JPH07277908A - Halocyanoacetamide-containing composition - Google Patents

Abstract

PURPOSE:To obtain a halocyanoacetamide-containing composition excellent in storage stability and aqueous solution stability, efficiently usable as a solution, useful especially as an insecticide for industrial use and having high stability against water by compounding with a cyclodextrin. CONSTITUTION:This halocyanoacetamide-containing composition is obtained by compounding with a cyclodextrin (preferably a cyclodextrin or a branched, especially preferably the latter) and has an improved stability against water. The composition can be used as a solution and especially as an insecticide for industrial use. The composition is preferably compounded with water and/or an organic solvent (especially preferably a glycol solvent). The halocyanoacetamide is a compound of the formula (X is a halogen; Y is a halogen or H; R is H or a lower alkyl), e.g. monochlorocyanoacetamide and monobromocyanoacetamide. Dibromocyanoacetamide is especially preferable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halocyanoacetamide-containing composition which is stable to water and which contains cyclodextrins.

[0002]

2. Description of the Related Art With the increasing demand for industrial water, the use of recirculation water systems is being actively used, and the control and suppression of the growth of microorganisms is an important problem in such use. In addition to these industrial water sources, with the diversification of industrial materials,
There are a wide range of disasters caused by the proliferation of microorganisms and fungi. In particular, water in the paper manufacturing process, industrial cooling water, or lubricating oil for metal processing, aqueous emulsion, paper, wood, plywood, paste, pulp, fungi parasitic on fibers, bacteria, yeast, slime problems such as algae, There is an urgent need to take measures against microbial disasters. Recently, it has been known that halocyanoacetamide has a wide application range and an excellent effect as an industrial bactericidal agent for the purpose of preventing or eliminating the generation of these microorganisms.

[0003]

Generally, it is preferable that the industrial bactericide of this kind is a liquid agent. However, these halocyanoacetamides are reductive nucleophiles,
It is known that it is easily decomposed by sunlight or hydrolysis (Journal of Agricultural and Food Chemistry Vol. 21, No. 5, 197).
3). Therefore, as an aqueous solution formulation, it is very unstable and its quality changes significantly. On the other hand, increasing the proportion of organic solvent in the liquid agent component causes storage problems due to the relationship with the Fire Service Law, etc. It was difficult to do. In order to solve such a problem, a method of preparing an ethylene glycol-aqueous solution preparation has been known so far (Japanese Patent Publication No. 61-44804), but it was not satisfactory. Further, a method of adding molybdate, chromate, zinc salt, copper salt or the like in order to stabilize the aqueous solution preparation is known (Japanese Patent Publication No. 63-201102). However, those containing metal ions are likely to cause turbidity or precipitation in the object. In particular, when it is added to the anionic polymer aqueous dispersion, a coagulated product is generated due to the coexisting metal stabilizer. Further, a method of adding a carboxylic acid organic acid such as succinic acid, oxalic acid, salicylic acid, citric acid is known (Japanese Patent Publication No. 57-5448).
1). However, it is not useful for suppressing decomposition of the active ingredient because it is affected by pH.

[0004]

[Means for Solving the Problems] In view of the above problems, the inventors of the present invention have conducted diligent research, and as a result, found that the incorporation of cyclodextrins can stabilize halocyanoacetamide against water. The invention was completed. That is, the present invention relates to providing a water-stable halocyanoacetamide-containing composition containing a cyclodextrin, and provides a halocyanoacetamide-containing aqueous preparation excellent in storage stability and aqueous solution stability. Regarding things. The halocyanoacetamide of the present invention has the general formula (1)

[Chemical 1] (In the formula, X represents a halogen atom, Y represents a halogen atom or a hydrogen atom, and R represents a hydrogen atom or a lower alkyl group.) And the like. Examples of the halogen atom for X and Y include fluorine, chlorine, bromine, iodine and the like. Preferable is bromine, and halocyanoacetamide in which both X and Y are bromine is preferably used.
Examples of the lower alkyl group for R include a methyl group, an ethyl group,
n-propyl group, iso-propyl group, n-butyl group, ter
Examples thereof include lower alkyl groups having 1 to 4 carbon atoms such as t-butyl group and iso-butyl group. A preferred example of R is a hydrogen atom or a methyl group.

Specific examples of the halocyanoacetamide represented by the general formula (1) used in the present invention include monochlorocyanoacetamide, monobromocyanoacetamide, dichlorocyanoacetamide, dibromocyanoacetamide, and monochloromonobromocyanoacetamide. ,
N-methyldibromocyanoacetamide and the like,
Preferred is dibromocyanoacetamide.
Cyclodextrins of the present invention include cyclodextrins and branched cyclodextrins. Examples of the cyclodextrin include α-cyclodextrin,
Examples include β-cyclodextrin and γ-cyclodextrin. The branched cyclodextrin is a cyclodextrin ring having a branch such as glucose or maltose, and G1-β-cyclodextrin and G1-γ having one glucose bound to the cyclodextrin ring.
-Glucosyl cyclodextrin such as cyclodextrin, G2-α- linked with maltose having two glucose
Cyclodextrin, G2-β-cyclodextrin,
Maltosyl cyclodextrins such as G2-γ-cyclodextrin, maltotriosyl groups such as G3-α-cyclodextrin, G3-β-cyclodextrin, G3-γ-cyclodextrin, etc. to which maltotriose of three glucose is bound. Examples include maltotriosyl cyclodextrins such as G1-Gl-, Gl-G2-, G2-G2- and the like in which is bonded to the 2-position or more of cyclodextrin. Preferred are glucosyl cyclodextrin and maltosyl cyclodextrin.

The halocyanoacetamide-containing composition of the present invention is preferably made into a liquid formulation, and preferably contains water. Further, from the viewpoint of solubility of halocyanoacetamide, an organic solvent may be further contained. Examples of the organic solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, and butyl alcohol, for example,
Acetone, methyl ethyl ketone, a ketone solvent such as methyl isobutyl ketone, for example, dichloroethane, chloroform, a halogenated hydrocarbon solvent such as carbon tetrachloride, for example, dioxane, an ether solvent such as tetrahydrofuran, for example, dimethylformamide, dimethyl sulfoxide, A polar solvent such as acetonitrile, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, die Glycol monoethyl ether, glycol solvents such as tripropylene glycol monomethyl ether, such as propylene carbonate, include carbonate solvents such as ethylene carbonate. Glycol-based solvent, particularly preferably ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether may be mentioned. Particularly preferred is diethylene glycol monomethyl ether.

The proportion of the halocyanoacetamide-containing composition of the present invention is 0.1 to 99.9 of halocyanoacetamide.
% By weight, cyclodextrins 0.1 to 99.1% by weight
It is mixed in the range of. When water is added, water 1 to 1 is added to 10 parts by weight of the halocyanoacetamide-containing composition.
It is used in the range of 00 parts by weight. Further, when an organic solvent is added, the amount of the organic solvent is 1 to 100 parts by weight with respect to 10 parts by weight of the halocyanoacetamide-containing composition. The ratio of cyclodextrin and branched cyclodextrin in cyclodextrins varies depending on the formulation, for example,
In a water-based preparation, when the water content is high, it is better to increase the proportion of branched cyclodextrin. In the preparation of a liquid agent, usually, a predetermined amount of each of these components is stirred and mixed using a stirrer until it becomes completely uniform. Particularly, in the liquid preparation, the final halocyanoacetamide is 0.1 to 40% by weight, preferably 5 to 20% by weight, and the cyclodextrin is 0.1 to 20% by weight.
It is adjusted to 1 to 60% by weight, preferably 5 to 40% by weight. Further, in the present invention, known additives such as a surfactant and an antioxidant may be added for their purposes and uses.

As the surface active agent, known surface active agents such as soaps, nonionic surface active agents, anionic surface active agents, cationic surface active agents, amphoteric surface active agents, polymer surface active agents and the like can be used. Can be used. Among them, nonionic surfactants and anionic surfactants are preferably used. Examples of the nonionic surfactant include polyoxyalkylene aryl phenyl ether, polyoxyethylene nonyl phenyl ether, ethylene oxide / propylene oxide block copolymer, and the like. Examples of the anionic surfactant include alkylbenzene sulfonic acid metal salt, alkylnaphthalene sulfonic acid metal salt, polycarboxylic acid type surfactant, dialkylsulfosuccinic acid ester metal salt, polyoxyethylene distyrenated phenyl ether sulfate ammonium salt, lignin. Examples thereof include sulfonic acid metal salts and lignin sulfonic acid metal salts, and examples of the metal salts include sodium salts and potassium salts.

As the antioxidant, 2,6-di-t-
Butyl-4-methylphenol, 2,2'-methylenebis [4-methyl-6-t-butylphenol] and other phenolic antioxidants, alkyldiphenylamine, N,
Examples include amine antioxidants such as N'-di-s-butyl-p-phenylenediamine. For example, in the case of a liquid agent, these surfactants and antioxidants are added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the liquid agent. The halocyanoacetamide-containing composition of the present invention exhibits a stable effect over a long period of time, for example, as a paper pulp mill, a slime control agent in a cooling water circulation process, a germicide, a germicidal detergent, and a metalworking oil agent, casein, and starch coating. It can be used as an industrial bactericidal agent such as a working solution and a preservative for water-based paints.

[0010]

The water-stable halocyanoacetamide-containing composition containing the cyclodextrin compound of the present invention has excellent storage stability and aqueous solution stability, and can be suitably used as a liquid formulation, and particularly, It is useful as an industrial germicide.

[0011]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the invention is not limited to the examples. The terms used in Examples and Comparative Examples are as follows. Dibromocyanoacetamide DBNPA Cyclodextrin CD Branched cyclodextrin (30% aqueous solution: Isoeryte L, containing 50% or more by weight of maltosyl cyclodextrin manufactured by Niken Chemical Co., Ltd.) Branched CD Diethylene glycol monomethyl ether DGMM Example 1 DBNPA 10 g was ethylene glycol. It was dissolved in 60 g of monoethyl ether. β-CD 12g in water 18
It melt | dissolved by heating at g. This was mixed with the previously prepared diethylene glycol monomethyl ether solution to obtain 100
g of liquid was obtained. Example 2 15 g of DBNPA was dissolved in 58.4 g of diethylene glycol monomethyl ether. β-CD 8.6g
Was dissolved by heating with 18 g of water. This was mixed with the previously prepared diethylene glycol monomethyl ether solution to obtain 100 g of a liquid agent.

Example 3 10 g of DBNPA was dissolved in 53 g of diethylene glycol monomethyl ether. Branch CD 10g water 2
Dissolved in 7 g. This was mixed with the previously prepared diethylene glycol monomethyl ether solution, and 100 g
To obtain a solution. Examples 4 to 12 In the same manner as in Example 3, liquid solutions of Examples 4 to 12 were obtained with the compositions (% by weight) shown in [Table 1].

[Table 1]

Comparative Example 1 10 g of DBNPA was dissolved in 70 g of diethylene glycol monomethyl ether. Add 20g of water,
100 g of product was obtained. Comparative Examples 2 to 4 In the same manner as Comparative Example 1, the liquid preparations of Comparative Examples 2 to 4 were obtained with the compositions (% by weight) described in [Table 2].

[Table 2]

Test Example 1 The liquid agents obtained in Examples and Comparative Examples were sealed in a glass container, placed in a constant temperature bath at 60 ° C., and two weeks later, the residual ratio of DBNPA in high performance liquid chromatography (% by weight). ) Was measured. The results are shown in [Table 3] and [Table 4].

[Table 3]

[0016]

[Table 4] The same water content is used in [Table 3], and DBNP
Those having the same A content were compared in Table 4 with Examples and Comparative Examples. It can be seen that the formulation having the same water content and DBNPA content has a good residual rate of the formulation containing cyclodextrins regardless of the amount of cyclodextrins.

Test Example 2 Method for measuring antibacterial activity Using the preparations of Example 12 and Comparative Example 1, a multiple dilution method using glucose agar was carried out at 33 ° C. for 18 hours for bacteria, at 28 ° C. for fungi and at 3 ° C. for yeast. The cells were cultured for a day to determine the minimum inhibitory concentration (MIC, μg / ml).

[Table 5] It can be seen that Example 12 has the same efficacy as Comparative Example 1 regardless of the presence or absence of CD.

Claims (9)

[Claims] 1. A halocyanoacetamide-containing composition which is stable to water and which contains a cyclodextrin compound. 2. The composition according to claim 1, which is a liquid agent. 3. The composition according to claim 1, which is an industrial germicide. 4. The composition according to claim 1, which further comprises water. 5. The composition according to claim 1, which further comprises an organic solvent. 6. The composition according to claim 1, wherein the halocyanoacetamide is dibromocyanoacetamide. 7. The composition according to claim 1, wherein the cyclodextrins are cyclodextrins and branched cyclodextrins. 8. The composition according to claim 1, wherein the cyclodextrins are branched cyclodextrins. 9. The composition according to claim 5, wherein the organic solvent is a glycol solvent.