JPH0717482B2 - Bactericidal 4,5-dichloro-1,2-dithiol-3-one composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has a bactericidal 4,5-dichloro-1,2, -dithiole-3- which has excellent solubility and storage stability and is easy to handle. On composition.

[Problems to be Solved by Conventional Techniques and Inventions]

4,5-dichloro-1,2-dithiol-3-one (hereinafter referred to as dithiol compound) has the formula Is a yellow crystalline powder having a melting point of 61 ° C. and is used as an excellent slime control agent for industrial cooling water, washing water, raw material water, power water, etc. (Japanese Patent Publication No. 52-14294).

The dithiol compound produced as a powder is extremely irritating to the skin and is extremely difficult to handle during the production process.
Also, when handling these as products, it is extremely inconvenient to handle them in such powder state.

Therefore, it is considered that it is advantageous to prepare a liquid preparation in which these powders are dissolved in a solvent or the like for convenience of workability, safety, storability, transportability and dispersibility during use.

In particular, these industrial germicides are transported as liquid formulations,
For storage, it is economical to have as high an active ingredient concentration as possible. In this case, the liquid preparation must also be safe during transportation and storage.

However, the dithiol compound itself is a poorly soluble substance having a solubility in water of less than 1%, and cannot be made into a high-concentration aqueous solution. Further, the dithiol compound is extremely unstable in the obtained aqueous solution and hydrolyzes in a short time, so that the aqueous solution cannot be put to practical use.

Therefore, as a research on liquid formulation of dithiol compound, JP-B-63-65641 discloses a liquid formulation in which a dithiol compound is dissolved using haloacetic acid ester which is a hydrophobic solvent (lipophilic solvent). ing. But,
When practically used 1,2-bis (bromoacetoxy) ethane is used as a solvent in haloacetic acid ester, the solubility of dithiol compound is about 22%. Not a formulation.

Further, Japanese Patent Publication No. 62-23721 discloses a liquid preparation in which a dithiol compound is dissolved in a mixed solvent which is a combination of diethylene recall monomethyl ether and dimethylformamide. The solubility of the dithiol compound in this solvent is very high at about 67% by weight at 25 ° C., which is quite effective in terms of solubility. However, dimethylformamide is highly toxic and originally, there is a problem in using it in a large amount as a solvent. In addition, this liquid preparation has insufficient long-term storage stability of the active ingredient. Further, a liquid preparation containing a dithiol compound in a high concentration has a problem that when exposed to a low temperature during transportation and storage, crystals are broken out and the whole liquid preparation is solidified. This solidified product is extremely hard, and it is difficult to take out the product from the container as it is, and it is necessary to re-dissolve it by applying heat in order to use it. This is very disadvantageous in terms of operation and thermo-economics.

[Means for Solving the Problems]

Therefore, as a result of intensive research aimed at solving the above-mentioned problems, the present inventors have excellent solubility and storage stability of the dithiol compound by using N-methyl-2-pyrrolidone as a solvent, The present invention has been completed by finding that a composition having a property that is easy to handle is obtained.

That is, the present invention is characterized by containing 4,5-dichloro-1,2-dithiol-3-one and N-methyl-2-pyrrolidone which are excellent in solubility and storage stability and are easy to handle. This invention relates to an industrial bactericidal composition.

Furthermore, the composition of the present invention is capable of obtaining a high-concentration dithiol solution, at the same time, hard to solidify even when exposed to low temperatures during transportation and storage, and even when solidified, a soft sherbet that can be easily scraped It becomes a solidified substance. Here, the sherbet-like solidified product is a partially frozen mixture of N-methyl-2-pyrrolidone and a dithiol compound, which can be easily separated from the container and subdivided. Further, the easiness of taking out the product from the container in this manner is called scooping property. That is, the composition of the present invention may be solidified at a low temperature, but even in that case, unlike the conventional solidified product, it becomes a sherbet shape with good rakeability, and further, redissolution is relatively easy. Is. Therefore, the composition of the present invention can be sufficiently used as a solidified product as a product.

In the dithiol composition of the present invention, the dithiol compound and N-methyl-2-pyrrolidone can be mixed in an appropriate amount ratio, but preferably the dithiol and N-methyl-2-pyrrolidone are in a weight ratio of 80:20 to 1: 1. Mix in the range of 99.

In order to produce the composition according to the present invention, a conventional melt mixing method is applied, for example, a powdered dithiol compound is added to N 2
It can be dissolved in methyl-2-pyrrolidone with stirring to give a liquid composition. In operation, it is preferable that the dissolution be performed in a closed system.

Further, at this time, in order to obtain a high-concentration dithiol composition, it is preferable to dissolve the dithiol composition under heating, but it is also possible to heat the dithiol composition to a temperature not lower than the melting point of dithiol and mix them in a liquid state.

The dithiol composition obtained in the present invention can be used as an industrial sterilizing / bacteriostatic composition as it is or after mixing and diluting with a solvent or a kind of surfactant usually used in the art.

As the solvent, amides such as dimethylformamide and diethylformamide, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether and diethylene glycol monomethyl ether, isopropyl alcohol, diethylene glycol, dipropylene glycol, polypropylene glycol Examples thereof include alcohols or glycols such as and ketones such as acetone and methyl isobutyl ketone, and two or more kinds of these may be used in combination. As the surfactant, a nonionic surfactant such as alkylolamide or polyoxyethylene polyoxypropylene alkyl ether or a cationic surfactant such as trimethylcell ammonium chloride is used. In particular, as the alkylolamide-type nonionic surfactant used, a fatty acid alkylolamide synthesized from a fatty acid and an alkylolamine (for example, “Synthesis of surfactants and basic applications: Oda and Teramura, Maki, Maki Bookstore, published June 30, 1975, pp. 150-151), preferably an alkylolamide obtained by the reaction of a higher fatty acid having 8 to 18 carbon atoms with ethanolamine or diethanolamine. Is.

The industrial sterilizing / bacteriostatic composition thus obtained can be used for various objects for the purpose of sterilizing and bacteriostatic, for example, process water in a papermaking process, industrial cooling water,
It is used for liquid objects such as washing water, heavy oil sludge, cutting oil, lignin waste liquid, water-based paint, antifouling paint, latex and fiber oil. For example, when it is added to the process water of the papermaking process, it is usually used in the range of 1 to 100 ppm in order to achieve the purpose of sterilization and bacteriolysis of microorganisms, although there are differences depending on the adhesion state of slime and the type of slime-forming bacteria. And preferably used in the range of 5 to 50 ppm.

[Action]

 The composition obtained according to the invention has the following characteristics.

(1) It has a solubility of about 70% by weight at room temperature (25 ° C).

(2) In the storage stability test (60 ° C., 30 days), the stability of the dithiol compound as an active ingredient is very high.

(3) It becomes a sherbet-like solidified preparation which is hard to solidify at low temperature and can be easily separated and subdivided as it is even when solidified, and has excellent rakeability.

(4) This sherbet-like solidified preparation can be redissolved relatively easily.

(5) N-methyl-2-pyrrolidone has an odor, flammability,
It is possible to prepare a composition which has few problems in terms of toxicity and has high operability and safety.

Therefore, it has characteristics not found in conventional dithiol compositions, is excellent in solubility and storage stability, and is easy to handle.

In addition, it is particularly easy to handle during manufacturing, transportation, and storage,
As the highly-concentrated dithiol composition of the present invention having excellent stability, it is preferable to use a dithiol compound and N-methyl-2-pyrrolidone in a weight ratio of 40:60 to 70:30.

〔Example〕

Hereinafter, the present invention will be described with reference to Experimental Examples and Examples, but it goes without saying that the present invention is not limited thereto.

Experimental Example 1: Solubility test Table 1 shows the solubility (% by weight) of the dithiol compound in 100 g of each solvent in Table 1 at 25 ° C.

Experimental Example 2: Storage stability test 50% of dithiol compound in a 50 ml transparent glass container.
An N-methyl-2-pyrrolidone composition (the composition of the present invention) and a 5 wt% diethylene glycol monomethyl ether-containing dimethylformamide composition (Reference Example) were prepared,
Stability tests were performed.

The test conditions were 60 ° C for 15 days and 30 days, then quantitative analysis by high performance liquid chromatography (HPLC) and 317 nm
Residual ratio (%) of dithiol compound by area ratio measurement at
I checked. The results are shown in Table 2.

As is clear from the table, the dithiol compound which is the active ingredient is hardly decomposed in the composition of the present invention even after being left for 15 days and 30 days, showing that the storage stability is superior to that of Reference Example.

Experimental Example 3: Crystal precipitation and re-dissolution test In a 50 ml transparent glass container, 4,5-dichloro-1,2-dithiol-3-one and N-methyl-2-pyrrolidone were mixed in predetermined concentration ratios. Mix as above and dissolve under heating if necessary. This solution was appropriately cooled to precipitate crystals, the state was observed, the crystal precipitation temperature was measured, and the crystallized product was heated to measure the crystal dissolution temperature. The results are shown in Table 3.

As is clear from the table, even at a high concentration of about 70% by weight at room temperature, even a composition having a very high concentration exists as a liquid, and even when solidified, crystals do not precipitate, and a sorbet-like excellent rake-off property is obtained. Present as a solidified formulation. Also,
It is shown that this solidified substance can also be redissolved at a relatively low temperature.

In addition, the compositions of Examples 2, 3 and 4 below do not show crystal precipitation or solidification even when stored for a long period of time, and can be stably handled in a liquid state.

Furthermore, even when the compositions of Examples 7, 8, 9 and 10 were used as slime control agents, the viable cell count of microorganisms such as industrial cooling water, washing water, raw water, and power water was not increased, Exhibits an excellent bactericidal effect.

The formulation examples of the composition of the present invention are shown below as examples.

Example 1 4,5-Dichloro-1,2-dithiol-3-one 80% N-Methyl-2-pyrrolidone 20% Example 2 4,5-Dichloro-1,2-dithiol-3-one 70% N -Methyl-2-pyrrolidone 30% Example 3 4,5-Dichloro-1,2-dithiol-3-one 50% N-Methyl-2-pyrrolidone 50% Example 4 4,5-Dichloro-1,2- Dithiol-3-one 40% N-Methyl-2-pyrrolidone 60% Example 5 4,5-Dichloro-1,2-dithiol-3-one 20% N-Methyl-2-pyrrolidone 80% Example 6 4, 5-dichloro-1,2-dithiol-3-one 1% N-methyl-2-pyrrolidone 98% trimethylcetylammonium chloride 1% Example 7 4,5-dichloro-1,2-dithiol-3-one 5% N-methyl-2-pyrrolidone 94% Trimethyl cetyl ammonium chloride 1% Implemented 8 4,5-Dichloro-1,2-dithiol-3-one 5% N-methyl-2-pyrrolidone 93% Polyoxyethylene polyoxypropylene alkyl ether 2% Example 9 4,5-Dichloro-1,2- Dithiol-3-one 8% N-Methyl-2-pyrrolidone 2% Diethylene glycol monomethyl ether 88% Polyoxyethylene polyoxypropylene alkyl ether 2% Example 10 4,5-Dichloro-1,2-dithiol-3-one 7 % N-Methyl-2-pyrrolidone 3% Diethylene glycol monomethyl ether 89% Trimethylcetyl ammonium chloride 1% Example 11 4,5-Dichloro-1,2-dithiol-3-one 5% N-methyl-2-pyrrolidone 5% Diethylene glycol monomethyl ether 89% Trimethyl cetyl ammonium chloride 1% Example 1 2 4,5-dichloro-1,2-dithiol-3-one 5% N-methyl-2-pyrrolidone 5% diethylene glycol monomethyl ether 88% polyoxyethylene polyoxypropylene alkyl ether 2% Example 13 4,5-dichloro -1,2-Dithiol-3-one 2% N-methyl-2-pyrrolidone 8% Diethylene glycol monomethyl ether 88% Polyoxyethylene polyoxypropylene alkyl ether 2% Example 14 4,5-Dichloro-1,2-dithiol -3-one 1% N-methyl-2-pyrrolidone 10% diethylene glycol monomethyl ether 88% trimethylcetylammonium chloride 1% [Effect of the invention] As is clear from the above experimental examples and examples, N-methyl-2 was used as a solvent. -By using pyrrolidone,
Higher concentration of 4,5- than the solvent used so far
A dichloro-1,2-dithiol-3-one composition can be obtained. The composition also contains 4,5-
The storage stability of dichloro-1,2-dithiole-3-one is high, and even when the composition is solidified, it can be used as a soft sherbet-like composition as it is or easily re-dissolved for use. . In addition, toxicity, odor,
It has low flammability and is extremely useful as a bactericide composition.

Claims (2)

[Claims] 1. An industrial bactericidal composition containing 4,5-dichloro-1,2-dithiol-3-one and N-methyl-2-pyrrolidone. 2. A weight ratio of 4,5-dichloro-1,2-dithiol-3-one and N-methyl-2-pyrrolidone of 80:20 to 1: 9.
The composition according to claim 1, which is contained in 9.