JPH02250805A - Industrial bactericide - Google Patents

Abstract

PURPOSE:To obtain an industrial bactericide for bactericidal and antiseptic use exhibiting excellent effect in small amount and effective in industrial field by using a 3-isothiazolone derivative or its metal salt complex and 5-bromo-5- nitro-1,3-dioxan as active components. CONSTITUTION:The objective bactericide contains, as active components, (A) one or more kinds of 3-isothiazolone derivative of formula (R1 and R2 are same or different H or halogen; R3 is H or 1-10C alkyl) or its metal salt complex and (B) 5-bromo-5-nitro-1,3-dioxan. The amount of the component B is preferably 0.1 to 64 pts.wt. (especially 0.5 to 32 pts.wt.) based on 1 pt.wt. of the component A (in the case of using two or more kinds of compounds as the component A, the sum is taken as 1 pt.wt.). In the case of using the agent as an antiseptic and mildew-proofing agent for industrial materials, the sum of the active components in the final product is preferably about 0.1 to 50ppm.

Description

[Detailed description of the invention] (b) Industrial application fields The bendicide of the present invention can be used especially in industrial products and materials.

To control and prevent deterioration and contamination caused by microorganisms in latex emulsions, water-based paints, metal processing oils, starch pastes, paper coating fluids, textile oils, lignin fluids, etc.

The present invention also relates to industrial disinfectants used to prevent slime damage caused by microorganisms in paper manufacturing processes and factory cooling water systems.

(b) Conventional technology Latex emulsions have traditionally been industrial products and materials. Water-based paints, paper coating fluids, textile oils.

Metallic oil! Harmful microorganisms such as bacteria, mold, and yeast can easily grow in air-insulating materials and in cooling water systems used in the paper valve industry and various industrial fields, which can cause product quality problems such as spoilage, deterioration, and contamination. This causes a decline in productivity due to slime problems. Until now, many fungicides have been used for the purpose of suppressing or controlling the occurrence of these harmful microorganisms.

(c) Problems to be Solved by the Invention Many agents have been used to control or prevent microbial disorders, including organometallic compounds, organic sulfur compounds, quaternary ammonium salt compounds, and phenolic compounds. Each compound has various drawbacks such as toxicity, pollution, and even foaming and deterioration of product quality when used for specific purposes. In terms of efficacy, it also has drawbacks such as insufficient bactericidal and bacteriostatic effects against certain types of microorganisms and lack of long-lasting effects, making it unsatisfactory as an industrial disinfectant. do not have.

The present inventor has conducted various studies to solve the problems of these conventionally used drugs and provide an industrial fungicide with useful bactericidal and preservative properties, and found that 3-isothiazolone derivatives, Abbreviated as MIT. ) or its metal salt complex and 5-bromo-5-nitro 1.3
- Dioxane (hereinafter referred to as

It was discovered that when used in combination with BNDO (abbreviated as BNDO), the bactericidal and sterilizing power is synergistically enhanced in a much smaller amount than when each is used alone, and exhibits excellent bactericidal effect and long-lasting preservative effect. Completed the invention.

(d) Means for Solving the Problems The present invention is based on the general formula (wherein R and R1 represent the same or different hydrogen atoms or halogen atoms, and R3 contains a hydrogen atom or a carbon number of 1 to IO. 5-bromo-5-nitro-1,3-dioxane and 5-bromo-5-nitro-1,3-dioxane are used together as active ingredients. This invention relates to industrial fungicides.

In MIT of the above formula, which is one of the active ingredients of the industrial disinfectant of the present invention, R+ and Rz represent a hydrogen atom or a halogen atom, and examples of the halogen atom include chlorine, bromine, and iodine. Further, R1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms.

Among these, methyl group is most preferred.

Specific examples of MIT and its metal salt complex are given below.

4-isothiazolin-3-one and its calcium chloride complex, zinc chloride complex 2-methyl-
4-inchazolin-3-one and its magnesium chloride complex 5-chloro-2-methyl-4-isothiazolin-3-one and its magnesium chloride complex.

Calcium chloride complex 4.5-dichloro-2-methyl-4-inthiazoline-
3-one and its zinc chloride complex 2-n-butyl-4-inchazolin-3-one and its zinc chloride complex 2-n-octyl-4-isothiazolin-3-one and its zinc chloride complex 4.5-one Dichloro-2-n-octyl-4-isothiazolin-3-one and its iron chloride complex 5-chloro-2-n-decyl-4-isothiazolin-3-one and its calcium chloride complex Other active ingredients in the present invention A certain BNDO is a cyclic acetal compound obtained by a dehydration condensation reaction of formaldehyde and 2-nitro-2-bromop-1 cobanediol (1,3).

The fungicide of the present invention is synergistic in suppressing and preventing rotting, deterioration, and contamination caused by bacteria and fungi in emulsion paints, spinning oils, latex emulsions, water-based paints, cutting oils, starch pastes, paper coating fluids, lignin fluids, etc. It exhibits sterilizing and antibacterial effects, and is also effective in preventing slime damage caused by microorganisms in paper manufacturing processes and factory cooling water systems. In addition, it is a useful industrial disinfectant with low toxicity and no concern about pollution, and does not cause foaming or any adverse effects on the target composition.

The composition of the present invention is prepared by dissolving or dispersing MIT or one or more of its metal salt complexes and BNDO in an appropriate solvent (water or an organic solvent such as alcohol or glycol).

If necessary, a surfactant can be added to prepare a preparation with an appropriate concentration. Further, a chelating agent (such as ethylenediaminetetraacetic acid) may be added as appropriate.

Examples of organic solvents include isopropyl alcohol.

Alcohols such as benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol,
dipropylene glycol, tetramethylene glycol,
Glycols such as polypropylene glycol, glycol ethers such as diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and diethyl carbonate.

Mention may be made of esters such as propylene carbonate, among which monomethyl ether of diethylene glycol or dipropylene glycol, as well as.

Preference is given to using one or more solvents of ethylene glycol, dipropylene glycol.

In addition, the active ingredient of this invention is preferably formulated into a liquid formulation using the above-mentioned solvent, but is not limited to this, and depending on the intended use, a solid diluent (such as kaolin, clay, CMC, etc.) may be used. It can also be used as a powder diluted with

According to this invention, it is also possible to synergistically perform sterilization by adding two active ingredients together as separate preparations to the system to be sterilized.

The mixing ratio of one or more of MIT or its metal salt complex and BNDO in the composition of the present invention is 1 for the former.
A strong synergistic effect is achieved by adding BNDO in the range of 0.1 to 64 parts by weight, preferably 0.5 to 32 parts by weight, based on the weight part (in the case of two or more types, the sum is 1 part by weight; the same applies hereinafter). shows.

When using the composition of the present invention, a target object.

The amount added varies depending on the purpose, but in general, when applied as a preservative or anti-mold agent for industrial products or materials, it is added simultaneously or separately so that the total content of active ingredients is about 0.1 to 50 ppII+ in the final concentration. It is preferable to add
11 When applied as a slime control agent in the paper process, the total content of this active ingredient in the white water system should be 0.1 to 20 pp.
Shock-add about 0.01 to 10 ppm for 30 to 60 minutes, 1 to 3 times a day, or about 0.01 to 10 ppm, 6 to 12 times a day
It is preferable to add it semi-continuously so as to maintain it for a certain period of time.Furthermore, when used as a slime inhibitor or algaecide for industrial cooling water systems, the sum of the contents of this active ingredient relative to the amount of water retained is 0.05~ It is preferable to add impact once a week so that the concentration is 10 ppn+.

(e) Examples The following is an example of the effects of the present invention.

explain.

[Synergy effect test method]

The synergistic effect of the two-component mixture is determined by the binary dilution method.

Both components were diluted to a predetermined concentration, and a certain amount of each was added to the bouillon medium.Next, a certain amount of the pre-cultured m solution was inoculated, and after culturing with shaking at 37 ° C. for 8 hours,
The concentration of both components at which no increase in absorbance is observed at 570 nm is determined as the minimum inhibitory concentration (hereinafter referred to as TDMIC) using the binary dilution method.
).

FIG. 1 is a graph in which the minimum inhibitory concentrations of each component are taken equally on both wheels using normal scale coordinates. The area above the curve of this graph, i.e. the TDMIC curve, indicates the growth inhibition zone, and the area below indicates the proliferation zone, and when the diagonal line and the TDMIC curve coincide, there is an additive effect.
A curve above the diagonal line indicates an antagonistic effect, and a curve below the diagonal line indicates a synergistic effect.

Example 1 (Seutomonas aeruginosa) 5-chloro-2-methyl-4-thiazolin-3-one (hereinafter referred to as compound A) and 5-bromo-5nitro-1,3-dioxane (BNDO) 1001 each
g/aa1<dimethylformamide was used as a solvent), and then the synergistic effect was examined according to the test method described above.

As a result, as shown in Figure 2, the TDMIC curve against Shutomonas aeruginosa clearly indicates a significant synergistic effect, and the synergistic effect of the two components that completely inhibited wound growth was 1. Concentration is 1.6m
g/+ml, and the concentration of BNDO was 3.2 mg/s+l. That is, this drug concentration is
The amount is 1/4 of the MIC of BNDO alone and 178 of that of BNDO alone, indicating a remarkable synergistic effect. In addition, there are nine combinations of concentrations of Compound A and BNDO that exhibit a synergistic effect, as shown in Table 1.

Table 1 () represents the number of minutes of a single MIC.

MIC of compound A alone: 6.3 (g/n+1) BND
MIC of O alone: 25 (more than/ml) For other combinations, see Figure 2 Example 2 (Bacillus subtilis) 4.5-dichloro-2-n-octyl-4-inthiazolin-3-one (hereinafter , Compound B) and BND
Table 2 and FIG. 3 show the results of the same test as in Example 1 using O.

Table 2 Table 3 Compound B alone M I C+ 1.6 (jg/steel!) B
MIC of NDO alone: 12.5 (jg/ml)
For other combinations, see Figure 3 Example 3 (Alcaligenes faecalis) 1 of 2-methyl-4-inthiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one
:5 mixture (hereinafter referred to as mixture C) and BNDO in the same manner as in Example 1. The results are shown in Tables 3 and 4.
5! Listed in l.

(Left below) MIC of mixture C alone: 3.2 (j1g/m1
) MIC of BNDO alone: 12.5 (meg/l) For other combinations, see Figure 4 Example 4 (Micrococcus luteus) 2-Methyl-4-inthiazolin-3-one magnesium chloride complex and 5 -chloro-2-methyl-4-
Table 4 and FIG. 5 show the results of a test conducted in the same manner as in Example 1 using a 1=3 mixture (hereinafter referred to as 1 mixture) with isothiazolin-3-one magnesium chloride complex and BNDO.

(Margins below) Engraving of the specification (no changes to the contents) Table 4 Table 5 Mixture alone MIC: 12.5 (#gAI)B
MIC of NDO alone: 50 (sg/ml) For other combinations, see Figure 5 Example 5 For starch liquid preservative, compound B used in Example 2 and BNDO were added to a 30% aqueous dispersion of oxidized starch. A mixture of 1=1 (weight ratio) was added in an amount equivalent to 5 ppm, and the mixture was heated to temperature 3.
The starch solution was left in an incubator at 7° C. and 90% humidity to determine the number of days the starch solution was inhibited from rotting.

The results are shown in Table 5.

(Margin below) Example 6 For preservative protection of synthetic polymer emulsions.

Mixture C and BNDO used in Example 3 were each dissolved in dipropylene glycol, and each single agent and mixture C:
A formulation containing BNDO and BNDO at a ratio of 4:1 (weight ratio) was prepared. These preparations were added to styrene-butadiene latex so that the total amount of active ingredients was 10 pp-, and the temperature was 37°C.

The sample was placed in a thermostatic chamber with a humidity of 90%, and changes in the number of raw materials in the sample were measured over time. (11 companies [B43 Nsha Tsuru) The results above are shown in Table 6.

Engraving of the 6th specification (no changes to the contents) Number of viable bacteria/ml Example 7 A 20% aqueous solution of the mixture used in Example 4 was transferred to the machine chest of a newspaper manufacturing factory so that the concentration in water was 20 ppva. After continuous addition for 6 hours a day and continued operation, 1
A slime consisting mainly of bacteria formed and adhered to the inner wall of the machine during the interleaving process, causing a piece of paper.9 After cleaning the machine, a 20% solution of BNDO (dipropylene glycol 79
．． When 5L nonionic surfactant (contained in Te)Onic 7020.5) was continuously added to Machine Chest for 8 hours a day at a concentration of 30 ppm in water, on the 6th day, a lot of slime formed and continuous operation became difficult. Ta. Therefore, after cleaning the machine, we added each of the above-mentioned liquids to the machine chest at a rate of 10pp for 6 hours a day and continued operation, and no slime was observed in any part of the machine even after one month had passed. Not a single piece of paper was broken.

(F) Effects of the Invention In the present invention, as an industrial disinfectant, one or more of the 3-isothiazolone derivatives of the general formula or metal salt complexes thereof and 5-bromo-
When used in combination with 5-nitro and 1,3-dioxane, the bactericidal and bacteriostatic power is synergistically enhanced in a much smaller amount than when each is used alone, resulting in excellent bactericidal effects and sustained antiseptic effects. It was found that it works.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. means an alkyl group containing 10. ) and one or more of the 3-isothiazolone derivatives or metal salt complexes thereof represented by 5-bromo-5
- Nitro-1,3-dioxane as an active ingredient. The mixing ratio of one or more 2,3-isothiazolone derivatives or metal salt complexes thereof and 5-bromo-5-nitro-1,3-dioxane is 1 part by weight (2 parts by weight) of the former.
In the case of more than one species, the sum is 1 part by weight. ) for 5
-Bromo-5-nitro-1,3-dioxane from 0.1 to
The industrial fungicide according to claim 1, wherein the amount is 64 parts by weight. The mixing ratio of one or more 3,3-isothiazolone derivatives or metal salt complexes thereof and 5-bromo-5-nitro-1,3-dioxane is 1 part by weight (2 parts by weight) of the former.
In the case of more than one species, the sum is 1 part by weight. ) for 5
-Bromo-5-nitro-1,3-dioxane from 0.5 to
The industrial fungicide according to claim 1 or 2, which is 32 parts by weight. 4. One or more 3-isothiazolone derivatives or metal salt complexes thereof and 5-
An industrial sterilization and preservation method characterized by synergistically performing sterilization and preservation by adding bromo-5-nitro-1,3-dioxane simultaneously or separately.