JPH10114771A - Liquefied agent of tetrahydrothiophene-1,1-dioxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquefied agent of the subject compound less irritating smell, easy to handle and excellent in storage stability without a decomposition for a long period of time, and useful as an industrial bactericide by liquefying it by adding a specific glycol derivative. SOLUTION: This liquefied tetrahydrothiophene-1,1-dioxide is obtained by adding (B) a compound of formula II (R is a lower alkyl: (m) is 1-6; (n) is 2,3)(e.g. diethylene glycol monomethyl ether or diethylene glycol menoethyl ether) is added to (A) a compound of formula I (X is H or a haloge)(e.g. 3,3,4,4 tetrachlorotetrahydrothiophene 1,1-dioxide) so as to make 10-50wt.% component (A) in the liquefied agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a liquid tetrahydrothiophene-1,1-dioxide derivative.

[0002]

2. Description of the Related Art With the increase in demand for industrial water, the use of recirculating water systems has been actively promoted. In such use, control and suppression of the growth of microorganisms are important issues.
In addition to these industrial waters, with the diversification of industrial materials, the damage caused by the proliferation of microorganisms and the occurrence of molds has been widespread. In particular, water in the papermaking process, industrial cooling water, or lubricating oil for metalworking, aqueous emulsion, paper, wood, plywood, glue, pulp, slime problems such as bacteria, yeast, algae, etc. parasitic on fibers, Countermeasures against microbial disasters are urgently needed.

Recently, industrial bactericides have been widely used for the purpose of preventing or eliminating the generation of these microorganisms, and tetrahydrothiophene-1,1 has been widely used as an agent for suppressing or controlling the generation of harmful microorganisms. -Dioxide derivatives are well known. This tetrahydrothiophene-1,1-dioxide derivative has a broad antibacterial spectrum in a wide pH range as an industrial bactericide and antibacterial agent, and is effective against, for example, bacteria and yeast molds, and is also extremely persistent. Good.

[0004]

However, this tetrahydrothiophene-1,1-dioxide derivative is liable to solidify powder, has a very irritating odor in a powder or solid state, and has skin irritation. Therefore, handling is inconvenient. On the other hand, if it is stored as a disinfectant for industrial use as a disinfectant in organic solvents,
It is colored or decomposed, and cannot effectively exert its effect as an industrial germicide.

Therefore, this tetrahydrothiophene-1,1
-It is desired that the dioxide derivative be stored in a stable state for a long period of time without being easily decomposed.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the stable storage of tetrahydrothiophen-1,1-dioxide derivatives. When a specific compound was added to form a liquid formulation, it was found that it was easy to handle, for example, with little pungent odor, and could be stably stored without being decomposed for a long period of time, and completed the present invention.

That is, the present invention provides: (1) (a) a general formula

[0008]

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Wherein X represents the same or different hydrogen atom or halogen atom, and (b) a compound represented by the general formula:

[0010]

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(Wherein R represents a lower alkyl group, n represents an integer of 2 or 3, and m represents an integer of 1 to 6). (2) wherein, in the formula of the compound represented by (a), X is a halogen atom, the liquefied tetrahydrothiophene-1,1-dioxide derivative according to (1), 3) The liquefied tetrahydrothiophen-1,1 according to (1), wherein the compound represented by (a) is 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide.
-A dioxide derivative, (4) a liquefied tetrahydrothiophen-1,1-dioxide derivative according to (1), wherein R is a methyl group or an ethyl group in the formula of the compound represented by (b), (5) In the formula of the compound represented by (b), the liquefied tetrahydrothiophene-1,1-dioxide derivative according to (1) or (4), wherein n is 2 and m is 2; The liquefied tetrahydrothiophen-1,1-dioxide derivative according to (1), wherein the compound represented by b) is diethylene glycol monomethyl ether and / or diethylene glycol monoethyl ether; (7) represented by (a) The liquefied tetrahydrothiophen-1,1-dioxide derivative according to (1), wherein the compound is contained in an amount of 10% by weight or more, (8) The liquid according to (1), which is used as an industrial germicide Of tetra hydro-1,1-dioxide derivatives, (9) (a) the general formula

[0012]

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(Wherein, X represents the same or different hydrogen atom or halogen atom);

[0014]

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(Wherein R represents a lower alkyl group, n represents an integer of 2 or 3, and m represents an integer of 1 to 6). ) Regarding the storage method.

[0016]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, the compound represented by the general formula (a)

[0017]

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(Wherein X represents the same or different hydrogen atom or halogen atom) is a tetrahydrothiophene-1,1-dioxide derivative useful as an industrial bactericide. Wherein, as the halogen atom for X, for example, fluorine, chlorine, bromine, iodine and the like can be mentioned, and if each X is a hydrogen atom or a halogen atom, each X may be a different atom, preferably chlorine. Can be

The tetrahydrothiophen-1,1-dioxide derivative is disclosed in, for example, JP-A-35-3517 and JP-A-52-10263.
1, can be manufactured by the method described in JP-A-2-43685, JP-A-5-193369, or the like, and contains production intermediates and other impurities that cannot be completely removed in the production process. May be. These tetrahydrothiophen-1,1-dioxide derivatives are specifically, for example, 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide, 3,3,4,4-tetrabromotetrahydrothiophene -1,1-dioxide, 3,4-dichlorotetrahydrothiophen-1,1-dioxide, 3,3,4-trichlorotetrahydrothiophen-1,1-dioxide, 3,3,4-tribromotetrahydrothiophen-1, 1-dioxide and the like, preferably 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide wherein X is all chlorine.

In the present invention, general formula (b)

[0021]

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Wherein R is a lower alkyl group, n is an integer of 2 or 3, and m is an integer of 1 to 6. The compound represented by the formula: is a tetrahydrothiophene-1,1-dioxide derivative Wherein the lower alkyl group represented by R is a compound having 1 to 1 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl and the like. 6 linear or branched alkyl groups, preferably lower alkyl groups having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.

N is an integer of 2 or 3;
When, an oxyethylene group can be mentioned,
When n is 3, an oxyisopropylene group, an oxy
-n-propylene group. Preferably,
An oxyethylene group wherein n is 2 can be mentioned.
Further, m is an integer of 1 to 6, and preferably, m is
1 to 3, and more preferably 2.

Specific examples of such a compound (b) include, for example, ethylene glycol monomethyl ether,
Ethylene glycol monoalkyl ether such as ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Propylene glycol monoalkyl ethers such as glycol monoisopropyl ether and propylene glycol monobutyl ether, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono Diethylene glycol monoalkyl ethers such as tyl ether, for example, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monoalkyl ether such as dipropylene glycol monobutyl ether For example, triethylene glycol monoalkyl ethers such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monoisopropyl ether, and triethylene glycol monobutyl ether, for example, tripropylene glycol monomethyl Ether, bird B propylene glycol monoethyl ether, this include tripropylene glycol monopropyl ether, tripropylene glycol monoisopropyl ether, tripropylene glycol monoalkyl ethers, such as tripropylene glycol monobutyl ether and the like. These may be used alone or in combination of two or more kinds. In addition, polyethylene glycol monoalkyl ether, for example, polyethylene glycol monomethyl ether having m of 4 to 6 (trade name:
EXP-M-45, manufactured by Toho Chemical Co., Ltd.) or the like may be used alone or in combination.

Of these, preferred are ethylene glycol monoalkyl ether and diethylene glycol monoalkyl ether, and more preferred are diethylene glycol monomethyl ether and diethylene glycol monoethyl ether. Then, the compound represented by (a), a tetrahydrothiophen-1,1-dioxide derivative, is contained in the liquid preparation in an amount of 10 to 50% by weight, preferably 15 to 40% by weight.
The compound represented by (b) is added to the tetrahydrothiophen-1,1-dioxide derivative so that the ratio becomes as follows. In this case, since the compound is used as a liquid, the tetrahydrothiophen-1,1-dioxide derivative contains at least 10
It is preferable that it be contained in an amount of at least% by weight.

In the preparation of the liquid preparation, the compound represented by (b) is added to the tetrahydrothiophene-1,1-dioxide derivative at a predetermined ratio, and mixed with a stirrer or the like until the compound is completely and uniformly dissolved. I do. Further, in the present invention, tetrahydrothiophene
As far as the storage stability of the -1,1-dioxide derivative is not impaired, known additives such as other bactericides, surfactants, antioxidants and the like may be added as appropriate.

The fungicides include 1,2-benzisothiazolin-3-one and 5-chloro-2-methyl-4-isothiazoline.
-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-
Dichloro-2-octyl-4-isothiazolin-3-one, 2-
Octyl-4-isothiazolin-3-one, 2,2-dibromo-3
-Nitrilopropanamide, 2-bromo-2-nitropropane-1,3-diol, 3-iodo-2-propynyl-butylcarbamate, methyl-2-benzimidazole carbamate and its salts (eg, hydrochloride, methanesulfonic acid) salt,
p-toluenesulfonate), 2,2-dibromo-2-nitroethanol, 4,5-dichloro-1,2-dithiol-3-one, methylenebisthiocyanate, 2-methyl-4,5-trimethylene- Isothiazolin-3-one and the like.

Examples of the surfactant include soaps, nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, and polymeric surfactants.
Known surfactants may be mentioned, preferably nonionic surfactants and anionic surfactants.
Examples of the nonionic surfactant include polyoxyalkylene aryl phenyl ether, polyoxyethylene nonyl phenyl ether, ethylene oxide and propylene oxide block copolymer, and the like.

Examples of the anionic surfactant include metal salts of alkyl benzene sulfonic acid, metal salts of alkyl naphthalene sulfonic acid, polycarboxylic acid type surfactants, metal salts of dialkyl sulfosuccinates, and polyoxyethylene distyrenated phenyl ether. Examples thereof include sulfate ammonium salts and metal salts of ligninsulfonic acid, and examples of the metal salts include sodium salts, potassium salts, and magnesium salts.

As the antioxidant, for example, 2,6-di-t
-Phenolic antioxidants such as butyl-4-methylphenol, 2,2'-methylenebis [4-methyl-6-t-butylphenol], alkyldiphenylamine, N, N'-di-s
-Amine-based antioxidants such as butyl-p-phenylenediamine and the like. These additives are the liquid 100
For example, 20 to 80 parts by weight is added to the parts by weight.

The liquefied tetrahydrothiophen-1,1-dioxide derivative of the present invention can be effectively used as an industrial bactericide.
Depending on the target, the purpose and the like, for example, a known method such as a dropping method, an intermittent addition method, a coating method, a spraying method, and a dipping method is appropriately used, and tetrahydrothiophene in a liquid agent is used for the target water-containing composition. The final concentration of the 1,1-dioxide derivative is 10-5000 ppm, preferably 50-1000 ppm
It is preferable to add so as to be about pm.

As the industrial disinfectant, preferably, white water, synthetic polymer emulsion,
Used as pigments, paints, processing liquids for printing boards, adhesives, cooling water, inks, cutting oils, cosmetics, nonwoven fabrics, spinning oils, leather, etc., and more preferably used as white water in papermaking processes. Can be

[0033]

As described above, the liquefied tetrahydrothiophen-1,1-dioxide derivative of the present invention is
It has good handling such as little pungent odor and can be stably stored without decomposition for a long period of time. Even after long-term storage, it can be effectively used as a chemical for industrial germicides without a decrease in antibacterial activity.

[0034]

The present invention will be described more specifically below with reference to examples and comparative examples. Example 1 70 g of diethylene glycol monomethyl ether was added to 30 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed until homogeneously dissolved to obtain 100 g of a liquid. The solution had almost no pungent odor. Example 2 80 g of diethylene glycol monomethyl ether was added to 20 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed until uniformly dissolved to obtain 100 g of a liquid. The solution had almost no pungent odor.

Example 3 70 g of diethylene glycol monoethyl ether was added to 30 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed until uniformly dissolved to obtain 100 g of a liquid. . The solution had almost no pungent odor. Example 4 80 g of diethylene glycol monoethyl ether was added to 20 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed until uniformly dissolved to obtain 100 g of a liquid. The solution had almost no pungent odor.

EXAMPLE 5 To 25 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide was added ethylene glycol monomethyl ether.
75 g was added and mixed until uniformly dissolved to obtain 100 g of a liquid preparation. The solution had almost no pungent odor. Example 6 To 25 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide was added ethylene glycol monoethyl ether.
75 g was added and mixed until uniformly dissolved to obtain 100 g of a liquid preparation. The solution had almost no pungent odor.

Example 7 15 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide was added with 85 g of dipropylene glycol monomethyl ether and mixed until homogeneously dissolved.
Was obtained. The solution had almost no pungent odor. Example 8 80 g of triethylene glycol monomethyl ether was added to 20 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed until homogeneously dissolved.
Was obtained. The solution had almost no pungent odor.

Example 9 To 15 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide was added 85 g of tripropylene glycol monomethyl ether and mixed until homogeneously dissolved.
g of solution was obtained. The solution had almost no pungent odor. Example 10 80 g of polyethylene glycol monomethyl ether (m = 4 to 6, trade name: EXP-M-45, manufactured by Toho Chemical Co., Ltd.) in 20 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide Was added and mixed until homogeneously dissolved to obtain 100 g of a liquid preparation. The solution had almost no pungent odor.

Comparative Example 1 95 g of ethylene glycol was added to 5 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed until homogeneously dissolved to obtain 100 g of a liquid. The solution had almost no pungent odor. In addition, initially, 85 g of ethylene glycol was added to 15 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed, but did not dissolve.

Comparative Example 2 95 g of dipropylene glycol was added to 5 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed until uniformly dissolved to obtain 100 g of a liquid. Was. The solution had almost no pungent odor. Note that initially, 85 g of dipropylene glycol was added to 15 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed, but did not dissolve.

Comparative Example 3 70 g of N-methylpyrrolidone was added to 30 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed until uniformly dissolved to obtain 100 g of a liquid. . The solution had almost no pungent odor. Comparative Example 4 70 g of dimethylformamide was added to 30 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed until uniformly dissolved to obtain 100 g of a liquid preparation. The solution had almost no pungent odor.

Comparative Example 5 70 g of dimethyl sulfoxide was added to 30 g of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixed until homogeneously dissolved to obtain 100 g of a liquid. The solution had almost no pungent odor. Test Example Each of the liquid preparations obtained in the above Examples and Comparative Examples was sealed in a glass container, placed in a thermostat at 60 ° C., taken out after 4 weeks, and visually observed for the appearance state, particularly the color tone, and The residual ratio (% by weight) of 3,3,4,4-tetrachlorotetrahydrothiophen-1,1-dioxide was measured by gas chromatography.

Each of the examples and comparative examples was placed in a refrigerator at -5 ° C., and it was visually observed whether or not turbidity or a precipitate was formed. These results are summarized in Table 1.

[0044]

[Table 1]

From Table 1, it can be seen that Examples 1 to 10 showed no change in appearance even after 4 weeks, and
99.5% or more of 4,4-tetrachlorotetrahydrothiophene-1,1-dioxide also remains, and it can be seen that turbidity and precipitation did not occur even at a low temperature. On the other hand, from Comparative Examples 1 and 2, those in which glycols were added caused turbidity / precipitation or a decrease in the residual ratio, and those using the organic solvents of Comparative Examples 3 to 5 were: Coloring was observed, and a decrease in the residual ratio was observed.

Claims (9)

[Claims] (A) a general formula: (Wherein X represents the same or different hydrogen atom or halogen atom), and (b) a compound represented by the following general formula: (Wherein, R represents a lower alkyl group, n represents an integer of 2 or 3, and m represents an integer of 1 to 6). 1-
Dioxide derivatives. 2. In the formula of the compound represented by (a), X is
The liquefied tetrahydrothiophen-1,1-dioxide derivative according to claim 1, which is a halogen atom. 3. The liquefied tetrahydrothiophene-1,1 according to claim 1, wherein the compound represented by (a) is 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide. -Dioxide derivatives. 4. The liquefied tetrahydrothiophen-1,1-dioxide derivative according to claim 1, wherein in the formula of the compound represented by (b), R is a methyl group or an ethyl group. 5. The compound of the formula (b), wherein n is 2
5. The liquefied tetrahydrothiophen-1,1-dioxide derivative according to claim 1, wherein m is 2. 5. 6. The liquefied tetrahydrothiophen-1,1-dioxide derivative according to claim 1, wherein the compound represented by (b) is diethylene glycol monomethyl ether and / or diethylene glycol monoethyl ether. 7. The liquefied tetrahydrothiophen-1,1-dioxide derivative according to claim 1, wherein the compound represented by (a) is contained in an amount of 10% by weight or more. 8. The method according to claim 1, which is used as an industrial bactericide.
A liquid tetrahydrothiophene-1,1-dioxide derivative as described in the above. (A) General formula: (Wherein, X represents the same or different hydrogen atom or halogen atom), and (b) a compound represented by the following general formula: (Wherein, R represents a lower alkyl group, n represents an integer of 2 or 3, and m represents an integer of 1 to 6). Method.