JPH02247104A - Industrial germicidal composition - Google Patents

Abstract

PURPOSE:To obtain the title industrially effective composition having excellent immediate effects and sustained effects on whole microorganisms containing 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and a fungicide selected from a specific compound group as active ingredients. CONSTITUTION:An industrial germicidal composition containing 2,2'- dihydroxy-5,5'-dichlorodiphenylmethane and at least one fungicide selected from a group consisting of (A) an alkylene bisthiocyanate, (B) a halocyanoacetamide and (C) an isothiazolone-based compound as active ingredients. The blending ratio of 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and the component A or B (50:1)-(1:50) and the blending ratio of 2,2'-dihydroxy-5,5'- dichlorodiphenylmethane and the component C is (100:1)-(1:50). When two or three of the component A to the component C are used, the blending ratio of 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and the total amounts of the component A to the component C is (100:1)-(1:50).

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to an industrial sterilizing composition, particularly an industrial sterilizing composition that has extremely excellent antibacterial activity and also has excellent fast-acting and long-lasting antibacterial effects. Regarding the composition.

[Conventional technology] In the cooling water systems of various industrial plants, slime consisting of bacteria, filamentous fungi, algae, etc. is generated in the system, resulting in a decrease in thermal efficiency, blockage of water pipes, corrosion of pipe metal materials, etc. A failure occurs.

In addition, in the paper valve paper making system, slime mainly composed of microorganisms such as bacteria and filamentous fungi is formed on the inner wall surface of the system using various additives such as cellulose and starch as nutritional sources. and,
When such slime peels off from the wall surface, it can become mixed into the product as foreign matter, reducing product quality, or causing paper breakage in the papermaking process, impeding continuous operation.
This can cause problems such as significantly reducing production efficiency.

Particularly in the pulp and paper industry, large amounts of additives such as starch, latex, and casein are used, but since these additives serve as nutritional sources for the growth of microorganisms, they are putrefied by microorganisms, resulting in product deterioration. It is a major cause of

In addition, various problems caused by microorganisms occur in related fields such as emulsion paints, emulsion adhesives, and metal processing oils.

Conventionally, such microbial disorders in various industrial fields have been treated with antibacterial agents because they are relatively simple and economical to implement.

Typical antibacterial agents conventionally used include thiocyanate compounds, halocyanacetamide compounds, and isothiazolone compounds.

[Problems to be Solved by the Invention] Among the above-mentioned conventional antibacterial agents, thiocyanate-based compounds have a weak bactericidal activity and have the disadvantage that slime-constituting bacteria tend to develop resistance when used for a long period of time. In particular, this antibacterial agent has a drawback in that it has weak antibacterial activity against Microbacterium, which often appears as a constituent of slime.

Halocyanoacetamide compounds have excellent bactericidal activity and have the advantage of being fast-acting, but they also have the disadvantage that their bactericidal activity is short-lived and their efficacy is significantly reduced in alkaline systems. There is. Furthermore, it also has the disadvantage of having a weak bactericidal effect against mold.

Although isothiazolone compounds have some degree of bactericidal activity, they are not fast-acting, tend to develop resistance when used for a long period of time, and do not have excellent antibacterial activity against all types of bacteria. Therefore, when it is added alone to water-based microbial treatment where various miscellaneous bacteria exist, there is a drawback that resistant bacterial species are generated and sufficient effects cannot be obtained.

As described above, all of the antibacterial agents commonly used in the past have disadvantages in terms of antibacterial effects, and the use of these compounds alone has not always been able to sufficiently prevent slime damage.

It is an object of the present invention to solve the above-mentioned conventional problems and to provide an industrial sterilizing composition that has extremely high antibacterial activity and has excellent fast-acting and long-lasting antibacterial effects.

[Means for Solving the Problems] The industrial sterilizing composition of the present invention comprises 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and the following
and @, that is, at least one fungicide selected from the group consisting of: (1) alkylene bisthiocyanate (2), helocyanoacetamide (2), and isothiazolone compounds.

That is, the present inventors aimed to solve the drawbacks of conventionally used antibacterial agents and to provide an industrial sterilizing composition that has extremely high antibacterial activity and also has excellent fast-acting and long-lasting antibacterial effects. As a result of extensive research, along with the disinfectants listed above,
The following characteristics (1) to (2) are as follows: (1) Excellent bactericidal effect and long-lasting antibacterial effect.

■It is highly effective against bacteria that are highly resistant to the disinfectants listed in ■■ to ■, such as Microbacterium.

■ By combining with the disinfectants from ■ to ■, the antibacterial activity is synergistically improved.

2. By combining or blending an antibacterial agent with
．． It has been discovered that 2'-dihydroxy-5,5'-dichlorodiphenylmethane satisfies the above characteristics (■) to (■) and exhibits excellent antibacterial effects when used in combination with or blended with the disinfectants (■) to (@) above, and the present invention has been achieved. completed.

The present invention will be explained in detail below.

The industrial sterilizing composition of the present invention comprises 2,2'-dihydroxy-55'-dichlorodiphenylmethane (hereinafter abbreviated as "dichlorophene") and one or two of the above
Preferred specific examples of the compounds (1) to (2) to be used in combination with dichlorofen include the following.

(2) Alkylene bisthiocyanate Examples include methylene bisthiocyanate and ethylene bisthiocyanate, with methylene bisthiocyanate being particularly preferred.

■ Hecyanoacetamide Examples include compounds represented by the following general formula.

Examples include monobromocyanoacetamide, dibromocyanoacetamide, monochlorocyanoacetamide, dichlorocyanoacetamide, and bromochlorocyanoacetamide.

■ Isothiazolone compounds Examples include compounds represented by the following general formula.

Or for example, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-inchazolone, 2ethyl-3-inchazolone, 4,5-dichloro-2-octyl-3-
Isothiazolone, 1,2-benzisothiazoline-3-
on, 5-chloro 2-methyl-3-isothiazolone magnesium nitrate, 2-methyl-3-isothiazolone magnesium nitrate, 2-ethyl-3-inchazolone calcium chloride, 45-dichloro-2-
Examples include octyl-3-isothiazolone magnesium nitrate.

The blending ratio of dichlorofen and the disinfectants listed in ■ to ■ above (
When using one of (1) to (2), the weight ratio is preferably within the following range.

Mixing ratio of dichlorophene and ■alkylene bisthiocyanate 50:1 to 1.5゜Dichlorophene and ■
Blending ratio with halocyanacetamide 50; 1 to 1:
50 Mixing ratio of dichlorophene and ■ isothiazolone compound 100:1 to 1:50 In addition, when using two or more or three of ■ to ■ in combination, the total of dichlorophene and ■ to ■ It is preferable that the blending ratio is in the range of 100:1 to 1:5o.

In the industrial sterilizing composition of the present invention, if the blending ratio of dichlorophenone and the sterilizing agent (■ to @) is outside the above range, the synergistic effect of both will not be sufficiently obtained, and the antibacterial effect will not be sufficiently improved. There are some cases where this cannot be done.

There are no particular restrictions on the method of adding the industrial disinfectant composition of the present invention, and dichlorophenone and the disinfectants listed in ■ to ■ above may be added to the target system in a premixed state, or each may be added separately. You may do so. When the object to be treated is a synthetic resin emulsion, starch paste, glue, etc., the industrial sterilizing composition of the present invention may be added directly to these materials, or it may be added to coating color liquids, paints, adhesives, etc. that are pot products. You may also do this.

The amount of the industrial sterilizing composition of the present invention to be added varies depending on the components of the industrial sterilizing composition, the blending ratio, the target system to be treated, etc., but in normal cases, dichlorofen and the above-mentioned sterilizing agents It is preferable to add the active ingredient in an amount of about 0.1 to 10 μg/m It % for paper valve paper making systems, and about 1 to 500 μs/mρ for synthetic resin emulsions or starch pastes.

[Effect] Dichlorophene is ■ Excellent bactericidal power and long-lasting effect.

(2) Against Microbacterium, which appears as a slime-constituting bacteria, the fungicides (2) to (a) above are weakly effective, but dichlorofen is highly effective.

(2) It exhibits a synergistic effect when used in combination with the fungicides listed in (1) to (2) above.

It has excellent characteristics.

Therefore, according to the industrial sterilizing composition of the present invention, which contains dichlorophene and the sterilizing agents described in (1) to (3) above in combination or in combination,
An industrial sterilizing composition that has an antibacterial effect against all types of bacteria due to the extremely excellent synergistic effect of the two, has extremely high antibacterial activity, and also has excellent fast-acting and long-lasting antibacterial effects. is provided.

[Examples] The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

Example 1: Paper valve bacteriostatic test on white water Using neutral white water from a paper mill manufacturing coated base paper, dichlorophene (A) and methylene bisthiocyanate (Bl),
Dibromcyanoacetamide (C1) or 5-chloro-
The synergistic effect of the bacteriostatic effect due to the combined use with 2-methyl-3-inchazolone (Dl) was evaluated by the minimum inhibitory concentration measurement method (MIC measurement method).

That is, test white water (pH near, 0, bacterial concentration 2.0
After removing the suspended matter components of O' cells/mJZ) with N011 filter paper, 10% by weight of bouillon liquid medium was added as a test solution, and each drug was added to this test solution as shown in Figures 1 to 3. Add the mixture prepared to the desired blending ratio (weight ratio) at a predetermined concentration, and incubate at 30°C for 2 hours using a shaking incubator.
After culturing for 4 hours, the minimum concentration that inhibited bacterial growth was measured. The presence or absence of bacterial growth was determined by measuring the absorbance at 660 nm and determining whether there was an increase in absorbance.

The results are shown in FIGS. 1 to 3.

In FIGS. 1 to 3, the broken line represents the additive effect of both drugs, and when the test results form a concave curve with respect to this broken line, it indicates that there is a synergistic effect.

Therefore, from Figures 1 to 3, dichlorofen (A)
It is clearly recognized that the combination of B, C, and D above has a synergistic effect.

The above results demonstrate that dichlorofen is effective against bacteria that are highly resistant to fungicides B, C, or Dl among the various bacteria growing in white water; This suggests that the two drugs synergistically cause high damage to the same bacterial species due to differences in their antibacterial effects.

Example 2: Bacteriostatic test against Microbacterium By the same MIC measurement method as shown in Example 1, Microbacterium
Borescens IFO3750) was pre-cultured in a bouillon culture medium at 30° C. for 24 hours and used as the test bacteria to investigate the synergistic effect of the bacteriostatic effect.

That is, in the same manner as in Example 1, B used in Example 1 was added to dichlorofen (A) in a 10% by weight bouillon liquid medium.
After adding the drug containing C or Dl, a certain amount of the cultured bacteria was inoculated, and after culturing at 30° C. for 24 hours, the minimum inhibitory concentration of the drug was determined.

The results are shown in FIGS. 4 to 6.

As shown in FIGS. 4 to 6, a clear synergistic effect was observed when dichlorophene (A) was used in combination with B, C, or Dl.

Example 3 Styrene-butadiene latex and open circulation cooling water were used as samples, and 20% of each of the chemicals shown in Table 1 was added to the samples.
．． 5 μg/m 1 was added and 3 was added under the conditions shown in Table 1.
It was stored at 0°C and the number of viable bacteria was measured over time. For comparison, measurements were also conducted in the same manner without the addition of any drug. The number of viable bacteria was determined by the plate method using a bouillon agar medium.

The results are shown in Table 1.

As is clear from Table 1, when dichlorophene (A) and B, C, or Dl coexisted, superior bactericidal activity was exhibited compared to when a single compound was used. Furthermore, while dichlorophene (A) maintains its bactericidal activity over a long period of time, with B+, C+, and Dl alone, the number of bacteria increases over time, and the sustainability of the bactericidal effect is affected. It shows scarcity. On the other hand, when dichlorofen was used in combination with B+, C+, or Dl, the number of bacteria decreased with the passage of days, indicating that the bactericidal effect was sustained.

Example 4 White water (PUS, 1) from which newspaper base paper is made was used as a test liquid, and the chemicals shown in Table 2 were added at 5 μg/m Il.
After contacting at 30°C for 1 hour, the number of viable bacteria was measured by the plate method using a bouillon agar medium. In addition, for comparison, measurements were also made in the same way for samples without any drug added.

The results are shown in Table 2.

As is clear from Table 2, antibacterial agents containing dichlorophene (A) combined with alkylene bisthiocyanate, hecyanoacetamide, or isothiazolone compounds have superior bactericidal activity compared to the use of each alone. Indicated.

In addition, in Table 2, A, B 1. B2C1~C,,
D, to D5 represent the following.

A: Dichlorophene B1: Methylene bisthiocyanate B2: Ethylene bisthiocyanate C1 Nidibromocyanoacetamide C2: Monobromocyanoacetamide C3 Nidichlorocyanoacetamide D1: 5-Chlor-2-methyl-3-inchazolone B2: 4,5- Dichloro-2-octyl-3-inchazolone B3: 1,2-benzisothiazolin-3-one 5-chloro-2-methyl-3-inchazolone magnesium nitrate B6: 4.5-dichloro-2-octyl-3 - Isothiazolone Magnesium Nitrate Condolence Table Example 5 In a factory manufacturing coated base paper, 5-chloro-2-methyl-3-inchazolone (abbreviated as CMIT) was used alone at 1.5 to 2.0 μg/mu. The treatment was carried out three times a day by continuously injecting water into the white water circulation system for four hours. However, woody plants are rich in nutrients and the number of bacteria in the white water is high, making it easy for slime to form.Conventional treatments have not been able to sufficiently treat the slime, and paper breakage problems often occur due to slime. .

When such a system was treated with an antibacterial agent containing dichlorophene and CMIT in a composition ratio of 40:1 by injecting 4 μg/mj for 2.30 minutes three times a day, the paper breakage disappeared and the problem persisted for more than 3 weeks. Continuous operation became possible.

These results demonstrate that the IA treatment using the antibacterial agent of the present invention exhibits an excellent slime prevention effect with a small amount used per day.

[Effects of the Invention] As detailed above, the industrial sterilizing composition of the present invention has extremely excellent antibacterial activity against all types of bacteria,
Furthermore, an industrial sterilizing composition with excellent fast-acting and long-lasting antibacterial effects is provided.

Therefore, according to the industrial sterilizing composition of the present invention, it is possible to efficiently perform antibacterial treatment on any system with a small amount added.

[Brief explanation of drawings]

FIG. 1, FIG. 2, and FIG. 3 are graphs showing the results of Example 1, respectively. FIG. 4, FIG. 5, and FIG. 6 are graphs showing the results of Example 2, respectively. Agent Patent Attorney Tsuyoshi Shigeno Figure 1 compound B1 (JJg/nil) Figure 2 compound C1 (p9/rr+j)

Claims (1)

[Claims] (1) It is characterized by containing 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and at least one fungicide selected from the group consisting of the following (a), (b) and (c). Industrial disinfectant composition. (a) Alkylene bisthiocyanate (b) Halocyanoacetamide (c) Isothiazolone compound