JPS60231603A - Antimicrobial agent - Google Patents

Abstract

PURPOSE:An antimicrobial agent, obtained by combination of a halogenated aliphatic nitroalcohol and a halocyanoacetamide derivative in a specific proportion, capable of exhibiting excellent antimicrobial action by synergistic action regardless of the kind of molds, bacteria, yeasts, etc. thereon. CONSTITUTION:An antimicrobial agent containing a halogenated aliphatic nitroalcohol expressed by formula I (R<1> and R<2> are H, halogen or alkyl; X is halogen) and a halocyanoacetamide derivative expressed by formula II (X is halogen; Y is halogen or H; R<3> is H or lower alkyl), optimally combination of 3-bromo-3-nitro-pentanediol-2,4 and dibromocyanoacetamide at 1:10-10:1, preferably 1:5-5:1 weight ratio. USE:Usable in fields of water systems for paper pulp industry, aqueous coating materials, pastes, leather, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel antibacterial agents that contain two types of bactericidal compounds, a compound of general formula (1) and a compound of general formula (11), and exhibit a synergistic effect. It is crowded with people.

Conventionally, in various water systems such as wastewater from the papermaking process in the paper pulp industry and circulating cooling water in each glaze industry, industrial water f, water-based paints made using it, and the number of rough coatings have been used. , latex, printing paste, and leather are susceptible to the proliferation of microorganisms, which is the cause of the decline in productivity and quality.

In particular, in wastewater systems in the paper pulp industry, slime is generated due to the proliferation of bacteria, filaments, and yeast, and even in waterways where pulp slurry is present, it can be found in dirty areas on walls and chests where the slurry comes in contact with. Slime adheres to and forms on slurry contact parts such as flow zenox, transport pipes, and other parts where pulp slurry stagnates due to low flow velocity, and this slime often comes off as the process progresses, causing paper breakage. In addition to causing contamination of paper valve products, six other problems are occurring due to the proliferation of pests.

The occurrence of such failures causes an unnecessarily large amount of time and trouble when using high-speed machines, a considerable decrease in productivity, and economic losses.

In addition, microorganisms can grow in the circulating water system for cooling metal processing fluids, impairing the cooling performance and emulsifying properties of processing fluids.
In addition, bad odors are generated, deteriorating the working environment and causing undesirable phenomena in terms of public health.

Other problems caused by the growth of harmful microorganisms are found in industrial products such as water-based materials, paper coatings, polymer latex, paper pulp, glues, leather bases, and metalworking fluids.

Therefore, as agents for suppressing or controlling the occurrence of harmful microorganisms in water systems or the above-mentioned industrial products,
Until now, the examples have been 4 types of sheet metal compounds, 1 type of chlorine compound,
Compounds such as aquaternary ammonium salts, etc. have been used, but these compounds are toxic to the human body, emit foul odors, and are effervescent. undesirable phenomena such as In addition, when water systems containing these pesticides are used for general turbidity or are discharged into the sea, they give a negative impact on the environment and cause environmental pollution.

The inventor of the present invention, Nagisa et al., completed the present invention as a result of intensive research into antibacterial agents in order to eliminate the above-mentioned deficiencies.

However, the present invention is an antibacterial agent.

A halogenated aliphatic nitroalcohol represented by the general formula (wherein R1 and R2 represent a hydrogen atom, a halogen atom, an alkyl group which may carry a substituent, or a halogen atom).

Halocyanoacetamide derivative represented by the general formula (wherein,
An antibacterial agent characterized in that it is contained in a ratio of 10:10 parts by weight.

Halogenated aliphatic nitroalcohol compounds have sufficient activity against yeasts, and the desired effect cannot be obtained against bacteria and filamentous fungi at low concentrations.

In addition, halocyanacetamide compounds were disclosed in Japanese Patent Publication No. 42-10
Although it is a self-killing agent described in Japanese Patent Application No. 386, its activity against filamentous fungi is extremely poor, and the desired effect against bacteria and yeast cannot be obtained at low LT degrees.

The antibacterial agent of the present invention exhibits an extremely excellent antibacterial effect against harmful microorganisms such as filamentous 1, bacteria, yeasts, etc., irrespective of the type thereof, which cannot be expected from the constituent components alone.

Hereinafter, the antibacterial agent of the present invention will be explained in detail.

First, as the compound of general formula (1) in the present invention,
For example, 2-chloro-2-nitroethanol, 1-chloro-1-nitropropanol-2,3-chloro-3-ditroptanol-2,2-chloro-2-nitrobutanediol-1,3,1-chloro -1-nitrobutanol-2,2-chloro-2-nitrobutanol, 2-chloro-
2-Nitropentanol-3,2,2-cyclo2-
Nitroethanol, 2-10-2-bromo-2-nitroethanol, 3-chloro-3-nitro-pentanedio-2゜4.4-chloro-4-nitrohexanol-
3,2-bromo 2-nitroethanol, 2-bromo 2-nitrobrobanol, 2-bromo 2-ditrobutanediol-1; 3,3-bromo 3-nitropentanediol 2,4.2. 2-cyclomo-2-nitroethanol, 4-/'lomo-4-nitrohexanol-3,
2-fluoro-2-nitroethanol, 2-fluoro-
2-Nitrobutanediol-1,3,3-iodo-3-
Nitrobutanol-2,2-fluoro-2-chloro-2
-nitroethanol, 2-iodo-2-bromo-2-nitroethanol, 2-chloro-2-nitro-propanediol-1゜3.2-from-2-nitro-propanediol-1,3 etc. It will be done.

Examples of the compound of general formula (1) include monochlorocyanoacetamide, motupromcyanoacetamide, dichlorocyanoacetamide, dibromcyanoacetamide, and N-methyldibromcyanoacetamide.

It goes without saying that the above-mentioned halogenated aliphatic nitroalcohol compounds and halocyanoacetamide compounds are not limited to only one type, and 2fjli or more may be used in combination.

The most preferred composition of the present invention is one in which one component is dibromcyanoacetamide.

The compounding ratio of the compound of general formula (1) and the compound of general formula (It) is 1:10 to 10:1, preferably 1:5 to s:
x (if ratio). If either one is too small, a satisfactory effect cannot be achieved.

The antibacterial agent of the present invention is basically prepared by uniformly mixing the two components described above, but is generally prepared as an aqueous solution,
It can be used as a solvent solution, dairy dispersion, etc.

Examples of solvents that can be used here include alcohol solvents, ketone solvents, ether solvents, and hydrocarbon solvents. There are no particular restrictions on the manner of use, and various methods can be employed.

The amount of this antibacterial agent added varies depending on the concentration of microorganisms, but in the case of water systems in fields such as the pulp and paper industry, it is generally 0.
．． 01 to 1,100 ppm, and in the fields of water-based paints, glues, and leather products, exhibits good bactericidal activity at about 1 to 500 ppm.

It should be noted that there is no problem in adding stabilizers, surfactants, etc. to the antibacterial agent of the present invention as long as it does not impede the purpose of the present invention. , all parts in the examples indicate 1 part by weight.

Example 1 A vibration damping agent was obtained by mixing the following components.

3-furomor 3-nitro-pentanedio-2,4 (BNPE) 20 parts dibromocyanoacetamide 10 parts diethylene glycol 70 parts Example 2 The following ingredients were mixed to prepare a fungicide.

2-bromo 2-nitro-propane Diol-1,32Q part Dibromocyanoacetamide 10 parts Diethylene glycol 70 parts Example 3 A fungicide was obtained by mixing the following components.

BNPE 20 parts Motupromcyanoacetamide 10 parts Diethylene glycol 70 parts Example 4 A fungicide was obtained by mixing the following components.

2-Bromo-2-nitro-propanediol - 1,320 parts Monobromocyanoacetamide 10 parts Diethylene glycol 70 parts Comparative Example 1 A fungicide was obtained by mixing the following components 0 BNP1 30 parts Diethylene glycol 70 parts Comparative Example 2 A fungicide was obtained by mixing the following components.

2-bromo 2-nitro-10 pan Diol - 1,330 parts Diethylene glycol 70 parts Comparative example 3 A fungicide was obtained by mixing the following components.

Dibromocyanoacetamide 30 parts Diethylene glycol 70 parts Comparative example 4 A fungicide was obtained by mixing the following components.

Monobromocyanoacetamide 30 parts Diethylene glycol 70 parts Next, the antibacterial agents prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were tested according to the following test method. The microbial growth inhibitory concentration, slime generation prevention effect, and antiseptic effect were investigated.

Test 1 Microbial Growth Inhibitory Concentration Test This test was conducted for each of the following test bacteria. The test method itself is
The same applies to both cases of madder, and the details are as follows. That is, the culture solution contained 0.1% peptone and 0.1% glucose.
Using a mixed aqueous solution of 0.05% potassium phosphate, 0.01% magnesium sulfate, and 0.05% magnesium sulfate, suspend one of the following test bacteria in this culture solution, and add a certain amount of this to the culture solution. Pour into 6 clean test tubes, and for 5 of them, add 5, 10, 20, 40° 80 ppm.
Added antibacterial agent of each specified quality level, and no antibacterial agent was added to the remaining one tube. Using the six test tube samples obtained, shake at 32°C for U hours. Culture was performed.

Immediately after this 24-hour culture, the growth rate of the microorganisms was determined based on the turbidity produced by the proliferation of the bacteria. The concentration level of the antibacterial agent in test tube samples in which no bacterial growth was observed was investigated, and the lowest concentration was taken as the minimum concentration that completely inhibited the growth of the microorganism.

The results are shown in Table 1.

Test bacteria (The bacterial name abbreviation is shown in the heading.) J)ai: Jvizzc? eyaeyhaz at
ywyLrbybaJ, α: J44tyI! rac difference L411144&p47L4J, 8. , a: -&
c#fJv, a i-■L L LiJ, y: ノ1
calLg4nhi vi+ic, tyiii, 7.
n: Noribanru J-J-w,b nRishinni,,p
: Hesitation QQ4.

Table 1 (Note 1) The numerical value indicates the minimum concentration pm that completely inhibits growth.

(Note 2) + indicates completion of the test piece 1.

As is clear from Table 1 above, the antibacterial agent of the present invention (Examples 1 to 4) was effective against all test bacteria at a low concentration of 10 ppm or less; Test Example 2 Test for preventing bacterial growth and slime generation in wastewater after papermaking process In the papermaking process of a certain paper mill The antibacterial agents prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were added to the white water pit three times a day for 2 hours so that the water concentration was 20 ppm for 7 days. The number of microorganisms was measured.

The test method involved diluting a white water sample with sterilized water, placing a certain amount of this in a Petri dish, and pouring dissolved Waxman agar medium into it, mixing it, and solidifying it into a flat plate. After culturing in a thermostatic chamber (32° C.) for 2 days, microbial colonies generated were measured using a colony counter. The number of paper breaks during papermaking was also measured to confirm the antibacterial effect.

Table 2 From Table 2 above, it can be seen that the inhibitors of the present invention (Examples 1 to 4) have excellent l increase W4 inhibiting action.

Test Example 3 A bouillon liquid medium and a coating solution which had been previously subjected to 1 rot were added to a starch-based coating solution with a pH of 10.0 and stirred.
The fungicidal agent adjusted above was added to the trap to reduce the concentration to ppm.

After storing this in a thermostatic chamber at t-32°C for 5 days, the number of viable bacteria in each solution was measured. The result JJ is shown in Fuki 3-sa below.

Table 3

Claims (1)

[Claims] General formula % Formula % (In the formula, R1 and R2 are hydrogen atoms) - A halogen atom or an alkyl group which may have a substituent, X represents a halogen atom. ) and a rogenated aliphatic nitroalcohol. General formula (in the formula, X is a halogen atom, Y is a halogen atom), a halogen atom or a hydrogen atom, R3ki represents a hydrogen atom or a lower alkyl group. ) and the halocyanoacetamide derivative represented by 1=
An antifungal agent that causes wheezing when contained in a ratio of 10 to 10:1.