JP2007039388A - Industrial germicidal composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a microorganism-controlling agent capable of being prepared as a liquid preparation containing a bis-quaternary ammonium salt compound of an active ingredient in high concentration while reducing the amount of the used organic solvent. <P>SOLUTION: A mixed solvent of a 2-3C alcohol/water is prepared by mixing one of the alcohols (2-3C alcohols) having two to three carbons with the water so that the content of the 2-3C alcohol may be 40-90 wt.%, preferably 60-80 wt.%. The bis-quaternary ammonium salt compound such as N,N'-hexamethylene-bis(4-carbamoyl-1-decylpyridinium bromide) is formulated with the obtained mixed solvent of the 2-3C alcohol/water so that the concentration of the compound may be ≥10 wt.%, preferably ≥30 wt.% based on the whole amount of the microorganism-controlling agent to provide the microorganism-controlling agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a microbial control agent, and more particularly to a microbial control agent used as a control agent for bacteria, fungi, yeasts and algae.

Conventionally, harmful microorganisms such as bacteria, molds, yeasts, and algae are easily propagated in various industrial products, which causes a decrease in productivity and quality and generation of malodor. Therefore, in order to control the growth of such harmful microorganisms, various microorganism control agents that exhibit antibacterial, antifungal, antiseptic and antialgal effects are widely used.
In recent years, it has been reported that a bis-quaternary ammonium salt compound has a broad antibacterial spectrum and exhibits an excellent control effect as an active ingredient of such a microorganism control agent (see, for example, Patent Document 1). ).
JP 2004-143061 A

However, the bis-quaternary ammonium salt compounds described above, especially the compounds of inorganic salts of bis-quaternary ammonium, have the property of very low solubility in water and alcohol.
For example, N, N′-hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide) has a solubility in water of 2.1 g / L (25 ° C.) and a solubility in ethanol of 13.9 g / L (25 ° C.). It is.

Therefore, such a bis-quaternary ammonium salt compound is usually prepared as a powder, but it is cumbersome because it requires a dissolving operation to prepare as a powder, and a simple liquid that does not require such a dissolving operation. It is eager to prepare as.
On the other hand, from the viewpoint of reducing the environmental load, it is required to reduce the amount of organic solvent used.

  Accordingly, an object of the present invention is to provide a microorganism control agent that can prepare a bisquaternary ammonium salt compound as an active ingredient as a high-concentration liquid agent while reducing the amount of an organic solvent used.

  In order to achieve the above object, the present inventors have intensively studied to prepare a bisquaternary ammonium salt compound as a high-concentration liquid agent while reducing the amount of organic solvent used. We have found the knowledge that bisquaternary ammonium salt compounds can be dissolved at a high concentration by blending the compound with at least one of alcohols having 2 and 3 carbon atoms and water at a specific ratio, and further researched. As a result, the present invention has been completed.

That is, the present invention
(1) A microbial control agent containing a bis-quaternary ammonium salt represented by the following general formula (1), at least one alcohol having 2 and 3 carbon atoms, and water, wherein the carbon number is 2 and 3 Is contained in an amount of 40 to 90% by weight based on the total amount of at least one alcohol having 2 and 3 carbon atoms and water, and the bisquaternary ammonium salt is based on the total amount of the microbial control agent. A microorganism control agent, characterized by containing 10% by weight or more,

(2) The bis quaternary ammonium is contained in an amount of 50 to 80% by weight based on the total amount of at least any one of the alcohols having 2 and 3 carbons and water. The microbial control agent according to (1) above, wherein the salt is contained in an amount of 30% by weight or more based on the total amount of the microbial control agent,
(3) The microorganism according to (1) or (2) above, wherein the bis-quaternary ammonium salt is N, N′-hexamethylenebis (4-carbamoyl-1-decylpyridinium halide) Control agent,
(4) The at least one alcohol having 2 or 3 carbon atoms is at least one selected from the group consisting of ethanol, 1-propanol and 2-propanol. The microorganism control agent according to any one of 3) is provided.

  According to the microorganism control agent of the present invention, while reducing the amount of organic solvent used, it is prepared as a liquid agent containing an active ingredient bisquaternary ammonium salt at a high concentration. Can be used in a range.

The microorganism control agent of the present invention contains a bis-quaternary ammonium salt compound as an active ingredient.
The bisquaternary ammonium salt compound used in the present invention is represented, for example, by the following general formula (1).

(In the formula, R 1 and R 2 are the same or different and each represents a hydrocarbon group which may have a substituent, and R 3 and R 4 are the same or different and each optionally substituted a carbon group. A hydrogen group, an optionally substituted alkoxy group, a hydroxyl group, an amino group or a hydrogen atom; R5 represents an optionally substituted hydrocarbon group or a carbon-carbon single bond; Are —NRnCO—, —CONRn—, —NRnCS— (wherein Rn represents an optionally substituted hydrocarbon group or hydrogen atom), —COO—, —COS—, —O—, -S- or a carbon-carbon single bond, Y2 is -CONRn-, -NRnCO-, -CSNRn- (wherein Rn represents a hydrocarbon group or a hydrogen atom which may have a substituent). , -OOC-, -SOC-, -O-, S- or carbon - a single bond between carbon, Z is an inorganic anion, a is an integer of 1 or 2).
In the general formula (1), examples of the hydrocarbon group which may have a substituent represented by R1 and R2 include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group. Groups and aralkyl groups.

  Examples of the alkyl group include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, iso-pentyl, sec-pentyl, hexyl, heptyl, and n-octyl. , Isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and the like alkyl groups having 1 to 18 carbon atoms.

  Examples of the alkenyl group include vinyl, allyl, methallyl, isopropenyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, butenyl, pentenyl, hexenyl, heptynyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, C2-C18 alkenyl groups, such as tetradecenyl, hexadecenyl, octadecenyl, etc. are mentioned.

Examples of the alkynyl group include alkynyl groups having 2 to 8 carbon atoms such as ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, octenyl and the like.
Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

Examples of the aryl group include aryl groups having 6 to 14 carbon atoms such as phenyl, tolyl, xylyl, biphenyl, naphthyl, anthryl, phenanthryl, and azulenyl.
Examples of the aralkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, diphenylmethyl, o, m or p-methylbenzyl, o, m or p-ethylbenzyl, o, m or p-isopropylbenzyl, o, m or p-tert-butylbenzyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylbenzyl, 2,3,4-, 3,4,5- or 2,4,6-trimethylbenzyl, 5-isopropyl-2-methylbenzyl, 2-isopropyl-5-methylbenzyl, 2- Methyl-5-tert-butylbenzyl, 2,4-, 2,5- or 3,5-diisopropylbenzyl, 3,5-di-tert-butylbenzyl, 1 (2-methylphenyl) ethyl, 1- (3-methylphenyl) ethyl, 1- (4-methylphenyl) ethyl, 1- (2-isopropylphenyl) ethyl, 1- (3-isopropylphenyl) ethyl, 1- (4-Isopropylphenyl) ethyl, 1- (2-tert-butylphenyl) ethyl, 1- (4-tert-butylphenyl) ethyl, 1- (2-isopropyl-4-methylphenyl) ethyl, 1- (4 -Isopropyl-2-methylphenyl) ethyl, 1- (2,4-dimethylphenyl) ethyl, 1- (2,5-dimethylphenyl) ethyl, 1- (3,5-dimethylphenyl) ethyl, 1- (3 , 5-di-tert-butylphenyl) ethyl and the like, and an aralkyl group having 7 to 16 carbon atoms.

  Examples of the substituent of the hydrocarbon group which may have a substituent represented by R1 and R2 include a hydroxyl group, a halogen atom (for example, chlorine, fluorine, bromine and iodine), a cyano group, an amino group, Carboxyl group, alkoxy group (for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, etc. Alkoxy groups), aryloxy groups (eg, phenoxy groups), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxyca) C1-C6 alkoxycarbonyl groups such as bonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, hexyloxycarbonyl, etc., alkylthio groups (for example, methylthio, ethylthio, propylthio, butylthio) Etc.) and arylthio groups (for example, phenylthio groups). These substituents may be the same or different and may be substituted by 1 to 5, preferably 1 to 3.

The hydrocarbon group which may have a substituent represented by R1 and R2 described above is preferably a hydrocarbon group having no substituent or a hydrocarbon group having a hydroxyl group. A group or a hydroxyalkyl group is preferred.
The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably heptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl having 7 or more carbon atoms, Examples thereof include alkyl groups having 7 to 18 carbon atoms such as tetradecyl, hexadecyl, and octadecyl.

  The hydroxyalkyl group is preferably a hydroxyalkyl group having 1 to 18 carbon atoms, more preferably a hydroxytrimethylene, hydroxytetramethylene, hydroxypentamethylene, hydroxyhexamethylene, hydroxy group having 3 to 12 carbon atoms. Examples thereof include hydroxyalkyl groups having 3 to 12 carbon atoms such as heptamethylene, hydroxyoctamethylene, hydroxynonamethylene, hydroxydecamethylene, and hydroxydodecamethylene.

R1 and R2 are the same or different and both are alkyl groups having 1 to 18 carbon atoms, or one is an alkyl group having 1 to 18 carbon atoms and the other is a hydroxyalkyl group having 3 to 12 carbon atoms. Is preferred.
In the general formula (1), the hydrocarbon group optionally having substituents represented by R3 and R4 is the same as the hydrocarbon group optionally having substituents represented by R1 and R2. Preferably, an alkyl group, more preferably, for example, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, iso-pentyl, sec- C1-C6 alkyl groups, such as pentyl and hexyl, are mentioned.

  Examples of the alkoxy group which may have a substituent represented by R3 and R4 include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy , An alkoxy group having 1 to 8 carbon atoms such as isopentyloxy, neopentyloxy, hexyloxy, octyloxy and the like.

In addition, the substituent of the alkoxy group which may have a substituent represented by R3 and R4 is the same as the substituent of the hydrocarbon group which may have a substituent represented by R1 and R2. Is mentioned.
The alkoxy group which may have a substituent represented by R3 and R4 described above is preferably an alkoxy group having no substituent, and among them, carbon number 1 such as methoxy, ethoxy, propoxy, isopropoxy, etc. ˜3 alkoxy groups.

R3 and R4 are the same or different and are each preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, an amino group, or a hydrogen atom. It is preferable that
In the general formula (1), the hydrocarbon group which may have a substituent represented by R5 is preferably an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group. And divalent hydrocarbon groups.

  Examples of the alkylene group include methylene, ethylene, propylene, iso-propylene, butylene, iso-butylene, sec-butylene, pentylene, iso-pentylene, sec-pentylene, hexylene, heptylene, octylene, 2-ethylhexylene and nonylene. , Alkylene groups having 1 to 18 carbon atoms such as decylene, isodecylene, dodecylene, tetradecylene, hexadecylene, and octadecylene.

As an alkenylene group, C2-C18 alkenylene groups, such as vinylene, propenylene, butenylene, butadienylene, octenylene, decenylene, undecenylene, dodecenylene, tetradecenylene, hexadecenylene, octadecenylene, are mentioned, for example.
Examples of the alkynylene group include C2-C8 alkynylene groups such as ethynylene, propynylene, butynylene, pentynylene, and octenylene.

Examples of the cycloalkylene group include cycloalkylene groups having 3 to 8 carbon atoms such as cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene.
As an arylene group, C6-C10 arylene groups, such as phenylene, tolylene, xylylene, naphthylene, are mentioned, for example, Preferably, phenylene and xylylene are mentioned.

  In addition, the substituent of the hydrocarbon group which may have a substituent represented by R5 is the same as the substituent of the hydrocarbon group which may have a substituent represented by R1 and R2. Preferably, C1-C6, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, etc. Alkoxy groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxy Carbonyl, an alkoxycarbonyl group having 1 to 6 carbon atoms such as hexyl oxycarbonyl and the like.

The hydrocarbon group which may have a substituent represented by R5 is preferably an alkylene group having 2 to 18 carbon atoms, a phenylene group, a xylylene group or a carbon-carbon single bond.
In the general formula (1), -NRnCO-, -CONRn-, -NRnCS- represented by Y1, and Rn of -CONRn-, -NRnCO-, -CSNRn- represented by Y2 are substituted. The hydrocarbon group or hydrogen atom which may have a group is mentioned, and the hydrocarbon group which may have a substituent is a hydrocarbon which may have a substituent represented by R1 and R2. The same thing as a group is mentioned. Preferably, an alkyl group or a hydrogen atom is exemplified, and examples of the alkyl group include methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, sec-butyl, pentyl, iso-pentyl, sec-pentyl, hexyl. , Heptyl, n-octyl, isooctyl, 2-ethylhexyl and other alkyl groups having 1 to 8 carbon atoms.

In the general formula (1), Y1 is preferably —NHCO—, —CONH—, —COO—, —O—, —S— or a carbon-carbon single bond, and Y2 is Examples include -CONH-, -NHCO-, -OOC-, -O-, -S-, or a carbon-carbon single bond.
In the general formula (1), examples of the inorganic anion represented by Z include halogen ions (for example, F-, Cl-, Br-, I-, etc.), iodate ions (IO _3- ), bromic acid. ion (BrO ₃ -), chlorate ion (ClO ₃ -), periodate ion (IO ₄ -), perchlorate ion (ClO ₄ -), sulfate ion _(SO ^{4 2} -), nitrate ion (NO ₃ -), Phosphate ion (PO ₄ ^3- ), sulfite ion (SO ₃ ^2- ), nitrite ion (NO _2- ) and the like.

These inorganic anions may be used alone or in combination of two or more. Preferably, a halogen ion is used.
A represents an integer of 1 or 2, and is specifically determined as appropriate according to the type of the bis-quaternary ammonium salt compound and the inorganic anion. a is particularly preferably 1.
Such a bis-quaternary ammonium salt compound can be produced by a known method according to the specific compounds shown below. Specific examples thereof include, for example, N, N′-hexamethylene-bis (4 -Carbamoyl-1-octylpyridinium salt), N, N′-hexamethylenebis (4-carbamoyl-1-decylpyridinium salt), N, N′-hexamethylene-bis (4-carbamoyl-1-dodecylpyridinium salt) N, N ′ such as N, N′-hexamethylene-bis (4-carbamoyl-1-tetradecylpyridinium salt), N, N′-hexamethylene-bis (4-carbamoyl-1-hexadecylpyridinium salt) -Alkylene-bis (4-carbamoyl-1-alkylpyridinium salts), for example N, N'-hexamethylene-bis (3-carbamoy Ru-1-octylpyridinium salt, N, N′-hexamethylene-bis (3-carbamoyl-1-decylpyridinium salt), N, N′-hexamethylene-bis (3-carbamoyl-1-dodecylpyridinium salt), N, N′-hexamethylene-bis (3-carbamoyl-1-tetradecylpyridinium salt), N, N′-hexamethylene-bis (3-carbamoyl-1-hexadecylpyridinium salt), N, N′-hexa N, N′-alkylene-bis (3-carbamoyl-1-alkylpyridinium salt) such as methylene-bis (3-carbamoyl-1-octadecylpyridinium salt), for example, 4,4 ′-(tetramethylenedicarbonyldiamino) Bis (1-octylpyridinium salt), 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-deci Pyridinium salt), 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-dodecylpyridinium salt), 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-tetradecylpyridinium salt), 4,4 4,4 '-(alkylenedicarbonyldiamino) bis (1-alkylpyridinium salt) such as'-(tetramethylenedicarbonyldiamino) bis (1-hexadecylpyridinium salt), such as 4,4'-(hexamethylene 4,4 ′-(alkylenedithio) bis (1-alkylpyridinium salts) such as dithio) bis (1-octylpyridinium salts), for example, 4,4 ′-(p-xylyldithio) bis (1-butylpyridinium salts) 4,4 ′-(p-xylyldithio) bis (1-hexylpyridinium salt), 4,4 ′-(p-xylyldi) Thio) bis (1-octylpyridinium salt), 4,4 ′-(p-xylyldithio) bis (1-decylpyridinium salt), 4,4 ′-(p-xylyldithio) bis (1-dodecylpyridinium salt), 4 , 4 ′-(p-xylyldithio) bis (1-tetradecylpyridinium salt), 4,4 ′-(p-xylyldithio) bis (1-hexadecylpyridinium salt), 4,4 ′-(p-xylyldithio) bis 4,4 ′-(p-xylyldithio) bis ((1-alkyl) pyridinium salt) such as (1-octadecylpyridinium salt), for example, 3,3 ′-(m-xylyldithio) bis (1-tetradecylpyridinium salt) 3,3 ′-(m-xylyldithio) bis (1-alkylpyridinium salts) such as N, N ′-(p-phenylene) bis (4-carbamoyl) 1-hexylpyridinium salt), N, N ′-(p-phenylene) bis (4-carbamoyl-1-octylpyridinium salt), N, N ′-(p-phenylene) bis (4-carbamoyl-1-decylpyridinium) Salt), N, N ′-(p-phenylene) bis (4-carbamoyl-1-dodecylpyridinium salt), N, N ′-(p-phenylene) bis (4-carbamoyl-1-tetradecylpyridinium salt), N, N ′-(p-phenylene) bis (4-carbamoyl-1-hexadecylpyridinium salt), N, N ′-(p-phenylene) bis (4-carbamoyl-1-octadecylpyridinium salt), N ′-(p-phenylene) bis (4-carbamoyl-1-alkylpyridinium salt), for example, N, N ′-(m-phenylene) bis (3-carbamoyl) N, N ′-(m-phenylene) bis (3-carbamoyl-1-alkylpyridinium salt) such as 1-dodecylpyridinium salt), for example, 4,4 ′-(p-phthalamido) bis (1-butylpyridinium salt) Salt), 4,4 ′-(p-phthalamido) bis (1-pentylpyridinium salt), 4,4 ′-(p-phthalamido) bis (1-hexylpyridinium salt), 4,4 ′-(p-phthalamide) ) Bis (1-heptylpyridinium salt), 4,4 ′-(p-phthalamido) bis (1-octylpyridinium salt), 4,4 ′-(p-phthalamido) bis (1-decylpyridinium salt), 4, 4 ′-(p-phthalamido) bis (1-dodecylpyridinium salt), 4,4 ′-(p-phthalamido) bis (1-tetradecylpyridinium salt), 4,4 ′-(p-phthalamido) De) 4,4 ′-(p-phthalamido) bis (1-alkylpyridinium salt) such as bis (1-hexadecylpyridinium salt), 4,4 ′-(p-phthalamido) bis (1-octadecylpyridinium salt) For example, 3,3 ′-(m-phthalamido) bis (1-alkylpyridinium salt) such as 3,3 ′-(m-phthalamido) bis (1-octadecylpyridinium salt), 1,4-tetramethylenebis ( 4-carbamoyl-1-hexadecylpyridinium salt), 1,6-hexamethylenebis (3-carbamoyl-1-dodecylpyridinium salt), 1,6-octamethylenebis (3-carbamoyl-1-tetradecylpyridinium salt) , 3,3 ′-(1,3-trimethylenedicarbonyldiamino) bis (1-dodecylpyridinium salt) Dicarbonyldiamino) bis (1-alkylpyridinium salt) such as 4,4 ′-(1,8-octamethylenedioxy) bis (1-dodecylpyridinium salt), 3,3 ′-(1,6-hexa) (Alkylenedioxy) bis (1-alkylpyridinium salts) such as methylenedioxy) bis (1-hexadodecylpyridinium salt), such as 4,4 ′-(1,6-hexamethylenedioxydicarbonyl) bis ( (Alkylenedioxydicarbonyl) bis (1-alkylpyridinium salt) such as 1-octylpyridinium salt), 3,3 ′-(1,6-tetramethylenedioxydicarbonyl) bis (1-dodecylpyridinium salt), For example, 4,4 ′-(1,4-tetramethylenedicarbonyldioxy) bis (1-octylpyridinium salt) (Alkylenedicarbonyldithioxy) such as 4,4 '-(1,8-octamethylenedicarbonyldithioxy) bis (1-octadecylpyridinium salt) Bis (1-alkylpyridinium salt), for example, 3,3 ′-(p-phthaloyldioxy) bis (1-decylpyridinium salt), 3,3 ′-(m-phthaloyldithioxy) bis (1-decyl) (Phthaloyldithioxy) bis (1-alkylpyridinium salts) such as 1-octyl-1 ′-(3-hydroxytrimethylene) -4,4′-dipyridinium salt, 1-octyl- 1 ′-(6-hydroxyhexamethylene) -4,4′-dipyridinium salt, 1-octyl-1 ′-(8-hydroxyoctamethylene) ) -4,4′-dipyridinium salt, 1-octyl-1 ′-(10-hydroxydecamethylene) -4,4′-dipyridinium salt, 1-octyl-1 ′-(12-hydroxydodecamethylene)- 4,4′-dipyridinium salt, 1-decyl-1 ′-(3-hydroxytrimethylene) -4,4′-dipyridinium salt, 1-decyl-1 ′-(6-hydroxyhexamethylene) -4, 4′-dipyridinium salt, 1-decyl-1 ′-(8-hydroxyoctamethylene) -4,4′-dipyridinium salt, 1-decyl-1 ′-(10-hydroxydecamethylene) -4,4 ′ -Dipyridinium salt, 1-decyl-1 '-(12-hydroxydodecamethylene) -4,4'-dipyridinium salt, 1-dodecyl-1'-(3-hydroxytrimethylene) -4,4'-di Pyridinium salt, 1-dodecy -1 ′-(6-hydroxyhexamethylene) -4,4′-dipyridinium salt, 1-dodecyl-1 ′-(8-hydroxyoctamethylene) -4,4′-dipyridinium salt, 1-dodecyl-1 1-alkyl-1 'such as'-(10-hydroxydecamethylene) -4,4'-dipyridinium salt, 1-dodecyl-1'-(12-hydroxydodecamethylene) -4,4'-dipyridinium salt -(12-hydroxyalkylene) -4,4'-dipyridinium salt and the like.

The pyridinium salt of the bis-quaternary ammonium salt compound is not particularly limited as long as it is a salt with the inorganic anion represented by Z. For example, bromide (pyridinium bromide), iodide (pyridinium iodide), etc. And the like (pyridinium halide).
Of these, N, N′-hexamethylene bis (4-carbamoyl-1) such as N, N′-hexamethylene bis (4-carbamoyl-1-decylpyridinium bromide) (Dimer 38, manufactured by Inui) is preferable. 4,4 ′-(tetramethylenedicarbonyldiamino) bis such as 4-decylpyridinium halide) and 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide) (Dimer 136, manufactured by Inui) (1-decylpyridinium halide). More preferably, N, N′-hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide) (Dimer 38, manufactured by Inui Co.) is used. These bis-quaternary ammonium salt compounds may be used alone or in combination of two or more.

And the microorganism control agent of this invention mix | blends the above-mentioned bis quaternary ammonium salt compound, at least any one of C2 and C3 alcohol (henceforth C2-3 alcohol), and water. Can be prepared.
Examples of the C2-3 alcohol include ethanol, 1-propanol, and 2-propanol. These C2-3 alcohols may be used alone or in combination of two or more. From the viewpoint of dissolving the bisquaternary ammonium salt compound at a high concentration, 1-propanol and / or 2-propanol is preferably used. From the viewpoint of safety, ethanol and / or 2-propanol are preferably used. From the viewpoint of economy, 2-propanol is preferably used.

The blending ratio of C2-3 alcohol to the total amount of C2-3 alcohol and water is 40 to 90% by weight, preferably 50 to 80% by weight, and more preferably 60 to 80% by weight. If the blending ratio of the C2-3 alcohol is within this range, the bisquaternary ammonium salt can be dissolved at a high concentration as described below.
The blending ratio of the bis quaternary ammonium salt to the total amount of the microorganism control agent is 10% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and usually 60% by weight or less. Preferably, it is 55 weight% or less, More preferably, it is 50 weight% or less.

By dissolving the bis quaternary ammonium salt in such a high concentration, a high concentration liquid preparation can be prepared, and it can be used in a wide concentration range over various fields.
More specifically, in the microorganism control agent of the present invention, for example, first, C2-3 alcohol and water are mixed so as to have the above-described blending ratio to prepare a mixed solvent of C2-3 alcohol / water. Then, it can prepare by adding a bis quaternary ammonium salt to this C2-3 alcohol / water mixed solvent so that it may become the above-mentioned mixture ratio, and stirring and mixing.

  The microorganism control agent of the present invention is prepared as a solution as described above, but may be formulated into various dosage forms such as a suspension, paste, powder, granule, microcapsule and the like thereafter. it can. In addition, it may be prepared as an inclusion compound, and further formulated into montmorillonite such as layered silicate (such as smectite) or adsorbed on clay, silica, white carbon, talc, etc. You can also

In addition, the microorganism control agent of the present invention may be added with known additives such as other active ingredients, surfactants, antioxidants, light stabilizers and the like within a range not inhibiting the excellent effects of the present invention. Also good.
The microorganism control agent of the present invention thus obtained exhibits excellent antibacterial, antifungal, antiseptic and antialgal effects, and can be used as a control agent for bacteria, fungi, yeasts, algae and the like. . Moreover, it is prepared as a solution containing a high concentration of the bis-quaternary ammonium salt, which is an active ingredient, and can be used in a wide concentration range by diluting to a desired concentration over various fields. Moreover, since the bis quaternary ammonium salt is prepared by adding it to the C2-3 alcohol / water mixed solvent, the amount of the organic solvent used can be reduced, and the environmental load can be reduced.

  The microorganism control agent of the present invention includes, for example, various industrial waters such as paper pulp mills, cooling water circulation processes, metal processing oils such as cutting oil, casein, starch paste, glue, coated paper, and paper coating liquid. , Surface sizing agents, paints, adhesives, synthetic rubber latex, inks, polyvinyl alcohol films, vinyl chloride films, resin products, cement admixtures, sealing agents, joint products, and other industrial products Can be used effectively.

More specifically, for example, slime control agents for paper pulp mills, antiseptics for metal processing oils, antiseptics and fungicides for paints, antiseptics and fungicides for resin emulsions, antiseptics for cement admixtures, and antiseptics for inks It is suitably used as an industrial harmful microorganism control agent such as a fungicide, an antifungal agent for dampening water, an antifungal agent for cement water reducing agent, and a life prolonging agent for plants.
In addition, although the addition amount of the microorganism control agent of the present invention may be appropriately determined depending on the application target, for example, 1 to 1000 mg (total active ingredients) / kg (product), preferably 5 to 500 mg (total It can be used after diluting to a concentration of active ingredient) / kg (product).

In addition, the microorganism control agent of the present invention can be used for an application target having a pH of 3 to 13, preferably 4 to 12. Further, for example, SO ₂ ²⁻ , SO ₃ ²⁻ , HSO ₂ ⁻ , HSO ₃ ⁻ , S ₂ O ₃ ²⁻ , preferably SO ₃ ²⁻ , HSO ₃ ⁻ , S ₂ O ₃ ^{2−, and the} like can be effectively exhibited even in the presence of a reducing agent. . In addition, it is preferable that the density | concentration of the reducing agent in this case is 1-10000 ppm in a product, for example.

  Various solvents such as methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, and propylene glycol are mixed with water, and the solvent concentration (solvent / (solvent + water)) is 0 (100% by weight of water). ), 30 wt% (water 70 wt%), 60 wt% (water 40 wt%), 80 wt% (water 20 wt%), 100 wt% (water 0 wt%) Prepared.

For methanol, ethylene glycol, and propylene glycol, only those having a solvent concentration of 0 (100% by weight of water), 60% by weight (40% by weight of water), and 100% by weight (0% by weight of water) were prepared. .
Next, the saturation concentration (% by weight) of dimer 38 (N, N′-hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide: 99% by weight, manufactured by Inui Co.) with respect to each mixed solvent was determined according to the following method. The results are shown in Table 1 and FIG.

Method for Measuring Saturation Concentration Dimer 38 was added to each mixed solvent so as to be supersaturated, and left overnight with shaking. Each mixed solvent was decanted and then filtered, and the filtrate was quantitatively analyzed with a high performance liquid chromatograph to obtain a saturated concentration.

  As is clear from FIG. 1, ethanol, 1-propanol, and 2-propanol, which are alcohols having 2 or 3 carbon atoms, are mixed with water, so that dimer 38 can be mixed with alcohol alone or water alone, respectively. It could be dissolved at a higher concentration than it was dissolved. When the solvent concentration is in the range of 40 to 90% by weight, the saturation concentration of the dimer 38 is 11% by weight or more, and when the solvent concentration is in the range of 60 to 80% by weight, the saturation concentration of the dimer 38 is It became 30 weight% or more.

On the other hand, for methanol, which is an alcohol having 1 carbon, the saturation concentration of the dimer 38 could be increased somewhat by mixing methanol and water. Could not be dissolved at a high concentration.
In addition, regarding the glycols such as ethylene glycol and propylene glycol, the synergistic effect by mixing them with water was not confirmed, and the dimer 38 could be dissolved at a higher concentration by dissolving the glycol alone. However, when the glycol alone was dissolved, the amount of organic solvent used increased.

Formulation Example 1
Ethanol and water were mixed to prepare a mixed solvent having a solvent concentration (solvent / (solvent + water)) of 60% by weight (water 40% by weight). Subsequently, the dimer 38 was mix | blended with the prepared mixed solvent so that it might become 40 weight% in the whole liquid agent obtained, and the liquid agent was prepared.
Formulation Example 2
Ethanol and water were mixed to prepare a mixed solvent having a solvent concentration (solvent / (solvent + water)) of 80 wt% (water 40 wt%). Subsequently, the dimer 38 was mix | blended with the prepared mixed solvent so that it might become 30 weight% in the whole liquid agent obtained, and the liquid agent was prepared.

Formulation Example 3
1-propanol and water were mixed to prepare a mixed solvent having a solvent concentration (solvent / (solvent + water)) of 60% by weight (water 40% by weight). Subsequently, the dimer 38 was mix | blended with the prepared mixed solvent so that it might become 50 weight% in the whole liquid agent obtained, and the liquid agent was prepared.
Formulation Example 4
1-propanol and water were mixed to prepare a mixed solvent having a solvent concentration (solvent / (solvent + water)) of 80% by weight (water 40% by weight). Subsequently, the dimer 38 was mix | blended with the prepared mixed solvent so that it might become 50 weight% in the whole liquid agent obtained, and the liquid agent was prepared.

Formulation Example 5
2-Propanol and water were mixed to prepare a mixed solvent having a solvent concentration (solvent / (solvent + water)) of 60% by weight (water 40% by weight). Subsequently, the dimer 38 was mix | blended with the prepared mixed solvent so that it might become 45 weight% in the whole liquid agent obtained, and the liquid agent was prepared.
Formulation Example 6
2-Propanol and water were mixed to prepare a mixed solvent having a solvent concentration (solvent / (solvent + water)) of 80% by weight (water 40% by weight). Subsequently, the dimer 38 was mix | blended with the prepared mixed solvent so that it might become 45 weight% in the whole liquid agent obtained, and the liquid agent was prepared.

It is a graph which shows the saturation density | concentration of the dimer 38 with respect to the solvent density | concentration of various mixed solvents.

Claims (4)

A microbial control agent containing a bisquaternary ammonium salt represented by the following general formula (1), at least one alcohol having 2 or 3 carbon atoms, and water,
40 to 90% by weight of at least one alcohol having 2 or 3 carbon atoms is contained with respect to the total amount of at least one alcohol having 2 or 3 carbon atoms and water,
A microbial control agent, wherein the bisquaternary ammonium salt is contained in an amount of 10% by weight or more based on the total amount of the microbial control agent.

50 to 80% by weight of at least one alcohol having 2 or 3 carbon atoms is contained with respect to the total amount of at least one alcohol having 2 or 3 carbon atoms and water,
The microbial control agent according to claim 1, wherein the bisquaternary ammonium salt is contained in an amount of 30% by weight or more based on the total amount of the microbial control agent.   The microbial control agent according to claim 1 or 2, wherein the bisquaternary ammonium salt is N, N'-hexamethylenebis (4-carbamoyl-1-decylpyridinium halide).   4. The alcohol according to claim 1, wherein the alcohol having 2 or 3 carbon atoms is at least one selected from the group consisting of ethanol, 1-propanol and 2-propanol. Microbial control agent.

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