JPS6216401A - Nonmedical germicide - Google Patents

Abstract

PURPOSE:The titled germicide, containing 2,2-dibromo-3-nitrilopropionamide (DBNPA) and/or 2-bromo-2-nitrilopropane-1,3-diol (BNP) and tetrafluoroisophthalonitrile as active constituents, having antimicrobial activity against a wide range of microorganisms and capable of exhibiting improved germicidal effect with a lower concentration than the use of the single agent by the synergistic effect. CONSTITUTION:A nonmedical germicide containing 2,2-dibromo-3- nitrilopropionamide (DBNPA) and/or 2-bromo-2-nitrilopropane-1,3-diol (BNP) and tetrafluoroisophthalonitrile respectively known as antimicrobial agents as active constituents. The compounding weight ratio of the above-mentioned former to the latter is 1:4-4:1. Preferably, a carrier or adjuvant is added to the above-mentioned active constituents and formulated into water-soluble liquid solution, emulsifiable solution, wettable powder, etc., for use. The above- mentioned germicide is used as a slime controlling agent in paper manufacturing process, water treatment slime controlling agent in industrial cooling water system, air conditioning cooling water system, e.g. buildings, etc., preservative in metal working oil, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a non-medical disinfectant used in water systems and the like.

[Conventional technology]

In the white water system of the paper manufacturing process and the cooling water system of chemical plants, microorganisms grow using organic matter mixed in the water as a nutrient source, causing unpleasant odors, slime generation, deterioration of product quality due to peeling, and continuous operation for cleaning. This causes problems such as shutdowns and reduced cooling efficiency, resulting in significant damage.

In addition, microbial damage often occurs in general industrial products due to their raw material composition and product storage conditions, and their prevention has become important. However, due to their strong toxicity to humans and animals and environmental pollution, non-metallic compounds have been increasingly used in recent years. As such a drug, 2,2-dibromo-3-nitrilopropionamide (hereinafter referred to as DBNPA) was published in
No. 10386, 2-bromo-2-nitropropane-1
,3-diol (hereinafter referred to as BNP)
-8917, tetrafluoroisophthalonitrile (hereinafter referred to as TFPN) was also used in Contrib, B
oyce Thompson In5t, 24 (6)
139-147 (1969), 24 (10) 203
-212 (1970), etc., are known as antimicrobial agents.

[Problem that the invention seeks to solve]

However, both of these drugs pose problems when used alone. For example, DBNPA and BNP have low efficacy against filamentous fungi, and cannot be sufficiently effective in paper mills that use waste paper raw materials, which are prone to troubles mainly caused by filamentous fungi. Furthermore, unlike DBNPA and BNP, TFPN is highly effective against filamentous fungi, but has problems such as insufficient efficacy against bacteria.

[Means for solving problems]

This invention is intended to solve the above-mentioned problems.By using the above-mentioned drugs in combination, it has antibacterial activity against a wide range of microorganisms, and a non-medical sterilizer that can sterilize at low concentrations due to synergistic action. The aim is to provide a drug.

This invention uses one or two compounds selected from 2,2-dibromo-3-nitrilopropionamide and 2-bromo-2-nitropropane-1°3-diol and tetrafluoroisophthalonitrile as active ingredients. It is a non-medical disinfectant characterized by containing:

DBNPA and BNP, which are one of the components of the present invention, may be used alone or both may be used in any proportion. The blending ratio of one or two compounds selected from DBNPA and BNP and TFPN is preferably in the range of 1=4 to 4:1 by weight.

The disinfectant of the present invention has the above-mentioned active ingredient as an essential ingredient, and may contain other antimicrobial components or adjuvants, etc., as long as the above-mentioned active ingredients coexist when used as a disinfectant. Although these may be formulated separately and mixed at the time of use, it is preferable to mix them in advance and use them as the same formulation. As for the formulation form, it can be used as a water-soluble liquid preparation, an emulsifiable liquid preparation, a wettable powder, a granule, a flowable preparation, and the like.

When formulated as an aqueous solution, the active ingredient DBNPA
As a solvent that can sufficiently dissolve BNP and TFPN and is compatible with water, amides such as N,N dimethylformamide, polyethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polypropylene glycol 7-methyl ether, etc. Hydrolic alcohols or derivatives thereof, ketones such as acetone, isophorone, and cyclohexanone, and solvents such as dimethyl sulfoxide can be used alone or in combination. In addition, in order to improve dispersibility in water or in products, anionic,
A nonionic surfactant or an anion-nonionic mixed surfactant can be used.

When formulated as an emulsifiable liquid, benzene, xylene,
Hydrocarbons such as kerosene, 1. Halogenated hydrocarbons such as L, 1-trichloroethane and the like can be used as the solvent.

In this case as well, the surfactant necessary for emulsification can be selected from anionic, nonionic, anionic-nonionic mixed surfactants, etc. depending on the solvent used.

When formulating as wettable powders, granules, flowables, etc., solid fillers such as clay, calcium carbonate, white carbon, and surfactants are blended and then finely ground to form the respective dosage forms.

[For production]

The non-medical disinfectant of the present invention is used by adding it to systems that require disinfection. Its application fields include slime control agents in paper manufacturing processes, slime control agents for water treatment such as industrial cooling water systems and air conditioning cooling water systems for buildings, preservatives for metal processing oils and metal processing diluted liquids, and water-based water bases for construction. It can be used as a disinfectant for paints and paper coatings in paper factories, as a disinfectant for thickeners such as starch and casein, and as a disinfectant for other industrial products and manufacturing processes.

In the case of slime control agents for paper manufacturing and slime control agents for water treatment, the concentration used is 10% of the water used.
It is preferably about 200 ppm and can be used by impact addition or continuous addition. In the case of preservatives such as metal processing oil, it is 15 to 200 ppm relative to the processing diluent, and in the case of disinfectants for paints and pastes, it is 150 to 20 ppm relative to the paint and paste.
It is preferable to use it by adding about 00 ppm.

The disinfectant of the present invention has antibacterial activity against a wide range of microorganisms including bacteria and filamentous fungi, and due to the synergistic effect, it can perform disinfection at a lower concentration than when used alone. As a microorganism with remarkable antibacterial activity, Enterobacter a
erogenes, Bacillus 5ubtil
is.

Escherichia coli, Pseudom
onas aeruginosa.

5taphylococcus aureus, Ps
eudomonas lacrymans.

Alcaligenes faecalis, Bac
Bacteria such as Illus cereus, Aspergi
llus niger, Penecellium
citrinum, Rh1zopus nigri
cans%Trichoderma Sp,, Chae
tomium giobosum, Penicill
um 5techkii.

Trichoderma viride, Geotr
ichum candidum, Rh1zopus n
igricans, Alternaria mali
.

Cladosporium herbarum, Au
filamentous fungi such as Reobasidium pullulans, Tromyces palustris (Corio
Coriol
us versicolor.

Examples include basidiomycetes such as 5erpula lacrymans.

〔Effect of the invention〕

According to the present invention, since the above-mentioned drugs are used in combination, they have antibacterial activity against a wide range of microorganisms, and due to their synergistic action, a far superior bactericidal effect is obtained than when using them alone, and sterilization can be performed at low concentrations. I can do it.

〔Example〕

Next, formulation examples and test examples of the present invention will be explained. In each example, parts indicate parts by weight.

Formulation Example I 15 parts of DBNPA, 5 parts of TFPN, and 80 parts of polyethylene glycol monomethyl ether are mixed to prepare a water-soluble solution.

Formulation example 2 DBNPA 10 parts, TFPN 10 parts, Tsurupol 2
564 (manufactured by Toho Kagaku Kogyo Co., Ltd., surfactant, trade name), 320,025 parts of polyethylene glycol, and 50 parts of xylene were mixed to prepare an emulsifying liquid.

Formulation example 3 DBNPA 5 parts, TFPN 15 parts, Tsurupol 80
0A 5 parts.

15 parts of polyethylene glycol monomethyl ether and 60 parts of xylene are mixed to prepare an emulsifiable liquid.

Formulation example 4 DBNPA 12 parts, TFPN 8 parts, Demol N (manufactured by Kao Soap Co., Ltd., trade name) 2 parts, Carplex #80
(Manufactured by Shionogi & Co., Ltd., White Carbon, trade name) 2
1 part, 5 parts of Kunilite #250 (manufactured by Kunimine Minerika Kogyo Co., Ltd., trade name) and 71 parts of clay were mixed and pulverized to obtain a wettable powder.

Formulation Example 5 10 parts of BNP, 10 parts of TFPN, and 80 parts of polyethylene glycol monomethyl ether are mixed to prepare a water-soluble solution.

Formulation Example 6 16 parts of BNP, 4 parts of TFPN, 40 parts of polyethylene glycol monomethyl ether, and 40 parts of cyclohexanone are mixed to prepare a water-soluble solution.

Formulation example 7 BNP 12 parts, TFPNa part, Tsurupol 800A
5 parts, 10 parts of cyclohexanone, and 65 parts of xylene were mixed to prepare an emulsifiable liquid.

Formulation Example 8 16 parts of BNP, 4 parts of TFPN, 2 parts of Thymol N, 4802 parts of Carplex, 54,882,505 parts of mites, and 71 parts of clay are mixed and ground to obtain a wettable powder.

Test Example 1 Bactericidal efficacy test sample bacteria: Enterobacter aerogene
s (hereinafter referred to as Ea) Filamentous fungi: Geotrichun+ candidum
(Hereinafter referred to as Gc) Test drug ■ DBNPA 10% acetone solution ■ BNP 10% acetone solution ■ TFPN 10% acetone solution Test method After pre-cultivating the test bacteria in a broth liquid medium, adjust the number of bacteria to be constant. Dilute with broth medium. Next, each test drug was diluted with sterilized water, a certain amount was added to the bacterial solution to obtain a predetermined concentration, and cultured with shaking at 32°C. After a certain period of time, a part of the bacterial solution was collected and viable bacteria were collected. Measure the number and determine the sterilization rate. The remaining bacterial solution is further cultured with shaking, and the turbid state after 24 hours is observed according to the following criteria.

Judgment criteria for turbidity after 24 hours A: No turbidity occurs at all.

B: Slight turbidity occurs.

C: Completely cloudy.

The results are shown in Table 1.

Test Example 2 Sterilizing effect and slime generation prevention effect using circulation device in paper manufacturing room Test bacterial liquid A bouillon liquid medium was added as a nutrient source to the circulating white water of a newspaper paper manufacturing machine.

Test drug■ Drug according to formulation example 1■ Drug according to formulation example 5■ DBNPA 10% cyclohexanone solution■ BNP
10% cyclohexanone solution ■ TFPN to%
Cyclohexanone liquid test method: Assemble a device indoors that simulates the white water circulation process of a papermaking machine at a paper mill, add chemicals such as an internal sizing agent to the circulating water, and operate at a circulation rate of 95%. Furthermore, the test agent was added by shock for 30 minutes three times a day so that the active ingredient concentration in running water was 15 ppm. The efficacy of the drug is determined by scraping off the slime generated in the system and measuring its weight.

The results are shown in Table 2.

Test Example 3 A DBNPA agent (DBNPA 10 parts,
When a formulation consisting of 89.3 parts of polyethylene glycol monomethyl ether and 25640.7 parts of Tsurpol was added three times a day for 30 minutes to a concentration of 45 ppm in water, on the 13th day of continuous operation, the slime adhering to the Saybol peeled off. This resulted in a decline in product quality. As a result, they were forced to shut down operations and clean up the process.

After that, the process was cleaned with alkali and restarted, and the chemical shown in Formulation Example 1 was added 3 times a day to a concentration of 15 ppm in water.
When the slime was added twice for 30 minutes, no slime was observed to adhere to any part of the process even after 30 days had passed since restarting operations, and a high-quality product could be made into paper.

The number of viable bacteria in white water when using DBNPA agent is 1.0 bacteria.
X10'/mQ, whereas for filamentous bacteria it is 1.3X10'/mA, when using the drug of Formulation Example 1, bacteria is 3.6X10''/mA.
12. Filamentous fungi are 1. OX 10"/mn or less.

Test Example 4 BNP agent (BNP2
0 parts, polyethylene glycol monomethyl ether 69
．． As a result of continuous addition of a formulation consisting of 3 parts and 25,640.7 parts of Tsurupol 25640.7 parts in water once a day for 6 hours at a concentration of 15 ppm in water, paper breaks occurred on the 9th day of continuous operation due to slime that was thought to have come off from the papermaking inlet. As a result, operations were suspended. The number of viable bacteria in white water at the time of suspension of operations was 1.7 x 10'/mQ for bacteria and 2.6 for filamentous fungi.
X 10s/*Q, and there were particularly many filamentous fungi.

After this, the process was steam cleaned and operations resumed, and the chemical shown in Formulation Example 5 was added once a day to a concentration of 5 ppm in water.
When continuously added for a period of time, no problems such as paper breakage due to slime generation occurred even after 30 days after restarting operations, and no deterioration in product quality occurred. In addition, the number of viable bacteria in white water 20 days after restarting operations was 1.5 x 10'/m Q
, filamentous fungi are 1. OX 102/mn or less.

Test Example 5 Test for anti-rotation effect of starch liquid Test bacteria Rotten liquid of oxidized starch liquid Test chemicals■ Drug according to Formulation Example 4■ Drug according to Formulation Example 8■ DBNPA 10% hydrating agent■ BNP 10% hydrating agent■ TFPN 10% hydrating powder test method 200g of starch paste sampled from the gelatinization process of oxidized starch is placed in a 300-mm polyethylene container, and the test agent is added to the specified concentration.1st: Add 1g of putrefaction liquid. After thoroughly stirring the starch paste, it was left in an incubator adjusted to 25℃, and after 4, 8, and 16 days, the number of viable bacteria and fungi in 1 g of starch paste was measured, and the rotten odor was detected after 16 days. is judged according to the following criteria,
The antiseptic efficacy of the drug was determined. In order to determine the durability of the drug, 1 g of the putrid liquid was added again after measuring the number of viable bacteria after 4 and 8 days.

Judgment criteria for putrid odor One: I don't feel invincible.

+: Slight sense of invincible odor.

++: It feels like an extremely invincible tool.

The results are shown in Table 3.

From the above results, it can be seen that the bactericidal agent of the present invention has a wide range of antibacterial activity, a much higher bactericidal effect, and a synergistic effect than a single formulation of each component.

Claims (2)

[Claims] (1) One or two compounds selected from 2,2-dibromo-3-nitrilopropionamide and 2-bromo-2-nitropropane-1,3-diol and tetrafluoroisophthalonitrile as active ingredients. A non-medical disinfectant characterized by containing. (2) The blending ratio of one or two compounds selected from 2,2-dibromo-3-nitrilopropionamide and 2-bromo-2-nitropropane-1,3-diol and tetrafluoroisophthalonitrile is Weight ratio: 1:4
A non-medical disinfectant that is ~4:1.