JP2018145157A - Industrial bactericidal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial bactericidal composition used for the treatment for the purpose of preservation and disinfection of propagation of bacteria, fungi, etc., which cause deterioration of quality, occurrence of malodor, etc., in paper making chemical preparations in the pulp and paper industry, industrial waters in various industries, or many industrial products.SOLUTION: Provided is an industrial bactericidal composition in which three components of glyoxime compound, 5-chloro-2-methyl-4-isothiazolin-3-one and halogenated aliphatic nitro alcohol based compound are combined, so that the composition has, when added by a small amount to an object to be disinfected, a longer-term effect and a spectrum of broad efficacy and has bactericidal and bacteriostatic activities, and thereby can disinfect microorganisms before they have an acquired tolerance.SELECTED DRAWING: None

Description

  INDUSTRIAL APPLICABILITY The present invention is effective as a papermaking chemical in the pulp and paper industry, various industrial cooling waters, metalworking oils, textile oils, pastes and other preservatives and bactericides, and has long been affected by decay by microorganisms such as bacteria and fungi It relates to an industrial disinfecting composition that can be protected over time.

  Papermaking chemicals in the pulp and paper industry are industrial water-based compositions based on water, such as paints, latex, starch slurry liquids, paper coating colors, and paper strength agents, which are contaminated by bacteria. Spoilage causes odor generation, deterioration of physical properties such as viscosity reduction and pH fluctuation, and fungal growth causes clogging of the strainer, coloring, and contamination.

  In addition, many industrial products such as metal processing oils such as cutting oil, casein, starch paste, glue, adhesives, synthetic rubber, ink, resin products, concrete admixtures, and other industrial products include bacteria, fungi, etc. Harmful microorganisms are easy to propagate, causing a decrease in productivity and quality, and generation of malodor. Therefore, industrial disinfectants are widely used to control the growth of such microorganisms.

  As such an industrial disinfectant, an oxime compound, a cyclic nitrogen sulfur compound, a bromine compound, a thiocyan compound, a quaternary ammonium salt compound or the like has been used singly or as a mixture thereof. However, these compounds have various drawbacks in use, for example, insufficient bactericidal effect of drugs, acquisition of microbial resistance when used for a long time, foaming in the working environment, etc. May have the disadvantage of having an adverse effect.

  As a technique using an oxime compound as an antibacterial agent, industrial sterilization, antiseptic, and algicidal agents that contain at least one compound selected from the glyoxime compound and the following compound group as active ingredients have been found (Patent Literature). 1). The following compound groups include halogenated aliphatic nitroalcohol compound (a), 1,2-benzisothiazol-3 (2H) -one (b), 2-bromo-2- (bromomethyl) glutaronitrile (c ), Methylenebisthiocyanate (d), 4,5-dichloro-3H-1,2-dithiol-3-one (e), 2,2-dibromo-2-cyanoacetamide (f), mucobromic acid (g) ), Halogenated acetate compounds (h), 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (i).

As a technique using 5-chloro-2-methyl-4-isothiazolin-3-one as a bactericide, nitrobromine compound (component A) and component B include dibromocyanoacetamide, methylenebisthiocyanate, 4,5-dichloro From -1,2-dithiol-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-octyl-4-isothiazolin-3-one, bisbromoacetoxybutene It has been found as an industrial disinfectant characterized by containing at least one or more selected compounds (Patent Document 2).

  Furthermore, as a technology combining a glyoxime compound and an isothiazolone compound, a combination of a glyoxime derivative and an isothiazolone derivative (free form), or a combination of a glyoxime derivative and an isothiazolone derivative (complex compound) exhibits excellent bactericidal and algicidal action. It is found as an industrial sterilizer, algaecide and preservative characterized by (Patent Document 3) Examples of glyoxime derivatives include monochloroglioxime and dichloroglyoxime. Examples of the isothiazolone derivative (free form) include 2-methyl-3-isothiazolone, 5-chloro-2-methyl-3-isothiazolone, 4,5-dichloro-2-methyl-3-isothiazolone, and 2-benzyl-5-chloro. -3-isothiazolone, 2-n-octyl-3-isothiazolone, 4,5-dichloro-2-n-octyl-3-isothiazolone, or a mixture thereof. Examples of isothiazolone derivatives (complex compounds) include 2-methyl-3-isothiazolone-magnesium nitrate complex compounds, 2-methyl-5-chloro-3-isothiazolone-magnesium nitrate complex compounds, and mixtures thereof.

As a technique using 2,2-dibromo-2-nitroethanol which is a halogenated aliphatic nitroalcohol compound as a bactericidal agent, a halocyanoacetamide compound (A), a halogenated aliphatic nitroalcohol compound (B) and It has been found as an industrial antibacterial composition characterized by containing three components of 2-bromo-2-bromomethylglutaronitrile (C) (Patent Document 4).

  However, although these compositions exhibit a certain level of effect, there are hopes for compositions that can achieve a higher effect with a small amount and compositions with a broad spectrum of efficacy in a new combination in terms of longer-term effects and cost. It is also true that they are rare.

Japanese Patent Laid-Open No. 7-2606 JP 2000-053502 A JP-A-5-105604 JP 2000-63211 A

  The present invention has been made in view of such circumstances, and a combination of three components comprising a glyoxime compound, 5-chloro-2-methyl-4-isothiazolin-3-one and a halogenated aliphatic nitroalcohol compound. By adding a small amount to an object to be sterilized, it has a long-term effect and a broad spectrum of efficacy, and has sterilizing power and bacteriostatic power before sterilizing microorganisms before gaining resistance An object of the present invention is to provide an industrial sterilizing composition capable of achieving the above.

  As a result of intensive studies to solve the above problems, the present inventor has combined glyoxime compounds, 5-chloro-2-methyl-4-isothiazolin-3-one and halogenated aliphatic nitroalcohol compounds, The inventors have found that microorganisms can be sterilized before they have acquired resistance by having a longer-term effect and a broad spectrum of efficacy, and having sterilizing power and bacteriostatic power, thereby completing the present invention.

（式中Ｘは水素又は塩素を示す）で表されるグリオキシム化合物、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、ハロゲン化脂肪族ニトロアルコール系化合物の３成分を含有することを特徴とする工業用殺菌組成物。
［２］一般式（１）

（式中Ｘは水素又は塩素を示す）で表されるグリオキシム化合物が、ジクロログリオキシムである［１］に記載の工業用殺菌組成物。
［３］ハロゲン化脂肪族ニトロアルコール系化合物が、２，２−ジブロモ−２−ニトロエタノール、２−ブロモ−２−ニトロプロパン−１，３−ジオールからなる群より選択される一種以上である［１］又は［２］に記載の工業用殺菌組成物。
［４］上記［１］〜［３］に記載の工業用殺菌組成物を製紙用薬剤に添加することを特徴とする殺菌方法。 That is, the present invention relates to the following inventions.
[1] General formula (1)

(Wherein X represents hydrogen or chlorine) and contains three components of 5-chloro-2-methyl-4-isothiazolin-3-one and a halogenated aliphatic nitroalcohol compound. Industrial disinfectant composition characterized.
[2] General formula (1)

The industrial sterilizing composition according to [1], wherein the glyoxime compound represented by the formula (X represents hydrogen or chlorine) is dichloroglyoxime.
[3] The halogenated aliphatic nitroalcohol compound is one or more selected from the group consisting of 2,2-dibromo-2-nitroethanol and 2-bromo-2-nitropropane-1,3-diol. The industrial disinfecting composition according to [1] or [2].
[4] A sterilization method comprising adding the industrial sterilization composition according to [1] to [3] to a papermaking chemical.

  By using the industrial sterilizing composition of the present invention, it is a papermaking chemical in the pulp and paper industry, industrial water in various industries, many industrial products, causing deterioration in quality, generation of malodor, bacteria, mold, Proliferation of yeast or the like can be prevented for a longer period and can be sterilized.

  The glyoxime compound used in the present invention is a compound having HON = C—C═NOH as a skeleton, and can be produced by a known technique, and examples thereof include monochloroglioxime and dichloroglyoxime. As the glyoxime compound, those commercially available as industrial raw materials can be used. For example, “DCG / MDG” (10% by weight of dichloroglyoxime, methyl diglycol solution) is commercially available from Fuji Sangyo Co., Ltd. There is something that is. As these glyoxime compounds, dichloroglyoxime is preferably used.

As a compounding quantity of the glyoxime compound used for the industrial bactericidal composition of this invention, it is preferable to contain in the density | concentration range of 0.1-20 weight%, The concentration range of 1-10 weight% is more preferable, Furthermore, 1 More preferably, it is contained in a concentration range of ˜5% by weight.

  5-Chloro-2-methyl-4-isothiazolin-3-one used in the present invention can be produced by a known technique, but those commercially available as general industrial raw materials can also be used. For example, commercially available from Rohm and Haas Japan as “KATHON (registered trademark) LX1400” (a solution containing 10.6% by weight of 5-chloro-2-methyl-4-isothiazolin-3-one and sodium nitrate). “KATHON® WT” (13.9 wt. As a 3: 1 mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one %, Magnesium nitrate-containing solution) commercially available from Rohm and Haas Japan, "KATHON (registered trademark) LXSF25" (19 weight of 5-chloro-2-methyl-4-isothiazolin-3-one % -Containing solution) commercially available from Rohm & Haas Japan, "ZONEN" ) FP "(5-chloro-2-methyl-4-isothiazolin-3-11.2 wt% of one, such as that commercially available propylene glycol solution) as Kemikurea Inc. is available.

As the blending amount of 5-chloro-2-methyl-4-isothiazolin-3-one used in the industrial sterilizing composition of the present invention, it is preferably contained in a concentration range of 0.1 to 10% by weight. A concentration range of 5 to 5% by weight is more preferable, and a concentration range of 1 to 3% by weight is more preferable.

  The halogenated aliphatic nitroalcohol compound used in the present invention can be produced by a known technique, but those commercially available as general industrial raw materials can also be used. For example, “DBNE-75” (75% by weight of 2,2-dibromo-2-nitroethanol, diethylene glycol solution) commercially available from Chemicrea, “BRONOPOL” (2-bromo-2-nitropropane-1 , 3-diol of 99% by weight or more) is commercially available from Chemicrea.

  The halogenated aliphatic nitroalcohol compound used in the industrial sterilizing composition of the present invention is preferably contained in a concentration range of 0.1 to 30% by weight, more preferably in a concentration range of 5 to 25% by weight. It is preferable to contain.

  In the industrial bactericidal composition of the present invention, a solvent can be used for preparation. Examples of such solvents include alcohols such as ethanol and isopropanol, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, and dipropylene glycol, methyl diglycol, butyl diglycol, isopropyl diglycol, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, glycol ethers such as dipropylene glycol monomethyl ether, glycerin solvents such as glycerin and diglycerin, γ-butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. It is possible to use. These solvents may be used alone or in combination of two or more.

Regarding the surfactant, it should not be necessarily added for the preparation of the industrial bactericidal composition of the present invention, but it may be added for the purpose of improving the solubility and mixing property at the time of use. Is possible. The surfactant is not particularly limited, and examples thereof include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. The type of nonionic surfactant is not particularly limited. For example, polyoxyethylene alkyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, sorbitan fatty acid ester, Examples thereof include oxyethylene sorbitan fatty acid esters. Examples of the anionic surfactant include alkyl benzene sulfonate, polyoxyethylene alkyl phenyl ether sulfate, and dialkyl sulfosuccinate. Cationic surfactants include aliphatic amine salts and quaternary ammonium salts thereof, and amphoteric surfactants include betaine surfactants and aminocarboxylates. Further, these nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants may be used alone or in combination of two or more.

The industrial bactericidal composition of the present invention contains a glyoxime compound, 5-chloro-2-methyl-4-isothiazolin-3-one and a halogenated aliphatic nitroalcohol compound, and a composition containing these compounds In order to prepare a thing, it is possible to mix | blend pH adjusters other than a solvent and surfactant, a chelating agent, a rust preventive agent, an antifoamer, a viscosity modifier, etc.

In addition to glyoxime compounds, 5-chloro-2-methyl-4-isothiazolin-3-one and halogenated aliphatic nitroalcohol compounds that are bactericidal components of the industrial bactericidal composition of the present invention, the efficacy and stability of the preparation It is also possible to use other sterilizing components at the same time as long as they do not affect the above. Such a bactericidal component is not particularly limited. For example, methylene bis thiocyanate, glutaraldehyde, iodopropynyl butyl carbamate, pyridinethiol-N-oxide zinc salt, 1,2-benzisothiazolone, 1,2- Dibromo-2,4-dicyanobutane, Nn-butylbenzisothiazolone, N-octylisothiazolone, 2- (4-thiazolyl) benzimidazole, methyl 2-benzimidazolylcarbamate, tetrachloroisophthalonitrile, diiodomethylpara Tolylsulfone, parachlorophenyl-3-iodopropargyl formal, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, o-phenylphenol, isopropylmethylphenol, parachlorometaxylenol, - hydroxybenzoic acid alkyl ester, and fatty acid glycerin esters.

The dosage form of the industrial bactericidal composition of the present invention is not particularly limited, and examples thereof include emulsions, solubilizers, flowable preparations, and suspoemulsion preparations. Of these dosage forms, a solubilizing agent in which a bactericidal component is dissolved in a solvent is suitable.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these. The blending ratios shown below are all by weight. Moreover, the industrial bactericidal composition of each Example and the comparative example was prepared by mixing and melt | dissolving each component at normal temperature. In addition, as long as there is no notice in particular, the following commercially available raw materials were used for the bactericidal component. Moreover, the display of a bactericidal component and a solvent is represented by the following abbreviations.

DCG · MDG: 10% by weight of dichloroglyoxime, methyldiglycol solution ZONEN FP: 11.2% by weight of 5-chloro-2-methyl-4-isothiazolin-3-one, propylene glycol solution DBNE-75: 2, 75% by weight of 2-dibromo-2-nitroethanol, diethylene glycol solution BRONOPOL: 2-bromo-2-nitropropane-1,3-diol MBTC: methylene bis-thiocyanate

MDG: Methyl diglycol

Examples 1-10, Comparative Examples 1-7
Preparations containing a glyoxime compound, 5-chloro-2-methyl-4-isothiazolin-3-one and a halogenated aliphatic nitroalcohol compound were prepared according to the formulations shown in Tables 1 to 4 to obtain an industrial bactericidal composition. It was.

Antiseptic efficacy test 1
30 g of oxidized starch slurry (starch content 30%, pH 6.3) obtained from Sumi Paper Company was dispensed into a sterilized plastic container, and the industrial sterilization compositions of Examples 1-10 and Comparative Examples 1-7 By adding the product to a predetermined concentration, inoculating 2% of the oxidized starch slurry spoiled by bacteria and fungi every week and measuring the number of viable bacteria and fungi one week after inoculation The antiseptic effect was evaluated. Various starch slurries during the test period were stored at 30 ° C.
The number of viable bacteria was measured by visually observing the number of viable bacteria by mixing an aqueous solution obtained by diluting various starch slurries with sterilized water 100 times in 1 ml standard agar medium and culturing at 30 ° C. for 2 days.
For the number of viable fungi, an aqueous solution obtained by diluting various starch slurries with sterilized water 100 times was mixed with 1 ml of potato dextrose agar medium, cultured at 25 ° C. for 2 days, and the viable cell count was visually measured.
In addition, about the judgment of bacteria or fungi, it implemented with the microscope.
Table 5 shows the results for bacteria, and Table 6 shows the results for fungi.

Antiseptic efficacy test 2
30 g each of polyacrylamide-based paper strength agent (pH 4.7) obtained from a paper manufacturing company was dispensed into a sterilized plastic container, and the industrial sterilizing compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were added thereto. Preservative efficacy by adding 2% of paper strength agent spoiled by bacteria and fungi at the start of the test and every week, and measuring the number of viable bacteria and fungi one week after inoculation. Evaluated. Various paper strength agents during the test period were stored at 30 ° C.
For the number of viable bacteria, an aqueous solution obtained by diluting various paper strength agents 100 times with sterilized water was mixed with 1 ml standard agar medium, cultured at 30 ° C. for 2 days, and the viable cell count was visually measured.
For the number of viable fungi, an aqueous solution obtained by diluting various paper strength agents 100 times with sterilized water was mixed with 1 ml of potato dextrose agar medium, cultured at 25 ° C. for 2 days, and the viable cell count was visually measured.
In addition, about the judgment of bacteria or fungi, it implemented with the microscope.
The results for bacteria are shown in Table 7, and the results for fungi are shown in Table 8.

  The industrial bactericidal composition of the present invention contains a glyoxime compound, 5-chloro-2-methyl-4-isothiazolin-3-one, and a halogenated aliphatic nitroalcohol compound as essential components. In many industrial products such as papermaking chemicals, metal processing oils such as cutting oil, casein, starch paste, glue, adhesives, synthetic rubber, and ink in the field, it may cause deterioration of quality and generation of bad odor. It is preferably used as a preservative and fungicide that can prevent and sterilize the growth of bacteria, fungi and the like for a longer period of time.

Claims (4)

General formula (1)

(Wherein X represents hydrogen or chlorine) and contains three components of 5-chloro-2-methyl-4-isothiazolin-3-one and a halogenated aliphatic nitroalcohol compound. Industrial disinfectant composition characterized. General formula (1)

The industrial bactericidal composition according to claim 1, wherein the glyoxime compound represented by the formula (X represents hydrogen or chlorine) is dichloroglyoxime. The halogenated aliphatic nitroalcohol compound is at least one selected from the group consisting of 2,2-dibromo-2-nitroethanol and 2-bromo-2-nitropropane-1,3-diol. The industrial disinfecting composition according to claim 1 or 2. A sterilization method comprising adding the industrial sterilization composition according to claim 1 to a papermaking chemical.