JPS6248603A - Industrial germicidal composition - Google Patents

Abstract

PURPOSE:An industrial germicidal composition obtained by blending at least two of DBNPA, DITHIOL and HCS, showing a strong mildewproofing effects with an extremely smaller amount than they are used individually. CONSTITUTION:An industrial germicidal composition containing at least two of 2,2-dibromo-3-nitropropionamide (namely, DBNPA), 4,5-dichloro-1,2-dithiol-3-one (namely, DITHIOL) and hexachlorodimethylsulfone (namely, HCS). This industrial germicide has high germicidal effects, synergistic effects, low toxicity and no fear of pollusion at all. It has high stability in preservation and in use, improved durability of effects and is inexpensively producible.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a new industrial disinfectant composition.

(Prior art) Conventional industrial products or materials such as latex emulsion, textile emulsion, emulsion paint, emulsion wax, and spinning oil. industrial cooling water,
Water-containing compositions, such as water used in the manufacture of valves, paper, etc. (so-called process water, e.g. white water), flood water used for secondary oil recovery, are susceptible to attack by microorganisms such as various bacteria, molds or yeasts. However, it has the disadvantage of being susceptible to rot and mold. A large number of fungicides are used to control microbial attack of these water-containing compositions.

(Problems to be Solved by the Invention) Heavy metal fungicides such as organomercury compounds and organotin compounds have been used to prevent microbial attack on aqueous compositions, but their strong toxicity Therefore, they were replaced by non-metallic organic fungicides. However, non-metallic organic fungicides may have insufficient bactericidal effects against certain types of microorganisms, may be unstable in target industrial products or materials, or may lack long-lasting effects. It has some drawbacks and is not satisfactory as an industrial disinfectant.

do not have.

The inventor of the present invention was conducting various researches in order to provide a useful industrial fungicide that exhibits excellent antiseptic and fungicidal effects on water-containing compositions that do not rot or emit. 2.2-dipromo-3-nitriloglobionamide (hereinafter abbreviated as DBNPA), 4.5-
Dichloro-1゜2-dithio-/l/-3-one (hereinafter referred to as
dithiol) and hexachlorodimethylsulfone (hereinafter abbreviated as HO2).
It was discovered that a composition containing more than 100% of the above species exerts a strong antiseptic and antifungal effect in a much smaller amount than when each of these is used in a car. The invention has been completed.

(Means for solving the problem) The present invention ij: 2, 2-dibromo-3-nitrilopropionamide (DBNPA), 4,5-dichloro-1,2
The present invention relates to an industrial sterilizing composition containing at least two or more of -dithio-yv-3-one (dithio-/L/) and hexachlorodimethylsulfone (HO2') as active ingredients.

The active ingredients of the industrial sterilizing composition of the present invention (hereinafter abbreviated as the composition of the present invention) are compounds having the following structures.

DBNPA ・ ・ ・ ・ 1 φNH2C0CBr
2CN1 (C8--・-----, -Cl30802CCI3) The composition of the present invention is suitable for use in water-containing materials such as Futex emulsion, textile emulsion, emulsion paint, emulsion wax, spinning oil, industrial cooling water, white water, flood water, etc. It exhibits excellent antiseptic and antifungal effects on the composition, and
There is no risk of residual toxicity or pollution, and there is no adverse effect on the target water-containing composition. Furthermore, the composition of the present invention is simple,
It is inexpensive and highly adaptable, exhibits antiseptic and antifungal effects, and is extremely useful as an industrial fungicide.

The composition of the present invention consists of: ■DBNPA and dithiol, ■DBNP
A and HO2, ■ dithiol and HO2, or ■ DBN
PA, dithiol, and HO2 are dissolved or dispersed in a suitable liquid (e.g., common solvent) and mixed with or mixed with a suitable solid carrier (e.g., diluent, filler). Adsorb and further if necessary.
Add emulsifier to this.

Dispersants, suspending agents, vegetable oils, mineral oils, higher alcohols, surfactants, stabilizing agents, etc. are added, such as oil agents, emulsions, water agents, water solvents, suspending agents, and powders.

It is used in appropriate dosage forms such as granules, fine powders, and pastes. These formulations can be prepared by methods known per se.

(1) DBNPA and dithio in the composition of the present invention.

or <1) The mixing ratio of DBNPA (!:HC8) is 1 to 9 parts by weight of dithio-/L' or HC8\rFJO, preferably about 0.
(1) Regarding dithiol and HO2, the amount of HO2 is about 0.1 to 9 parts by weight, preferably about 0.5 to 5 parts by weight, per 1 part by weight of dithiol. ,■D
In the three-component mixed composition of BNPA, dithio-μ, and ucs, D
Approximately 0.1 to 1 part of dithiol to 1 part by weight of BNPA
1 part of 4 parts, about 0.1 to 5 parts by weight of HO2, preferably about 0.2 to 2 parts of dithio-p, about 0.5 to 4 parts of HO2.
Parts by weight range.

The content of the active ingredients in the composition of the present invention, i.e., ■ the sum of the contents of DBNPA and dithio-/-, ■ the sum of the contents of DBNPA and HO2, ■ the sum of the contents of dithiol and HO2, ■ DB
The sum of the contents of NPA, dithio-~, and HO2 varies depending on the dosage form and purpose of use, but in general, it is appropriate to have a concentration of about 5 to 50% of the total composition. , for example, about 5 to 20% in the case of solutions.

For pastes, suspensions, powders, etc., the appropriate content is about 5 to 50% by weight.

Suitable liquid carriers include alcohols (
(e.g., methyl alcohol, alcohol, ethylene glycol, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), chemicals (e.g., dioxane, tetrahydrofuran, cellosolve, etc.), aliphatic hydrogen ash (e.g. gasoline, kerosene, kerosene, fuel oil, machine oil, etc.), aromatic hydrogenated compounds (e.g. benzene).

toludine, xylene, so-bento naphtha, methylnaphthalene, etc.), other halogenated hydrocarbon lamps I (e.g. chloroform, carbon tetrachloride, etc.), acid amides (e.g. dimethylformamide, etc.), esters (e.g. dimethylformamide, etc.) For example, methyl acetate, ethyl acetate, butyl acetate, fatty acid glycerin ester, etc.) or nitriles (such as acetonitrile) can be used; ~, propylene glycol colnato), cellulosophores (e.g., ethylene glycol/lemonoethyl ether, ethylene glycol/lemonomethyl ethyl ester, etc.), or cellulosophores (e.g., diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, etc.) etc.) are suitable. Examples of solid carriers include clays (e.g., kaolin, bentonite, acid clay, etc.), resins (e.g., talcum powder, waxite powder, etc.), and silicas (e.g., diatomaceous earth, silicic anhydride, silicate powder, etc.). ,
Examples include alumina, sulfur powder, activated carbon, etc., and these can be used alone or in combination of two or more.

Examples of emulsifiers, dispersants, etc. used in the composition of the present invention include soaps and higher alcohols f/l#r2!
Nt-, alky-μ sulfonic acid, a-μ-aryl-sulfonic acid, quaternary ammonium m, fatty acid ester, polyalkylene oxide type or anhydroso-pitot y
Surfactants such as surfactants are used, and it is generally preferred that the composition contains 0.5 to 10% by weight of surfactants. In addition, in place of these surfactants or as adjuvants therefor, if necessary, for example, alginic acid, agar, boxymethylcerone, polyvinyl alcohol/l/l, and monomer oil can be used.

Bentonite, Talesol soap, etc. can also be used. Furthermore, other types of fungicides (e.g., organic iodine fungicides, organophosphorus fungicides, benzimidazo fungicides, organic sulfur fungicides, phenol fungicides, antibiotics, etc.) may be added as necessary. ), insecticides (natural insecticides, carbamate insecticides, organic phosphorus insecticides, etc.), fragrances, low-molecular or high-molecular phosphates, etc. may be mixed as appropriate.

When using the composition of the present invention, depending on the object and purpose, for example, coating method, spraying method, dipping method, mixing method, etc.
An appropriate method such as a kneading method may be applied, and generally the total content of active ingredients in the target water-containing composition is 1 to 1 in the final concentration.
It is preferable to add it to about 500 ppm. To explain in more detail, for example, in the case of white water, this active ingredient (DBNP
A and dithio-I, DBNPA and HCS, dithio-μ
and H.C.S.

It is preferable to contain DBNPA, dithio-μ, and HCS at a final concentration of about 0.5 to 20 ppm. For example, when applied to a paper mill, the water-soluble liquid of the composition of the present invention may be applied to the process where sifting is likely to occur, that is, to the machine chain in the raw material system, or to the NuClean, head box, or white water pipe F in the white water system.
When applying the continuous addition method to a suitable addition location such as adding to water or shower water, the final concentration of the sum of the above active ingredients in white water is about 0.5 to 1.0 ppm, preferably 1. -5 ppm, and when applying the impact addition method, the final concentration of the sum of the above active ingredients is about 2-20 ppm, preferably 4-10 ppm.
It is preferable to add and contain each intermittently so as to maintain the desired level.

When added to paints, for example casein and formalin copolymers, water-soluble vinyl and acrylic)
Water-soluble polymer compounds such as V-based polymers, water-soluble vegetable oils, and poly-N T-y resins, or, for example, acrylic acid methylene/l/- L', vinyl acetate-maleic anhydride, styrene-butadiene, vinyl acetate μm methyl acrylate.

The composition of the present invention is preferably added to a latexne-based paint such as vinyl chloride and vinyl acetate so that the final concentration of the sum of the active ingredients is about 20 to 600 ppm.

In addition, when adding to spinning oil, for example, olive oil,
and vegetable oils such as mustard oil and peanut oil, and mineral oils.

By appropriately blending high-grade A-co-y, etc., and further adding a nonionic or anionic surfactant as necessary, the composition of the present invention is added to the uniformly mixed spinning oil until the final concentration of the sum of the active ingredients is 10. It is preferable to add and contain it so that it becomes about 100 ppm. In this case, intermittent addition is also effective;
It may be used alternately with other fungicides as needed.

(Effects of the Invention) The composition of the present invention is an excellent industrial fungicide having the following characteristics.

1) It has strong anti-shading power and has a synergistic effect.

U) Low toxicity and no risk of pollution.

m) high stability during storage and use;

iv) Excellent sustainability of effect.

■) Can be manufactured at low cost.

(Examples) Hereinafter, the present invention will be further explained in detail with reference to Examples and Experimental Examples, but the scope of the present invention is not limited by these in any way.

Example 1 2.2-dibromo-8-nitrilopropionamide 10
% (hereinafter all % in this specification indicates weight percentage), 4
．． 5-dichloride-1,2-dithiol-3-one 5%,
Hytenol N E 15 (of (Dai-Ko I1 Pharmaceutical) 2
%, methoxypolyethylene glyco-p (molecular weight approximately 215
~235)8. (%) to make 7 products. When using, add it directly or dilute it with a solvent to the specified concentration.

Example 2゜2.2-dibromo-3-nitrilo 10 pionamide 10
%, hexachlorodimethylsulfone 5%.

A product is prepared by mixing and dissolving 1% of New Ball P E 75" (manufactured by Sanyo Kasei) and 84% of polyethylene glyco-1v200. When used, it is sprinkled or diluted with a solvent to a predetermined concentration and added.

Example 8 10% 4,5-dichloro-1,2-dithio-/L/-a-one, 5% hexachlorodimethylsulfone.

Demo-A/N (manufactured by Kao Soap) 3% and 82% ethylene glyco-y henanomethi-ether were mixed and dissolved to prepare a product. When used, it is added as is or diluted with a solvent to a predetermined concentration.

Example 4 2.2-dibromo-3-nitrilopropionamide 5%
, 5% of 4,5-dichloro )82
% are mixed and dissolved to make a product. When used, it is added as is or diluted with a solvent to a predetermined concentration.

Experimental example I.

The antibacterial activity of the compositions of the present invention prepared in Examples 1 to 4 was compared with each single agent having the same active ingredient age. The test results are shown in Table 13. The test was performed using a multiple dilution method using a bouillon medium with a pH of 7.0, and after culturing at 33°C for 18 hours, the presence or absence of growth of the test bacteria was visually observed, and the minimum growth inhibition was determined. The concentration (MIC, μf/ml) was determined. Water was used for dilution.

Test drug 1 Composition 2 of Example 1 1 Composition 3 of 2 / 3 B1 Composition 4 Composition 5 of Example 4 DBNPA 15%, Hytenol NE15 ■
A solution prepared by mixing and dissolving 3% (Daiichi Kogyo Seiyaku) and 82% methoxypolyethylene glycol/L/(molecular weight approximately 215-235) is used after being diluted with a solvent to a predetermined concentration.

6 Dithio-/I/15%, Hitenol NEI 5■
(No. 1 Kogyo Pharmaceutical Tank) A solution prepared by mixing and dissolving 3% and 82% of methoxypolyethylene glyco-IV (molecular weight approximately 215 to 2a5) is diluted with a solvent to a predetermined concentration and used.

7 HC815%, Hitenor/l/NE15■ (Dai-Kogyo Pharmaceutical Tank) 8%, Metkin polyethylene glyco-/
A solution prepared by mixing and dissolving 82% of I/(molecular weight approximately 215-235) is used after being diluted with a solvent to a predetermined concentration.

As shown in Table 1, the industrial sterilizing compositions of Examples 1 to 4 of the present invention were more effective than each single agent when it was found that the wasp bacteria, which is the main cause of spoilage of industrial products and the formation of slime in irrigation water systems. Nu Zubutilnu, Stahyrokotsukas-Aureunu, Eshelichia
It showed antibacterial activity against coli, Pseudomonas niμginosa, Serratia marsetuscens, etc. at extremely low concentrations.

These antibacterial properties are synergistic, as is clear from the table.

Experimental Example 2゜The liquid agent obtained in Example 1 was transferred to the neutral paper machine chest of a paper mill for the amount of paper produced! 750 ppm was added once every 8 hours (30 minutes). Conventionally used 4 and 5
- With the 15% solution of dichloro u-1,2-dithiol-8-one, slime formation was observed in the mouth for two weeks after the start of operation, but by adding the composition of the present invention, continuous operation for one month was possible. Even after carrying out this procedure, no problems such as paper cuts caused by the slime occurred.

Experimental Example 3 The liquid agent obtained in Example 2 was added to the machine chest of a paper mill at a concentration of 100 ppm per papermaking amount once every 8 hours (8
0 minutes) was added. With the conventionally used 15% solution of 7'c2,2-dibromo-3-nitrilopropionamide, slime formation was observed at the mouth for two weeks after the start of operation.
By adding the composition of the present invention, even when continuous operation was carried out for one month, no problems such as paper cuts due to slime occurred.

Experimental Example 4 200 ppm of the solution obtained in Example 3 was added to a spinning oil bath in a textile factory and used for circulation. As a result, a 15% solution of hexachlorodimethypnuphon was mixed with 20%
The number of viable bacteria in the spinning oil bath with 0 ppmFAm was 14 for circulating use.
The number of viable bacteria in the spinning oil bath containing the composition of the present invention was 88 x 102 (cells/ml) on day 1, indicating the generation of slime.
ll1), no slime formation was observed.

Claims (1)

[Claims] 2,2-dibromo-3-nitrilopropionamide, 4
, 5-dichloro-1,2-dithiol-3-one, and hexachlorodimethylsulfone as active ingredients.