JPH0559881B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention provides a bactericidal and algae-preventing composition comprising a halocyanoacetamide compound in a solution of ethylene glycol and water, which is stable even in the presence of a metal. It concerns how to use it. (Prior art) General formula of the present invention (Here, X is a halogen atom, Y is a halogen atom or a hydrogen atom, and R is a hydrogen atom or a lower alkyl group.) The halocyanoacetamide compound represented by the formula has already been described in Japanese Patent Publication No. 10386/1986 as an antimicrobial compound. It is known to be effective as a drug. The above compounds are used as slime control agents, algaecides, and disinfectant cleaning agents in paper and pulp mills, cooling water circulation processes, metal processing oils, casein, starch coating fluids,
It has wide applicability as a preservative for water-based paints, and is expected to have excellent medicinal effects in all applications. As such, it is a drug with a wide range of applications. (Problems to be Solved by the Invention) However, in order to use these as antibacterial and antialgal agents, it is required that the agents be stable during production, storage, and use. That is, compositions containing halocyanoacetamide compounds exhibit significant quality changes, particularly significant decomposition of the active ingredients, and may sometimes fail to exhibit their intended antibacterial and algae-proofing effects. Although it is a drug with wide applicability and high efficacy, it is a drug with various problems in terms of stability, and research on stabilization has been continued for many years.
For example, polyethylene glycols and their mono- and dimethyl, ethyl, n-propyl or n-
A method has been disclosed for stabilizing an organic liquid such as butyl ether by incorporating a halocyanoacetamide compound (Japanese Patent Publication No. 5375/1983). However, although research on stabilization has been conducted in this way, the current situation is that fully satisfactory results have not been obtained. Especially metals, e.g.
Decomposition of this compound in liquid compositions in the presence of iron, stainless steel, tin, zinc, copper, or alloys thereof has become a significant problem. For example, when manufacturing a composition containing a halocyanacetamide compound, contact with metal is unavoidable, and if a stainless steel filter is used during the manufacturing process, the active ingredient will be significantly decomposed during manufacturing, resulting in the desired quality. liquid composition cannot be obtained.
In addition, when contact with metal occurs even at low concentrations, such as in cooling water circulation processes, metal processing oils, and water-based paints in metal cans, where this composition is actually used, the decomposition of the halocyanacetamide compound may occur. As a result, there is a decrease in the durability of the potency and corrosion of metal surfaces during the process, etc., and improvements are needed. As mentioned above, compositions containing halocyanacetamide compounds as active ingredients do not decompose even in the presence of metals, and in addition to stabilizing the formulation itself, they can also be used with confidence in the presence of metals. It is necessary to develop a stable drug that can be used. (Means for solving the problem) As a result of intensive research to solve the above problems, we have found that a liquid composition in which a halocyanacetamide compound is dissolved in a liquid mixture of ethylene glycol and water has been stabilized. The properties of the product were significantly improved, and the active ingredients remained intact even in the presence of metals, and various problems such as stability during production, storage, and use were solved. . The stable liquid composition of the present invention contains 5 to 25% by weight of a halocyanoacetamide compound represented by the above general formula in a mixed liquid of ethylene glycol and water.
75% by weight dissolved. Here, the ratio of ethylene glycol and water is 1:1/7 to 5. The composition of the present invention can be produced by dissolving a halocyanoacetamide compound in a liquid mixture of ethylene glycol and water. Specific examples of the halocyanoacetamide compound represented by the above general formula of the present invention include monochlorocyanoacetamide, monobromocyanoacetamide, dichlorocyanoacetamide, dibromocyanoacetamide, N-methyldibromocyanoacetamide, and the like. The stabilized composition of the present invention is a slightly viscous liquid that is colorless and transparent to slightly pale yellow in color, and can be easily added to a process using an ordinary metering pump. Next, examples and comparative examples will be described. However, parts indicate parts by weight. (Examples) Example 1 20 parts of dichlorocyanoacetamide, 70 parts of ethylene glycol, and 10 parts of water are mixed and dissolved to obtain a stable composition containing dichlorocyanoacetamide as an active ingredient. Example 2 20 parts of dibromocyanoacetamide, 70 parts of ethylene glycol, and 10 parts of water are mixed and dissolved to obtain a stable composition containing dibromocyanoacetamide as an active ingredient. Comparative Example 1 20 parts of monobromic cyanoacetamide and 80 parts of polyethylene glycol (#200) were mixed and dissolved.
A composition containing monobromic cyanoacetamide as an active ingredient is obtained. Comparative Example 2 20 parts of dibromocyanoacetamide and 80 parts of diethylene glycol are mixed and dissolved to obtain a composition containing dibromocyanoacetamide as an active ingredient. Comparative Example 3 20 parts of dibromocyanoacetamide and 80 parts of polypropylene glycol (#400) are mixed and dissolved to obtain a composition containing dibromocyanoacetamide as an active ingredient. Comparative Example 4 20 parts of dibromocyanoacetamide and 80 parts of polyethylene glycol (#200) are mixed and dissolved to obtain a composition containing dibromocyanoacetamide as an active ingredient. Comparative Example 5 20 parts of N-methyldibromocyanoacetamide and 80 parts of dimethyl sulfoxide are mixed and dissolved to obtain a composition containing N-methyldibromocyanoacetamide as an active ingredient. Comparative Example 6 20 parts of N-methyldibromocyanoacetamide and 80 parts of trimethylene glycol were mixed and dissolved to obtain N-
A composition containing methyldibromocyanoacetamide as an active ingredient is obtained. Comparative Example 7 20 parts of dibromocyanoacetamide, 15 parts of 1,4-bis(bromoacetoxy)-2-butene, 43.5 parts of ethylene glycol, 20 parts of 1,1,1-trichloroethane, 0.7 part of polyoxyethylene nonyl phenyl ether , 0.3 part of calcium dodecylbenzenesulfonate, and 0.5 part of lactic acid stabilizer are mixed and dissolved to obtain a composition containing dibromocyanoacetamide and 1,4-bis(bromoacetoxy)-2-butene as active ingredients. Comparative Example 8 20 parts of dibromocyanoacetamide, 15 parts of 1,4-bis(bromoacetoxy)-2-butene, 43.5 parts of ethylene glycol, 20 parts of 1,1,1-trichloroethane, 0.7 parts of polyoxyethylene nonyl phenyl ether , and 0.3 part of calcium dodecylbenzenesulfonate are mixed and dissolved to obtain a composition containing dibromocyanoacetamide and 1,4-bis(bromoacetoxy)-2-butene as active ingredients. Comparative Example 9 5 parts of dibromocyanoacetamide, 15 parts of ethylene glycol, and 80 parts of water are mixed and dissolved to obtain a composition containing dibromocyanoacetamide as an active ingredient. (Effects of the Invention) A composition according to the present invention was manufactured at a manufacturing factory and its drug stability was examined, and results were obtained that were satisfactory compared to comparative drugs. In addition, in a preservative test of a diluted metal cutting fluid, the antiseptic effect after 14 days of use, a sensory test of putrid odor, the weight loss rate of the test piece, and the metal corrosivity determined by visual observation revealed that the drug of the present invention was confirmed to be stable. The composition of the present invention significantly improves the stability of the halocyanoacetamide compound, and particularly when used in the presence of metals in the metallic series, the stability is significantly improved and the active ingredient is not impaired. This makes it possible to solve various problems such as stability during manufacturing, storage, and use. Therefore, the composition of the present invention can be used without decomposition of its active ingredients in situations where it comes into contact with metal, such as in cooling water circulation processes, metal processing oils, or water-based paints sealed in metal cans. Next, the effects of the present invention will be specifically explained using test examples. Test Example 1 Stability test of halocyanacetamide compound 150 ml of each of the compositions of Examples and Comparative Examples was weighed into a 200 ml transparent glass bottle. A stainless steel test piece (SOS304, 1.0 x 2.0 x 120 manufactured by Nippon Test Panel Industry Co., Ltd.) was placed in the glass bottle.
mm) was folded in half and immersed. After 10 days, the liquid composition was taken out, and the stability of the liquid composition was determined by analyzing the components and observing changes in appearance. For Comparative Example 7, two glass bottles were prepared, and the test was conducted with and without the stainless steel test piece immersed. The non-immersion test was shown in Comparative Example 7*. The results are shown in Table 1.

[Table] Test Example 2 Stability test of halocyanoacetamide compound manufactured in a factory The drugs of Example 2 and Comparative Example 4 were each tested at 1,000 ml in an ethanal-lined compounding pot in an actual factory.
Kg was produced. The product was filtered for 30 minutes using a stainless steel Ultraformer filtration device and stored in a stainless steel product tank for about 1 hour. The product stored in the product tank was filled into a polyethylene container after 1 hour. Then the filled product 1
Store the can in a constant temperature room at 40℃, and after 30 and 60 days,
Stability was tracked through component analysis and observation of changes in appearance. The results are shown in Table 2.

[Table] Test Example 3 Preservation test of diluted metal cutting fluid A diluted cutting fluid with advanced microbial contamination was obtained from a transfer machine in a factory that manufactures precision machine parts. The contents of the diluted cutting fluid obtained are as follows. Type: Emulsion type Dilution ratio: 35 times PH of diluted liquid: 8.1 Producing bacteria: Bacteria: 4.1×10 ⁷ /ml Filamentous fungi/yeast: 2.0×10 ⁴ /ml Small cutting oil diluted solution installed indoors in advance Add the microbial-contaminated diluted cutting fluid and the test material to the circulation process and start operation. The bactericidal power of the agent was determined by measuring the number of viable bacteria after a certain period of time, observing the putrid odor of the diluted cutting fluid, and observing the corrosivity of metals.
The antiseptic effect and effect on metal materials were confirmed. The results are shown in Table 3.

[Table] Putrid odor judgment criteria −: Odor from oil only
: Strong rotten odor Criteria for determining the amount of rust on the surface of the test piece (visual observation)
-: No rust formation +: Slight rust formation: Rust formation on area of 1〓3: 〃 of 2〓3
＋＋＋＋: Rust occurs in an area of 2〓3 or more

Claims (1)

[Claims] 1. General formula (Here, X is a halogen atom, Y is a halogen atom or a hydrogen atom, and R is a hydrogen atom or a lower alkyl group.) 5 to 25% by weight of a halocyanoacetamide compound represented by ethylene glycol and 95 to 95% of water are mixed with ethylene glycol and water.
A bactericidal and algaecide composition stabilized in the presence of a metal, which is formulated in a 75% by weight solution and is characterized in that the ratio of ethylene glycol to water is 1:1/7 to 5. 2. The antibacterial and algae-preventing agent composition according to claim 1, wherein a compound consisting of a halocyanoacetamide compound, ethylene glycol, and water is enclosed in a metal can. 3. The antibacterial and algaecide composition according to claim 1, which uses a combination of a halocyanoacetamide compound, ethylene glycol, and water in a metallic series. 4 General formula (Here, X is a halogen atom, Y is a halogen atom or a hydrogen atom, and R is a hydrogen atom or a lower alkyl group). A method for preventing bacteria and algae using a composition stabilized in the presence of a metal by blending the solution with a ratio of 1:1/7 to 5 at 95 to 75% by weight.