint.

On the other hand, using the sterilizing composition of the present invention can be prepared for the papering pool. Generally, the grass for the papering contains a large amount of organic components, so that the mold is easily decayed and mold is generated on the wallpaper after the papering. Such a papering pool is prepared by adding the mixed sterilizing composition to a content of 2.0 to 5.0% by weight to the papering pool in a state of mixing water. At this time, if the content of the mixed sterilization composition powder is less than 2.0% by weight, the problem of the sterilization power is lowered, if the content exceeds 5.0% by weight is economical due to the increased cost.

Preferably, the mixed bactericidal composition is added to the disinfectant composition (IPBC and BCM) powder 3 to 10% by weight of a surfactant, a viscosity modifier, an adhesive and water, blended in the form of dispersion in water It is preferably added to the pool. At this time, it is preferable to use an aqueous adhesive agent, and EVA adhesive agent is more preferable. The surfactants and viscosity modifiers mentioned above are used. However, it is used in an appropriate amount in consideration of the kind, use, etc. of the papering pool.

On the other hand, the sterilization composition of the present invention has a wide range of applications, such as can be applied to cement, wood, and leather for the prevention of mold.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

Example 1

Preparation of Sterilizing Compositions

Powders of IPBC (SK) and BCM (Bayer) were mixed in a weight ratio of 17:83, 15:85, 12:88, 10:90, and 7:93, respectively. There was no difficulty in the mixing process and it was easily mixed and there was no problem of separating according to the particle size even after mixing.

Example 2

Synergistic effect

IPBC and BCM used in Example 1 were mixed in a ratio of 100: 0, 17:83, 15:85, 12:88, 10:90, and 0: 100 (IPBC: BCM), respectively, and various types of fungicides and sterilizations were used. After preparing the composition, each of them was placed in a fungal culture, inoculated with the fungus, and then cultured at 30 ° C. for 5 days, and the results were observed. As mold, two types of black fungus, Aspergillus niger and blue fungus, Penicillium pinophilum , were used. The lowest turbidity concentration was determined as the minimum growth inhibitory concentration (hereinafter, abbreviated as 'MIC') of each type of bactericide and bactericidal composition.

Synergy of the bactericidal power is synergistic index represented by Equation 1 according to the method published in Kull et al. (Kull, F. C et al., (1961) Appl. Microbiol. 9, 538-541); Hereinafter, the abbreviation 'SI') is determined that the sterilization power is reduced when the value is greater than 1, and the sterilization power is increased when the value is smaller than 1. The results are shown in Tables 1 and 2 below.

Ascent Index (SI) = (Q _a / Q _A + Q _b / Q _B )

In Formula 1,

Q _A : MIC value when A fungicide is used alone, Q _B : MIC value when B fungicide is used alone, MIC value of A when Q _a : A + B, and MIC value of B when Q _b : A + B Value. At this time, A fungicide and B fungicide means IPBC, BCM, respectively.

Synergistic effect of fungicides on Aspergillus niger Mixed Ratio (IPBC: BCM) Qa (ppm) Qb (ppm) QA (ppm) QB (ppm) Qa / QA (ppm) Qb / QB (ppm) SI 100: 0 0.5 0 0.5 One One 0 One 17: 83 0.14 0.66 0.5 One 0.28 0.66 0.94 15: 85 0.06 0.34 0.5 One 0.12 0.34 0.46 12: 88 0.10 0.70 0.5 One 0.2 0.7 0.9 10: 90 0.08 0.72 0.5 One 0.16 0.72 0.88 7: 93 0.03 0.37 0.5 One 0.06 0.37 0.43 0: 100 0 One 0.5 One 0 One One

Synergy Effects of Fungicides on Penicillium Pinotfilum Mixed Ratio (IPBC: BCM) Qa (ppm) Qb (ppm) QA (ppm) QB (ppm) Qa / QA (ppm) Qb / QB (ppm) SI 100: 0 0.5 0 0.5 0.5 One 0 One 17: 83 0.03 0.17 0.5 0.5 0.06 0.34 0.4 15: 85 0.03 0.17 0.5 0.5 0.06 0.34 0.4 12: 88 0.02 0.18 0.5 0.5 0.04 0.36 0.4 10: 90 0.02 0.18 0.5 0.5 0.04 0.36 0.4 7: 93 0.01 0.19 0.5 0.5 0.02 0.38 0.4 0: 100 0 0.5 0.5 0.5 0 One One

As can be seen from Table 1 and Table 2, in the experiment for Aspergillus sneeger it was confirmed that the sterilization power is increased when used in combination with IPBC and BCM alone. Particularly, when the IPBC: BCM mixing ratio was 7:93, it was confirmed that the same bactericidal power was obtained even when only 6% of IPBC was used alone and 37% of BCM alone.

In addition, the experiments on the penicillium pinophyllum confirmed the effect of the sterilization by the mixing of IPBC and BCM, especially when the IPBC: BCM mixing ratio of 7:93, 2% when using IPBC alone, IPBC: When the BCM mixing ratio was 17:83, and 15:85, it was confirmed that even when 34% of BCM alone was used, the same bactericidal power was exhibited.

Example 3

Comparison of the Effectiveness of Sterilizing Compositions According to Mold

Sterilization of IPBC and BCM in a 10:90 weight ratio against five fungal strains, namely Aspergillus niger, Penicillium pinofilum, Ureobasidium pullulanse, Glioliodium viens, and Cathomium globosome MIC values for the composition and IPBC alone were measured. MIC values were measured in the same manner as in Example 2, and the results are shown in Table 3 below.

Results of measurement of MIC values of fungicidal composition and IPBC alone against mold Used strain Bactericidal Compositions MIC (ppm) MIC of IPBC (ppm) Aspergillus Niger 0.2 0.5 Eureobasidium pullulans 0.8 2 Penicillium Pinotfil Room 0.2 0.5 Gillio Cladium Viens 0.2 2 Cathomium Globosome 0.2 2

As shown in Table 3, in the experiments on the five types of fungal strains, the bactericidal power was increased when IPBC and BCM were mixed, and the amount of fungicide was reduced by up to 90%, compared to IPBC alone. Confirmed that it can.

Example 4

Disinfectant of fireproof coating

A sterilizing composition having a ratio of IPBC: BCM = 15:85 prepared in Example 1 and 0.1 wt% of a single disinfectant (IPBC, BCM) were mixed together with the other refractory coating raw materials, and then water was added in a 1: 1.3 weight ratio. Kneading to prepare a fireproof coating having a composition of Table 4. In order to use the fireproof coating material prepared by the above method as a test piece, a diameter of about 3 to 4 cm and a thickness of about 0.5 cm was prepared.

Composition of fireproof coverings (in batch production) ingredient Dosage (g) cement 170 pulp 30 Vermiculite 150 gypsum 130 Perlite 50 Calcium carbonate 25 Surfactants One Thickener 2

The fungus is a test piece prepared by uniformly spreading spores of Aspergillus niger and Penicillium pinofilum on a nutrient medium (Potato Dextrose Agar medium; 215 g of Potato-dextrose powder, 1 g of agar 15 g of distilled water). After placing the in the center and incubated for 2 weeks at 30 ℃. After incubation, the growth of the mold around the test piece and the test piece was observed, and the results are shown in Table 5 below.

Antifungal force test result (size of halo zone ¹ )     Test piece Additive-free control group (mm) IPBC + BCM (mm) BCM (mm) IPBC (mm) Penicillium Pinotfil Room ^-2 17.0 15.0 - Aspergillus Niger - 5.5 - 4.5

¹ : Size of halo zone = (diameter of total halo zone-diameter of specimen) / 2

² : Halozone is not generated.

As shown in Table 5, only the Aspergillus niger, which is a black mold, did not grow in the fireproof coating prepared by using IPBC alone, and the penicillium pino, which was blue mold, in the fireproof coating prepared by using BCM alone. Only the filament was not grown, but when the sterilizing composition mixed with IPBC and BCM was added, it was confirmed that neither Aspergillus niger nor penicillium pinofilum did not grow. Therefore, it was found that when the composition of the present invention is applied, it has a broader antimicrobial spectrum.

Example 5

Comparison of Sterilization Persistence of Fungicides

The sterilizing composition prepared in Example 1 was mixed with the refractory coating material and added to have a content of 0.05, 0.1, and 0.2% by weight, respectively, to prepare a refractory coating specimen, and then prepared into a size of about 4 cm in diameter and about 0.5 cm in thickness. Placed in the center of an agar-free medium without carbon sources, five fungal strains were identified according to ASTM G21: Aspergillus niger, Penicillium pinophilum, Eureovacidium pullulans, Jilliorumdium virens, and cathomium globosomes. Mixed spores were sprayed, inoculated and incubated for 4 weeks, and the growth of fungi on the specimens was observed. Refractory coating material without addition of the bactericidal composition was used as an additive-free control. The growth status was determined by setting the grade, and the mold was not grown in grade 0, the growth was less than 10% in grade 1, 10-30% in grade 2, 30-60% in grade 3, and 60-100% in grade 4. Each grade was set. The results are shown in Table 6 below.

Anti-mildew test result Additive-free control (grade) 0.05% addition (grade) 0.1% addition (grade) 0.2% addition (grade) IPBC + BCM 4 0 0 0 IPBC 4 One 0 0 BCM 4 One 0 0

As can be seen from Table 6, in order to prevent mold growth in fire-resistant coating, at least 0.1 wt% should be added when IPBC and BCM were used alone, and even at 0.05 wt% with IPBC and BCM mixed sterilization composition. It was confirmed that the fungus did not grow. As a result, it was confirmed that the bactericidal power of the IPBC and BCM mixed bactericidal composition lasted longer than when treated alone.

Example 6

Antimicrobial Compositions and Antibacterial Effects for Water-based Paints

First, IPBC and BCM were added to prepare a composition dispersed in water in the composition of Table 7 below.

Antimicrobial Composition for Water-based Paint ingredient Content (% by weight) IPBC 0.84 BCM 6.16 Tween 80 (surfactant) 3.50 Xanthan gum 0.2 Vangel B (viscosity regulator) 0.3 water 89.0 Sum 100

The composition prepared in the composition of Table 7 was added to the aqueous insulating paint in 1% by weight and mixed well, then coated on paper and dried at room temperature for 1 hour. Paint coated paper without the antimicrobial composition as a control was prepared in the same manner. Smear the spores of black mold and blue mold prepared by cultivation in nutrient agar medium, and cut the prepared paper test pieces to 3 cm in diameter at the center of the medium, and incubate for 2 weeks at 30 ° C. Confirmed. Criteria for measuring the antimicrobial activity was determined by the size of the halo zone according to the method of Example 4, the results are shown in Table 8.

Evaluation of antimicrobial activity Control Antibacterial treatment effect (㎜) Penicillium Pinotfil Room ^-1 22.3 Aspergillus Niger - 15.5

¹ : No halo zone is created.

As shown in Table 8, when the IPBC and BCM mixed antimicrobial composition was added to the water-based insulating paint, both the black mold Aspergillus niger and the blue mold penicillium pinofilum were grown only to a slight extent, and thus the bactericidal of the present invention. It was confirmed that the composition exhibited excellent antimicrobial activity.

Example 7

Antimicrobial Compositions and Antimicrobial Effects Added to Doubling Paste

IPBC and BCM mixed antimicrobial composition was prepared in the composition of Table 9 below.

Mixed Sterilization Composition Composition ingredient Content (% by weight) IPBC 0.48 BCM 3.52 Twin 80 3.00 Xanthan gum 0.2 Vanzel b 0.15 EVA adhesive 30.0 water 62.65 Sum 100

Then, 1 kg of the composition, and 13 kg of water were added to 18 kg of the paste for mixing and then mixed well. The grass prepared by the above method was applied to the paper for papermaking, and the grass mixed with water without mixing the fungicide as a control was also applied to the paper for papering separately. In the same manner as in Example 6, the strain was smeared on the medium in advance, the grass-laden paper specimens were cut to 3 cm in diameter, and the grass-coated side was brought into contact with the medium, followed by incubation at 30 ° C. for 2 weeks. The results were confirmed and shown in Table 10 below.

Evaluation of antimicrobial activity Control Sterilization composition treatment (mm) Penicillium Pinotfil Room Grows on the surface of the test piece 27.7 Aspergillus Niger Grows on the surface of the test piece 18.1

As shown in Table 10, while the papering paper using the papering paste without the antimicrobial composition grew mold to the surface, the papering degree using the papering paste to which the antimicrobial composition of the present invention is added, the degree of growth of mold As it was mild, it was confirmed that the antimicrobial activity of the antimicrobial composition of the present invention was very excellent.

As described above, the bactericidal composition of the present invention prepared by combining IPBC and BCM, which are used alone for various purposes, not only compensates for the disadvantage that IPBC and BCM have a sterilizing ability against some molds, but also increases the sterilizing power. By exhibiting the effect, it is economically advantageous because it can suppress the occurrence of mold in an effective and wide range in a small amount compared to the case of using each component alone. In particular, because it has a wide range of sterilization spectrum, it can be applied to various applications, can reduce the frequency of appearance of resistant strains, and can also improve the safety for workers. In addition, the problem of discoloration or processability when using IPBC alone can naturally be alleviated as the usage amount is reduced.

All simple modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of the present invention will be apparent from the appended claims.

Claims (8)

A sterilizing composition comprising 7 to 17 wt% of IPBC (3-Iodo-2-propynylbutylcarbamate) represented by the following Chemical Formula 1 and 83 to 93 wt% of BCM (2-Benzimidazolylcarbamine acid methylester) represented by the following Chemical Formula 2. Formula 1 IC≡CCH ₂ OOCNHC ₄ H ₉ Formula 2

A fireproof coating comprising the bactericidal composition of claim 1 at 0.05 to 0.2% by weight. The antimicrobial composition for water-based paint, characterized in that prepared in the form of dispersed in water by adding 7 to 10% by weight of the bactericidal composition of claim 1 to a surfactant, a viscosity control agent and water. The method of claim 3, wherein the surfactant is selected from the group consisting of Tween 80 and Tween 81, and the viscosity modifier is selected from the group consisting of Vangel B and Xanthan gum. An antibacterial composition for an aqueous paint, characterized in that. The antimicrobial water-based paint, characterized in that it contains 0.5 to 2.0% by weight of the antimicrobial composition of claim 3. A mixed sterilizing composition for dopalic paste, characterized in that it is prepared in a dispersed form in water by adding 3 to 10 wt% of the sterilizing composition according to claim 1 to the surfactant, the viscosity control agent, the adhesive and the water. 7. The method of claim 6, wherein the surfactant is selected from the group consisting of Tween 80 and Tween 81, the viscosity modifier is selected from the group consisting of Vangel B and Xanthan gum, and the adhesive is an aqueous adhesive. Mixed sterilization composition for Daffodil. The antimicrobial dosing pool, characterized in that it contains 2.0 to 5.0% by weight of the mixed sterilizing composition according to claim 6.