JPH022843B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (However, in the formula, X represents a halogen atom, and Y represents a halogen atom or a hydrogen atom.) A compound selected from the acetophenone compounds (hereinafter referred to as group A) shown in (a) 3, 5-dimel-1,3,5-2H-tetrahydrothiadiazine-2-thione (b) Methylenebisthiocyanate (c) 1,4-bis(bromoacetoxy)2-butene (d) 1,2-bis( one or more compounds selected from bromoacetoxy)ethane and (e) 2-bromo-2-nitro-1,3-propanediol (the compounds (a) to (e) above are hereinafter referred to as group B); The present invention relates to a non-medical antibacterial algae agent characterized by containing as an active ingredient. In recent years, the use of water has become essential in the chemical industry, and the amount used has been increasing. As a natural problem associated with this, problems such as clogging by slime caused by microorganisms, such as filamentous fungi, bacteria, or algae, occurring in cooling towers and the like, and a decrease in heat exchange performance, are increasing. In addition, in paper and pulp factories, slime due to the growth of filamentous fungi and bacteria in the industrial water is generated on pulp white water, riffler walls and screens, which are important parts of the manufacturing process, and some of the slime falls off. This causes problems such as deterioration of paper quality and causing paper breakage in production processes using high-speed machines.
Additionally, in metal processing plants, the growth of fungi and bacteria in the recirculating water systems for lubricating oil emulsions can corrode metal products by spoiling the water and producing slime, which is a collection of microorganisms. let There are also problems during storage of the lubricating oil emulsion itself. Furthermore, in addition to these disturbances in industrial water systems, there are also disasters caused by the growth of microorganisms. For example, industrial materials such as paint, pulp, fiber processing glue, and plywood may rot or grow mold, and these disasters are widespread. Conventionally, metal compounds such as organic mercury have been used as control agents for these microorganisms. but,
These compounds are highly toxic and have a negative impact on fish and shellfish if they are directly discharged into rivers during drainage. Furthermore, as its effects on the human body become clearer, it has become a serious pollution problem and its use is being regulated. For this reason, organic chlorine-based, organic sulfur-based, quaternary ammonium salts, etc. have been studied and used as alternative chemicals, but organic chlorine-based chemicals are irritating, and organic sulfur-based chemicals are harmful to products. These agents also have various disadvantages in use, such as the effect they have on color tone, and the strong foaming of quaternary ammonium salts. As a result of various studies to solve this problem, the present inventors discovered that a compound selected from Group A and a compound selected from Group B
It has been discovered that a composition containing one or more compounds selected from the group as active ingredients is extremely effective as a control agent for industrially harmful filamentous fungi, bacteria, algae, etc., compared to when each is used alone.The present invention This is the completed version. The following compounds are included in Group A. 2-Bromo-4'-hydroxyacetophenone 2-chloro-4'-hydroxyacetophenone 2,3'-dibromo-4'-hydroxyacetophenone 2,3'-Dichloro-4'-hydroxyacetophenone Also, the following are compounds of Group B. (a) 3,5-dimethyl-1,3,5-2H-tetrahydrothiadiazine-2-thione (b) NCSCH ₂ SCN Methylenebisthiocyanate (c) BrCH ₂ COOCH ₂ CH=CHCH ₂ OOCCH ₂ Br 1,4-bis (bromoacetoxy)2-butene (d) BrCH ₂ COOCH ₂ CH ₂ OOCCH ₂ Br 1,2-bis(bromoacetoxy)ethane (e) 2-Bromo-2-nitro-1,3-propanediol The drug of the present invention is prepared by mixing the compounds listed in Group A and Group B, further adding a solvent or a solid fine powder diluent and a surfactant, and adding water to the mixture. Use in a state where it can be emulsified or suspended. In addition, for the drug of the present invention, a compound of group A and a compound of group B are prepared separately and mixed at the time of use, or when either a compound of group A or group B is used first and another drug is used immediately. It also includes. Furthermore, the drug of the present invention can be used in combination of two or more compounds, either directly or dissolved in a solvent. For these drugs, compounds of Group A and Group B are preferably mixed in a ratio of 0.1 to 10 of the latter to 1 of the former. The drugs of the present invention are characterized by exhibiting extremely superior efficacy compared to when each drug is used alone. Acetophenone compounds included in Group A exhibit activity against bacteria, filamentous fungi, and algae in general, but have low activity against some bacteria and filamentous fungi. It is an unsuitable agent as an antibacterial and algae agent that requires high activity against bacteria, fungi, and algae in general, and has poor practical use when used alone. On the other hand, drugs included in group B also exhibit some activity against bacteria, filamentous fungi, and algae at high concentrations, but are extremely poor at low concentrations.
However, by combining these drugs of groups A and B, which have drawbacks when used alone, it is possible to control the proliferation of a wide range of microorganisms that cannot be predicted. The non-medical antibacterial algae agent of the present invention can be used in water used in paper and pulp manufacturing processes, industrial water such as industrial cooling water, cooling water for air conditioning and heating, lubricating oil for metal processing, aqueous emulsion, paper, wood, plywood, paint, glue, pulp,
It can also control filamentous fungi, bacteria, yeast, algae, etc. that grow parasitically on these finished products during the manufacturing or processing process of fibers, etc. In particular, the agent of the present invention is used to treat Aspergillus niger, which is a major causative agent of microbial damage to industrial water, metal processing lubricants, water-based emulsions, paper, wood, paint, plywood, etc. that cannot be controlled with each single agent. Filamentous fungi such as Penicillium stetskii, Geotrichum candedum, Cladosporium herbalum, etc.
It effectively acts on bacteria such as Aerobacter aerogenes and Bultis subtilis, and can completely suppress the occurrence of industrially harmful microorganisms with a small amount of chemical. In particular, it has been found to be effective as a slime control agent for paper manufacturing, a lubricant for metal processing, a preservative for aqueous emulsions, paints, and glues. Next, examples will be shown and explained, but the present invention is not limited to the range shown below. Example 1 10 parts of compound (1) (the following parts indicate parts by weight), 10 parts of compound (a), 30 parts of diethylene glycol, N,N
- Mix 48 parts of dimethylformamide and 2 parts of Solpol (manufactured by Toho Chemical Industries, Ltd.) to prepare an emulsion. Example 2 15 parts of compound (1), 5 parts of compound (b), 78 parts of ethylene glycol, and 2 parts of Solpol (manufactured by Toho Chemical Industries, Ltd.) are mixed to prepare an emulsion. Example 3 10 parts of compound (1), 10 parts of compound (c), 30 parts of methyl chloroform, 48 parts of polyethylene glycol, and 2 parts of Solpol (manufactured by Toho Chemical Industry Co., Ltd.) are mixed to prepare an emulsion. Example 4 10 parts of compound (1), 10 parts of compound (e), 78 parts of diethylene glycol, and 2 parts of Solpol (manufactured by Toho Chemical Industries, Ltd.) are mixed to prepare an emulsion. Example 5 10 parts of compound (3), 10 parts of compound (c), 30 parts of methyl chloroform, 48 parts of ethylene glycol, and 2 parts of Solpol (manufactured by Toho Chemical Industries, Ltd.) are mixed to prepare an emulsion. Example 6 10 parts of compound (1), 5 parts of compound (d), 30 parts of methyl chloroform, 53 parts of polyethylene glycol, and 2 parts of Solpol (manufactured by Toho Chemical Industry Co., Ltd.) are mixed to prepare an emulsion. Example 7 15 parts of compound (1), 5 parts of compound (d), 30 parts of methyl chloroform, 48 parts of polyethylene glycol, and 2 parts of Solpol (manufactured by Toho Chemical Industries, Ltd.) are mixed to prepare an emulsion. Example 8 10 parts of compound (3), 10 parts of compound (e), 78 parts of ethylene glycol, and 2 parts of Solpol (manufactured by Toho Chemical Industries, Ltd.) are mixed to prepare an emulsion. Next, the effects of the drug of the present invention will be explained with reference to tests. Test Example 1 (Growth inhibition test against various microorganisms) The minimum concentration of the drug of the present invention that inhibits the growth of various microorganisms on a broth liquid medium (PH7.5 for bacteria, PH4.5 for filamentous fungi) was measured by the agar dilution method. . The results are shown in Table 1.

[Table] As is clear from Table 1, compared to the use of each drug compound of the present invention alone, the bacteria of the genus Aerobacter, Bacillus, and Aspergis, which are responsible for microbial disasters in industrial water systems and industrial products, It exhibited antibacterial activity against Penicillium, Trichoderma, Geotrichum, etc. at extremely low concentrations. Test Example 2 (Paint liquid preservative test) Bouillon liquid medium and pre-rotted coating liquid were added to paper manufacturing coating liquid (PH8.3 starch coating liquid), stirred, and then each drug was added to the specified concentration. . After culturing this in an incubator at 30°C for 5 days, the number of viable bacteria, filamentous fungi, and yeast in each sample was measured to determine the antiseptic efficacy of each drug. The results are shown in Table 2.

[Table] (2) The number of bacteria in the table indicates the number of bacteria in 1 ml of sample.
The drug of the present invention was also extremely effective for coating liquids containing starch as the main binder compared to when used alone. Test Example 3 (Slime generation prevention test) Slime (viscous material formed by microorganisms) and white water that adhere to a paper manufacturing company that makes kraft paper during the paper manufacturing process were collected and used for testing. The slime is pulverized using a homogenizer and dispersed in white water in which 1% of bouillon liquid medium has been dissolved in advance. 19 ml of white water in which slime has been dispersed is placed in a 20 ml L-shaped tube, 1 ml of the drug of the present invention diluted to a predetermined concentration is added, and the mixture is continuously shaken using a monoshaker whose temperature is adjusted to 30°C. twenty four
After 72 hours, the number of viable bacteria in the white water was determined. The results are shown in Table 3.

【table】

[Table] (2) The number of viable bacteria in the table indicates the number of viable bacteria per ml.
As shown in Table 3, the agent of the present invention was extremely effective against slime-forming bacteria that adhered during the papermaking process and microorganisms in white water compared to single agent use. Test Example 4 (Glue Preservation Test) Each drug was added to a starch-based office glue that had just been produced by a glue company to a predetermined concentration. Next, equal amounts of the same type of glue that had rotted during the distribution stage were added, thoroughly stirred, and left in a warehouse for 2 and 8 weeks, and the efficacy of the drug was determined by measuring the number of viable bacteria in the paste and by observing the smell of rot. The results are shown in Table 4.

[Table] As shown above, the drug of the present invention was extremely effective compared to when used alone.

Claims (1)

[Claims] 1. General formula (However, in the formula, X represents a halogen atom, and Y represents a halogen atom or a hydrogen atom.) A compound selected from the acetophenone compounds represented by (a) 3,5-dimethyl-1,3,5 -2H-tetrahydrothiadiazine-2-thione (b) methylene bisthiocyanate (c) 1,4-bis(bromoacetoxy)2-butene (d) 1,2-bis(bromoacetoxy)ethane and (e) 2 A non-medical antibacterial and algae agent characterized by containing as an active ingredient one or more compounds selected from -bromo-2-nitro-1,3-propanediol.