JPH0370681B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a non-medical antibacterial and algal agent. 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 mills, 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 and becomes papery. It also causes problems such as paper cuts in the production process using high-speed machines. Furthermore, in metal fabrication plants, the growth of fungi and bacteria in the recirculating water systems for lubricating oil emulsions can cause the water to rot and corrode metal products by producing slime, which is a collection of microorganisms. , which also causes problems during storage of the lubricating oil emulsion itself. In addition to these disturbances in industrial water systems, there are also disasters caused by the proliferation of microorganisms. For example, industrial materials such as paint, pulp, fiber processing paste, 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 if they are directly discharged into rivers during drainage, they can have a negative impact on fish and shellfish, and can also be harmful to the human body. It has become a serious pollution problem due to its impact on the environment, and its use is being regulated. For this reason, organic chlorine, organic sulfur, and quaternary ammonium salts have been considered and used as alternative agents, but organic chlorine agents are irritating, and organic sulfur agents affect the color tone of the product. These agents also have various disadvantages in use, such as having a large effect and the quaternary ammonium salts foaming violently. The present invention is aimed at solving these problems, and uses a specific acetophenone compound and a specific isothiazolone complex compound as active ingredients to effectively control industrially harmful filamentous fungi, bacteria, algae, etc. The purpose of the present invention is to provide a non-medical antibacterial and algae agent that is highly effective compared to when each is used alone. The present invention is based on the general formula (In the formula, X represents a halogen atom, and Y represents a halogen atom or a hydrogen atom.) One or more compounds selected from the acetophenone compounds represented by the general formula (In the formula, Y represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and R
and R′ each represent a hydrogen atom, a halogen atom, or an alkyl group, and R and R′ may form a benzene ring together with the isothiazole ring skeleton, and M represents a cation consisting of a metal, ammonium, or amines. , X indicates an anion that has sufficient solubility to form a complex and forms a compound with cation M, a indicates an integer of 1 or 2, and n indicates that anion X satisfies the valence of cation M. Indicates an integer. This is a non-medical antibacterial and algae agent characterized by containing as an active ingredient one or more compounds selected from the isothiazolone complex compounds shown in ). In the formula [], examples of the halogen atom represented by X or Y include chlorine, bromine, and iodine. Depending on the selection of X and Y, one type of acetophenone compound of the formula [] may be used, or two or more types may be used. The following are representative examples of acetophenone compounds of the formula []. Compound [-1]: 2-bromo-4'-hydroxyacetophenone compound [-2]: 2-chloro-4'-hydroxyacetophenone compound [-3]: 2,3'-dibromo-4'- Hydroxyacetophenone compound [-4]: 2,3'-dichloro-4'-hydroxyacetophenone [] In the formula, an alkyl group represented by Y,
Examples of the alkenyl group, alkynyl group, or aralkyl group include methyl group, ethyl group, propyl group, butyl group, allyl group, propargyl group, and benzyl group. Examples of the halogen atom represented by R or R' include chlorine, bromine, and iodine, and examples of the alkyl group include methyl, ethyl, and propyl groups. Cations represented by M include calcium, magnesium, copper, iron, lead, manganese, nickel,
Examples include metal ions such as sodium, tin, and zinc, ammonium ions, and amines. Examples of the anion represented by X include chloride ion, bromide ion, iodine ion, sulfate ion, and acetate ion. Examples of MXn that form complex compounds are:
These include zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc acetate, copper chloride, nickel chloride, calcium chloride, magnesium chloride, manganese chloride, sodium chloride, ammonium chloride, and other amine chlorides. The isothiazolone complex compound of the formula [] also includes Y, R,
Depending on the selection of R', M, X, a, and n, one type or two or more types can be used. Representative examples of isothiazolone complex compounds of the formula [] include the following. Compound [-1]: 2-methyl-3-isothiazolone calcium () chloride compound [-2]: 2-ethyl-3-isothiazolone magnesium () chloride compound [-3]: Bis(2-n-butyl-3-
isothiazolone) zinc () chloride compound [-4]: 2-benzyl-4,5-dichloro-3-isothiazolone magnesium ()
Chloride compound [-5]: 2-allyl-3-isothiazolone ammonium chloride compound [-6]: 2-methyl-5-chloro-3
-Isothiazolone calcium () chloride compound [-7]: 2-propargyl-3-isothiazolone calcium () chloride compound [-8]: 1,2-benzothiazolone magnesium () chloride Non-medical antibacterial and algae prevention of the present invention The agent is a composition containing one or more compounds of the formula [] and one or more compounds of the formula []. The compounding ratio of the compound of the formula [] and the compound of the formula [] can be freely selected within the range that produces a synergistic effect, but the weight ratio is preferably 1:0.1 to 10. The drug of the present invention is prepared by mixing the compound of the formula [] and the compound of the formula [], further adding a solvent, a solid fine powder diluent, a surfactant, and other additives as necessary, and emulsifying the mixture with water. Or, it is preferable to formulate it in a form that can be suspended, but []
The compounds of the formula and [ ] may be prepared separately and mixed at the time of use, or may be added separately in any order for use. The non-medical antibacterial and algae agent of the present invention is suitable for use in paper and pulp manufacturing processes, industrial water such as industrial cooling water, cooling water for heating and cooling, lubricating oil for metal processing, aqueous emulsion, paper, wood, plywood, Molds that are added to the manufacturing and processing processes of paints, glues, pulps, fibers, etc., as well as finished products, etc., and that grow parasitic thereon.
Bacteria, yeast, algae, etc. can be controlled. Although the method of addition is not particularly limited, it is desirable to add the preparation in a state where it is emulsified or suspended in water. The amount added varies depending on the condition of the target system, the type of bacteria, etc., but generally the active ingredient is 3 to 3.
It exhibits antibacterial and algae-proofing effects at around 25ppm. The drugs of the present invention exhibit extremely superior efficacy compared to each drug used alone. The acetophenone compound of formula [] shows activity against bacteria, filamentous fungi, and algae in general, but has low activity against some bacteria and filamentous fungi, and is required to have high activity against bacteria, filamentous fungi, and algae in general. It is an unsuitable agent as an antibacterial and algae-proofing agent, and its practical use is poor when used alone. On the other hand, the isothiazolone complex compound of the formula [] shows activity against a relatively wide range of bacteria, fungi, and algae at high concentrations, but at low concentrations, its antibacterial spectrum is narrow and cannot be used against complex microbial disorders caused by bacteria. However, the expected effect was not achieved. However, by using these compounds of formula [] and [] together,
It is possible to control the growth of an unexpected wide range of microorganisms. As described above, the agent of the present invention is effective against Aspergillus, which is the main cause of microbial damage to industrial water, metal processing lubricants, water-based emulsions, paper, wood, paint, plywood, etc., which cannot be controlled by each single agent. niger, Penicillium stetskii, Geotrichum.
Effectively acts on filamentous fungi such as Candidum and Cladosporium herbalum, as well as bacteria such as Aerobacter aerogenes and Bacillus subtilis.
The occurrence of industrially harmful microorganisms can be completely suppressed with a small amount of chemicals. Therefore, it can be used as a slime control agent for paper manufacturing and other applications, lubricating oil for metal processing, water-based emulsion paints, and as a preservative for glue. Note that the drug of the present invention may be used in combination with other antibacterial and algal agents, adjuvants, and the like. Furthermore, the systems and fungi that are targeted for antibacterial and antialgal treatment are not limited to those mentioned above. As described above, since this invention is configured to use a specific acetophenone compound and an isothiazolone complex compound in combination, a synergistic effect can be obtained, and each component can effectively prevent bacteria and algae against microorganisms that are ineffective. be able to. Next, Examples and Test Examples of the present invention will be described, but the present invention is not limited thereto. In each example, parts and percentages are by weight. Example 1 15 parts of compound [-1] and compound [-1]
5 parts were dissolved in 80 parts of diethylene glycol to prepare an emulsion. Example 2 18 parts of compound [-1] and compound [-6]
Two parts were dissolved in 80 parts of diethylene glycol to form an emulsion. Example 3 10 parts of compound [-2] and compound [-5]
10 parts were dissolved in 80 parts of diethylene glycol to prepare an emulsion. Example 4 15 parts of compound [-3] and compound [-6]
5 parts were dissolved in 80 parts of diethylene glycol to prepare an emulsion. Example 5 18 parts of compound [-3] and compound [-2]
Two parts were dissolved in 80 parts of diethylene glycol to form an emulsion. Example 6 10 parts of compound [-4] and compound [-4]
10 parts were dissolved in 80 parts of diethylene glycol to prepare an emulsion. Example 7 10 parts of compound [-2] and compound [-7]
10 parts were dissolved in 80 parts of diethylene glycol to prepare an emulsion. Example 8 5 parts of compound [-1] and compound [-8]
15 parts were dissolved in 80 parts of diethylene glycol to form an emulsion. Example 9 18 parts of compound [-3] and compound [-3]
Two parts were dissolved in 80 parts of diethylene glycol to form an emulsion. Example 10 Compound [-1] 18 parts, Compound [-1] 0.5
and 1.5 parts of compound [-6] were dissolved in 80 parts of diethylene glycol to prepare an emulsion. Test Example 1 The minimum growth-inhibiting concentration of the compound of the formula [] and the composition of the present invention comprising the compound of the formula [] against various microorganisms was measured by the agar dilution method. A bouillon medium was used as the medium, and the pH was adjusted to 7.5 for bacteria and 4.5 for filamentous fungi. The microorganisms used in the test were
A: Aerobacter aerogenes, B: Bacillus subtilis, C: Esteritia coli, D:
Pseudomonas aeroginosa, E: Aspergillus niger, F: Penicillium stetskii,
G: Trichoderma sp., H: Geotrichum candidum. The results are shown in Table 1. In Table 1, test compounds [-1, 6] are compound [-
1]: a 1:3 mixture of compound [-6].
(Same in the following test examples).

【table】

[Table] Test Example 2 Slime (viscous material formed by microorganisms) that adheres to kraft paper during the paper-making process and white water were collected and used for testing. The slime was pulverized using a homogenizer and dispersed in white water in which 1% of a bouillon liquid medium had been dissolved in advance. After putting 19 ml of white water in which this slime was dispersed into a 25 ml L-shaped tube, 1 ml of the compound of the formula [] and the drug of the present invention consisting of the compound of the formula [] diluted to a predetermined concentration was added. The mixture was continuously shaken using a mono-type shaker whose temperature was adjusted to ℃, and the number of viable bacteria in the white water was determined after 24 and 72 hours. The results are shown in Table 2.

[Table] Test Example 3 Twice a day, 2 kg of the chemical of Example 10 was added by pump to the white water circulation system of a Fourdrinier paper machine producing 40 tons of kraft paper per day. The addition site was a paper machine with a capacity of about 25 m ³ , and the addition was carried out once over 4 hours. The test period was 15 days during which the factory was washed with water. The efficacy of the drug was determined based on the amount of slime attached to a slime board suspended in a white water pit and the number of times paper was broken by slime. For comparison, similar tests were conducted on 20% emulsions of Compound [-1] and Compounds [-1, 6]. Compound [-1] was dissolved in ethylene glycol, and 2% of Solpol (trade name, Toho Chemical Industries, Ltd.) was added to form an emulsion. The amount added to Chiest is the same as in Example 10. 3rd result
Shown in the table.

[Table] Test Example 4 Each drug listed in Table 4 was added to a starch-based office glue immediately after production to a specified concentration, and then an equal amount of the same type of glue that had rotted during the distribution stage was added. After stirring well, the mixture was left in a warehouse, and after 2 and 8 weeks, the efficacy of the drug was determined based on the number of viable bacteria and the smell of putrefaction. The results are shown in Table 4. In Table 4, all test chemicals are 20% emulsions, and the columns for bacteria and filamentous fungi indicate the number of viable bacteria in 1 ml. In addition, the evaluation of putrid odor in the table is as follows. -: No odor ±: Slight odor +: Slight odor ++: Strong odor +++: Strong odor

【table】

[Table] From the above results, it can be seen that the composition of the present invention has extremely superior antibacterial and antialgal effects compared to when used alone.

Claims (1)

[Claims] 1. General formula (In the formula, X represents a halogen atom, and Y represents a halogen atom or a hydrogen atom.) One or more compounds selected from the acetophenone compounds represented by the general formula (In the formula, Y represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group, and R
and R′ each represent a hydrogen atom, a halogen atom, or an alkyl group, and R and R′ may form a benzene ring together with the isothiazole ring skeleton, and M represents a cation consisting of a metal, ammonium, or amines. , X indicates an anion that has sufficient solubility to form a complex and forms a compound with cation M, a indicates an integer of 1 or 2, and n indicates that anion X satisfies the valence of cation M. Indicates an integer. ) A non-medical antibacterial and algae agent characterized by containing as an active ingredient one or more compounds selected from the isothiazolone complex compounds shown in (a). 2 The compound of formula [] is 2-bromo-4'-hydroxyacetophenone, 2-chloro-4'-hydroxyacetophenone, 2,3'-dibromo-4'-
Claim 1 is one or more selected from hydroxyacetophenone and 2,3'-dichloro-4'-hydroxyacetophenone.
A non-medical antibacterial and algae agent as described in Section 1. 3 Compounds of formula [] are 2-methyl-3-isothiazolone calcium () chloride, 2-ethyl-3-isothiazolone magnesium () chloride, bis-(2-n-butyl-3-isothiazolone) zinc () chloride, 2 -Benzyl-4,5-dichloro-3-isothiazolone magnesium () chloride, 2-allyl-3-isothiazolone ammonium chloride, 2-methyl-5-chloro-3-isothiazolone calcium () chloride, 2-propargyl-3-isothiazolone The non-medical antibacterial and algal agent according to claim 1 or 2, which is one or more selected from calcium () chloride and 1,2-benzothiazol-3-one magnesium () chloride. .