JP2003212706A - Microorganism-controlling agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a microorganism-controlling agent capable of developing excellent controlling effect on bacteria, fungi, yeasts, algae or the like. <P>SOLUTION: This microorganism-controlling agent comprises at least one kind of compound selected from a group consisting of a bis-quaternary ammoinium salt compound, an isothiazoline-based compound, a nitroalcohol- based compound, a dithiol-based compound, a thiophene-based compound, a haloacetylene-based compound, a phthalimide-based compound, a haloalkylthio- based compound, a pyrithione-based compound, a phenylurea-based compound, a triazine-based compound, a guanidine-based compound, a triazole-based compound and benzimidazole-based compound. The agent develops excellent synergistic effect as a controlling agent for bacteria, fungi, yeasts, algae, etc. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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.

[0002]

2. Description of the Related Art Conventionally, various industrial waters such as paper pulp mills and cooling water circulation processes, metal working oils such as cutting oils, casein, starch paste, glue, coated paper, paper coating liquid, surface Various industrial products such as sizing agents, paints, adhesives, synthetic rubber latex, inks, polyvinyl alcohol films, vinyl chloride films, resin products, cement admixtures, sealing agents, jointing agents, bacteria, fungi, yeasts, algae, etc. The harmful microorganisms are easily proliferated, which causes the deterioration of productivity and quality and the generation of malodor. Therefore, in order to control the reproduction of such harmful microorganisms, various microbial control agents exhibiting antibacterial, antifungal, antiseptic and antialgal effects are widely used.

As such a microbial control agent, recently, for example, JP-A-9-110692 and JP-A-1
0-95773, JP-A-10-287566, JP-A-2000-95763, JP-A-2000-
In Japanese Patent No. 136185 and Japanese Patent Laid-Open No. 2000-198879, it is reported that the bis-quaternary ammonium salt compounds described therein have a broad antibacterial spectrum and exhibit an excellent controlling effect.

[0004]

[Patent Document 1] JP-A-9-110692

[Patent Document 2] Japanese Patent Laid-Open No. 10-95773

[Patent Document 3] Japanese Patent Laid-Open No. 10-287566

[Patent Document 4] Japanese Patent Laid-Open No. 2000-95763

[Patent Document 5] Japanese Patent Laid-Open No. 2000-136185

[Patent Document 6] Japanese Patent Laid-Open No. 2000-198879

However, even if the above-mentioned bis-quaternary ammonium salt compound is used alone, the control effect may not be sufficient, and a novel microbial control agent capable of expressing a sufficient control effect. Development is desired.

Therefore, the present invention has been made in view of the above circumstances, and its purpose is to prevent bacteria, fungi,
It is an object of the present invention to provide a microbial control agent capable of expressing an excellent control effect on yeast, algae and the like.

[0006]

In order to achieve the above object, the inventors of the present invention have diligently studied a compound capable of exhibiting an excellent synergistic effect in combination with a bis quaternary ammonium salt compound. By using the compounds represented by the following general formulas (2) to (17) in combination with the quaternary ammonium salt compound, we found out that a synergistic control effect with the bis-quaternary ammonium salt compound can be found, and further research is conducted. As a result, the present invention has been completed.

That is, the present invention provides (1) a bis-quaternary ammonium salt compound represented by the following general formula (1) and an isothiazoline compound represented by the following general formula (2) and / or the following general formula (3). A nitro alcohol compound represented by the following general formula (4), a dithiol compound represented by the following general formula (5), a thiophene compound represented by the following general formula (6), and a general formula (7) Haloacetylene compounds, phthalimide compounds represented by the following general formula (8), haloalkylthio compounds represented by the following general formula (9), pyrithione compounds represented by the following general formula (10), and general formula (11) below. ), A triazine compound represented by the following general formula (12), a general formula (13) below, and / or a general formula (14 below) ) A guanidine compound represented by
The following general formula (15) and / or the following general formula (16)
A triazole compound represented by the following general formula (17)
A microbial control agent, which comprises at least one compound selected from the group consisting of benzimidazole compounds represented by the general formula (1)

[0008]

[Chemical 18] (In the formula, R 1 and R 2 are the same or different and each represents a hydrocarbon group which may have a substituent, R 3 and R 4
Are the same or different, a hydrocarbon group which may have a substituent, an alkoxy group which may have a substituent,
A hydroxyl group, an amino group or a hydrogen atom, R5 is
A hydrocarbon group which may have a substituent or a carbon-carbon single bond, Y1 is -NRnCO-, -CONRn.
-, -NRnCS- (Rn represents a hydrocarbon group which may have a substituent or a hydrogen atom), -COO.
-, -COS-, -O-, -S- or a carbon-carbon single bond, Y2 is -CONRn-, -NRnCO-,-.
CSNRn- (Rn represents a hydrocarbon group which may have a substituent or a hydrogen atom), -OOC-,-.
SOC-, -O-, -S- or a carbon-carbon single bond, Z is an anion, and a is an integer of 1 or 2. ) General formula (2)

[0009]

[Chemical 19] (In the formula, R6 is a hydrocarbon group or a hydrogen atom which may have a substituent, X1 and X2 are the same or different, and a hydrocarbon group (X1 and X2 are divalent hydrocarbon groups; (Including the case where a ring is formed), and a halogen atom or a hydrogen atom.) General formula (3)

[0010]

[Chemical 20] (In the formula, R7 represents a hydrocarbon group or a hydrogen atom which may have a substituent, and A ring represents a benzene ring which may have a substituent.) General formula (4)

[0011]

[Chemical 21] (In the formula, R8 represents a hydrocarbon group or a hydrogen atom,
Represents a hydrocarbon group having a hydroxyl group, a halogen atom or a hydrogen atom, and X3 represents a hydrocarbon group having a hydroxyl group or a halogen atom. ) General formula (5)

[0012]

[Chemical formula 22] (In the formula, X4 and X5 are the same or different and represent a halogen atom or a hydrogen atom.) General formula (6)

[0013]

[Chemical formula 23] (In the formula, X6, X7, X8 and X9 are the same or different and represent a hydrocarbon group which may have a substituent, a halogen atom or a hydrogen atom.) General formula (7)

[0014]

[Chemical formula 24] (In the formula, R10 and R11 are the same or different and each represents a hydrocarbon group or a hydrogen atom which may have a substituent, X10 represents a halogen atom, and z represents an integer of 0 or 1.) Formula (8)

[0015]

[Chemical 25] (In the formula, both X11 and X12 represent a halogen atom, X13 represents a hydrocarbon group having a halogen atom or a halogen atom, and ring B represents a cyclohexene ring or a benzene ring.) General formula (9)

[0016]

[Chemical formula 26] (In the formula, R12 is a hydrocarbon group which may have a substituent or -N (Ra) (Rb) (Ra and Rb are the same or different and may be a hydrocarbon group which may have a substituent). Hydrogen group), X14 and X15 are both halogen atoms, X16 is a hydrocarbon group or halogen atom having a halogen atom, and Y3 is —SO ₂ — or —CONH—.
And C ring represents a benzene ring which may have a substituent. ) General formula (10)

[0017]

[Chemical 27] (In the formula, M represents a metal, and n represents an integer of 1 to 4.) General formula (11)

[0018]

[Chemical 28] (In the formula, R13 and R14 are the same or different and each represents a hydrocarbon group or a hydrogen atom which may have a substituent which may be bonded to an adjacent nitrogen atom via an oxygen atom, X17 and X18 are the same or different and each represents a halogen atom or a hydrogen atom.) General formula (12)

[0019]

[Chemical 29] (In the formula, R15, R16, R17 and R18 are each a hydrocarbon group which may have a substituent or a hydrogen atom,
19 represents an alkylthio group or a halogen atom. ) General formula (13)

[0020]

[Chemical 30] (In formula, W shows a salt, m shows the integer of 1-30, p shows the integer of 2-8.) General formula (14).

[0021]

[Chemical 31] (In the formula, D ring represents a benzene ring which may have a substituent, and t represents an integer of 2 to 8.) General formula (15)

[0022]

[Chemical 32] (In the formula, R 19, R 20 and R 21 are the same or different and each represents a hydrocarbon group or hydrogen atom which may have a substituent, and F 1 represents an aryl group which may have a substituent or a substituent. An aralkyl group which may have a group,
q shows the integer of 1-3. ) General formula (16)

[0023]

[Chemical 33] (In the formula, R22 and R23 are the same or different and each represents a hydrocarbon group or hydrogen atom which may have a substituent, and F2 represents an aryl group or a substituent which may have a substituent. An aralkyl group which may have, q is 1
Indicates an integer of ˜3. ) General formula (17)

[0024]

[Chemical 34] (In the formula, R24 represents a hydrocarbon group or a hydrogen atom which may have a substituent, and E represents —NHCOOR25 (R2
5 represents a hydrocarbon group which may have a substituent. )
Represents a carbamate group or a thiazolyl group. (2) In the formula of the bis quaternary ammonium salt compound represented by the general formula (1), R 1 and R 2 are an alkyl group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 18 carbon atoms, and R 3 and R4 is a hydrogen atom, R5
Is an alkylene group having 2 to 18 carbon atoms, a phenylene group, a xylylene group or a carbon-carbon single bond, (3) a microbial control agent, (3) general formula (2) And in the formula of the isothiazoline compound represented by the general formula (3), R6 and R7 are an alkyl group having 1 to 8 carbon atoms or a hydrogen atom, and X1 and X2 are
Both are hydrogen atoms, one is a hydrogen atom and the other is a chlorine atom or both are chlorine atoms, the above (1)
Or a microbial control agent according to (2), (4) R in the formula of the nitroalcohol-based compound represented by the general formula (4)
8 is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R9 is an alkyl group having 1 to 4 carbon atoms having a hydroxyl group, a bromine atom or a hydrogen atom, and X3 is a carbon number having a hydroxyl group. 1 to 4 alkyl group, bromine atom or chlorine atom, characterized in that the microbial control agent according to any one of (1) to (3),
(5) In the formula of the dithiol compound represented by the general formula (5), X4 and X5 are both chlorine atoms or bromine atoms, one is a hydrogen atom and the other is a chlorine atom or a bromine atom, The microbial control agent according to any one of (1) to (4) above, (6) in the formula of the thiophene compound represented by the general formula (6), X6, X7, X8 and X9 are all chlorine atoms, or The microbial control agent according to any one of (1) to (5) above, wherein any three are chlorine atoms and one is a hydrogen atom.
(7) In the formula of the haloacetylene compound represented by the general formula (7), one of R10 and R11 is a hydrogen atom, the other is an alkyl group having 1 to 10 carbon atoms, and X10 is an iodine atom. A microbial control agent according to any one of (1) to (6) above, characterized by: (8) General formula (8)
In the formula of the phthalimide compound represented by, X11 and X12 are both chlorine atoms, and X13 is an alkyl group having 1 to 4 carbon atoms having a chlorine atom and / or a fluorine atom, a chlorine atom or a fluorine atom. (12) In the formula of the haloalkylthio compound represented by the general formula (9), R 12 has 1 to 4 carbon atoms. Or an -N (Ra) (Rb) (Ra and Rb are both alkyl groups having 1 to 4 carbon atoms), X14 and X15 are both chlorine atoms, and X16 is a chlorine atom and / or It is an alkyl group having 1 to 4 carbon atoms having a fluorine atom, a chlorine atom or a fluorine atom, and the C ring is benzene, an alkyl-substituted benzene, or a halogen-substituted benzene. The microbial control agent according to any one of (1) to (8) above, (10) in the formula of the pyrithione compound represented by the general formula (10), M is sodium, zinc, copper, nickel, or cobalt. R13 in the formula of the phenylurea compound represented by the general formula (11), wherein the microbial control agent according to any one of the above (1) to (9) is And R1
4 is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an alkynyl group having 1 to 8 carbon atoms, or 1 carbon atom
~ 8 is an alkoxy group, X17 and X18 is a chlorine atom or a hydrogen atom, characterized in that the microorganism control agent according to any one of (1) to (10),
(12) In the formula of the triazine-based compound represented by the general formula (12), R15 and R16 are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and R17 and R18 are
Alkyl group having 1 to 5 carbon atoms which may be substituted by alkoxy group having 1 to 4 carbon atoms or 3 to 6 carbon atoms which may be substituted by alkoxy group having 1 to 4 carbon atoms
X13 is a cycloalkyl group, wherein X19 is an alkylthio group having 1 to 4 carbon atoms or a halogen atom, and the microbial control agent according to any one of (1) to (11) above, In the formula of the guanidine-based compound represented by the general formula (13), W is an inorganic acid salt and p is 6, wherein the microorganism is any of the above (1) to (12). Control agent, (14) In the formula of the guanidine compound represented by the general formula (14), D ring is chlorophenyl and t is 6, (1)
To (13), the microorganism control agent according to any one of (13), (15)
In the formula of the triazole-based compound represented by the general formula (15), R19, R20 and R21 are a hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, and F1 is a halogen-substituted phenyl or a halogen-substituted phenylalkyl. The microorganism control agent according to any one of (1) to (14) above, (16) R22 and R23 in the formula of the triazole compound represented by the general formula (16),
Where one is a hydrogen atom and the other is a hydrocarbon group having 1 to 4 carbon atoms, or both are hydrogen atoms, and F2 is a halogen-substituted phenyl group, (1) to
(17) The microbial control agent as described in any of (15),
In the formula of the benzimidazole compound represented by the general formula (17), R24 is a hydrogen atom, and E is -NHCOO.
R25 (R25 is an alkyl group having 1 to 8 carbon atoms) or a thiazolyl group, the above (1)
To (16) are provided.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The microbial control agent of the present invention comprises a bis-quaternary ammonium salt compound represented by the following general formula (1) as an essential active ingredient, and the following general formula (2) and / or the following general formula ( 3) an isothiazoline-based compound, a nitroalcohol-based compound represented by the following general formula (4), a dithiol-based compound represented by the following general formula (5), a thiophene-based compound represented by the following general formula (6),
A haloacetylene compound represented by the following general formula (7),
A phthalimide compound represented by the following general formula (8), a haloalkylthio compound represented by the following general formula (9),
A pyrithione-based compound represented by the following general formula (10), a phenylurea-based compound represented by the following general formula (11),
A triazine compound represented by the following general formula (12), a guanidine compound represented by the following general formula (13) and / or a general formula (14), a general formula (15) and / or a general formula (16) shown below. And a benzimidazole compound represented by the following general formula (17). By containing at least one of these active ingredients, an excellent controlling effect can be exhibited.

The bis-quaternary ammonium salt compound used in the present invention is represented by the following general formula (1).

General formula (1)

[0028]

[Chemical 35] (In the formula, R 1 and R 2 are the same or different and each represents a hydrocarbon group which may have a substituent, R 3 and R 4
Are the same or different, a hydrocarbon group which may have a substituent, an alkoxy group which may have a substituent,
A hydroxyl group, an amino group or a hydrogen atom, R5 is
A hydrocarbon group which may have a substituent or a carbon-carbon single bond, Y1 is -NRnCO-, -CONRn.
-, -NRnCS- (Rn represents a hydrocarbon group which may have a substituent or a hydrogen atom), -COO.
-, -COS-, -O-, -S- or a carbon-carbon single bond, Y2 is -CONRn-, -NRnCO-,-.
CSNRn- (Rn represents a hydrocarbon group which may have a substituent or a hydrogen atom), -OOC-,-.
SOC-, -O-, -S- or a carbon-carbon single bond, Z is an anion, and a is an integer of 1 or 2. ) In the formula of the general formula (1), as the hydrocarbon group of the hydrocarbon group which may be substituted, represented by R1 and R2,
Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group and an aralkyl group.

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

As the alkenyl group, for example, vinyl,
Allyl, methallyl, isopropenyl, 1-propenyl,
2-propenyl, 2-methyl-1-propenyl, butenyl, pentenyl, hexenyl, heptynyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl,
Examples thereof include alkenyl groups having 2 to 18 carbon atoms such as tetradecenyl, hexadecenyl and octadecenyl.

Examples of the alkynyl group include alkynyl groups having 2 to 8 carbon atoms such as ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl and octenyl.

Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

As the aryl group, for example, phenyl,
6 to 14 carbon atoms such as tolyl, xylyl, biphenyl, naphthyl, anthryl, phenanthryl and azulenyl.
The aryl group of is mentioned.

The aralkyl group is, for example, 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-te
rt-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
Examples include aralkyl groups having 7 to 16 carbon atoms such as -dimethylphenyl) ethyl, 1- (3,5-dimethylphenyl) ethyl and 1- (3,5-di-tert-butylphenyl) ethyl.

Examples of the substituent of the hydrocarbon group which may have a substituent represented by R1 and R2 include, for example, a hydroxyl group, a halogen atom (eg chlorine, fluorine, bromine and iodine), a cyano group, Amino group, carboxyl group, alkoxy group (eg, methoxy, ethoxy,
Propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, and other alkoxy groups having 1 to 6 carbon atoms), aryloxy groups (eg, phenoxy) Group), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,
Isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t
ert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, hexyloxycarbonyl, and other alkoxycarbonyl groups having 1 to 6 carbon atoms), alkylthio groups (eg, methylthio, ethylthio, propylthio,
(C1-4 alkylthio groups such as butylthio)
And arylthio groups (eg, phenylthio groups, etc.)
And so on. 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 is preferably a hydrocarbon group having no substituent or a hydrocarbon group having a hydroxyl group. Of these, an alkyl group or a hydroxyalkyl group is preferable.

The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably 7 carbon atoms.
And above, heptyl, n-octyl, isooctyl,
Examples thereof include alkyl groups having 7 to 18 carbon atoms such as 2-ethylhexyl, nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl and octadecyl.

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

R1 and R2 are the same or different and each is an alkyl group having 1 to 18 carbon atoms, or one is an alkyl group having 1 to 18 carbon atoms and the other is 3 to 1 carbon atoms.
It is preferably 2 hydroxyalkyl groups.

In the formula (1), the hydrocarbon group represented by R3 and R4, which may have a substituent, is
Examples thereof include the same hydrocarbon groups that may have a substituent represented by R1 and R2, preferably an alkyl group, more preferably, for example, methyl, ethyl, n-
Propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl,
Examples thereof include alkyl groups having 1 to 6 carbon atoms such as iso-pentyl, sec-pentyl and hexyl.

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

The substituent of the alkoxy group which may have a substituent represented by R3 and R4 is R1
And the same as the substituent of the hydrocarbon group which may have a substituent represented by R2.

The alkoxy group which may have a substituent represented by R3 and R4 is preferably an alkoxy group which does not have a substituent, and among them, methoxy, ethoxy, propoxy, isopropoxy and the like. An alkoxy group having 1 to 3 carbon atoms can be mentioned.

R3 and R4 are the same or different and each is an alkyl group having 1 to 6 carbon atoms or 1 to 3 carbon atoms.
Is preferably an alkoxy group, a hydroxyl group, an amino group or a hydrogen atom, and among them, both are preferably hydrogen atoms.

In the formula (1), the hydrocarbon group which may have a substituent represented by R5 is preferably an alkylene group, an alkenylene group, an alkynylene group or a cycloalkylene group. , 2 such as arylene group
Included are valent hydrocarbon groups.

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

Examples of the alkenylene group include vinylene, propenylene, butenylene, butadienylene, octenylene, decenylene, undecenylene, dodecenylene, tetradecenylene, hexadecenylene, octadecenylene and the like having 2 to 18 carbon atoms.

Examples of the alkynylene group include alkynylene groups having 2 to 8 carbon atoms such as ethynylene, propynylene, butynylene, pentynylene and octenylene.

Examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene,
Examples thereof include cycloalkylene groups having 3 to 8 carbon atoms such as cyclohexylene, cycloheptylene and cyclooctylene.

The arylene group includes, for example, phenylene, tolylene, xylylene, naphthylene and the like having 6 carbon atoms.
The arylene group of 10 to 10 is mentioned, Preferably, phenylene and xylylene are mentioned.

The substituent of the hydrocarbon group optionally represented by R5 is the same as the substituent of the hydrocarbon group optionally represented by R1 and R2. The preferred examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy and the like. ~ 6 alkoxy groups, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl,
Examples thereof include alkoxycarbonyl groups having 1 to 6 carbon atoms such as sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl and hexyloxycarbonyl.

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--, which is represented by Y1,
And -CONRn- and -NRnCO represented by Y2
Examples of Rn of-and -CSNRn- include a hydrocarbon group which may have a substituent or a hydrogen atom, and examples of the hydrocarbon group which may have a substituent include R1 and R
The same as the hydrocarbon group which may have a substituent represented by 2 can be mentioned. Preferably, an alkyl group or a hydrogen atom is mentioned, and examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl and n-.
Butyl, iso-butyl, sec-butyl, pentyl,
Examples thereof include alkyl groups having 1 to 8 carbon atoms such as iso-pentyl, sec-pentyl, hexyl, heptyl and n-octyl.

In the formula (1), Y1 is preferably --NHCO--, --CONH--, --COO--, --O.
-, -S- or a carbon-carbon single bond, and as Y2, -CONH-, -NHCO-, -OO.
C-, -O-, -S- or a carbon-carbon single bond is mentioned.

In the formula (1), examples of the anion represented by Z include an inorganic anion and an organic anion.

Examples of the inorganic anion include halogen ions (for example, F-, Cl-, Br-, I-, etc.), iodate ion (IO _3- ), bromate ion (BrO _3- ),
Chlorate ion (ClO _3- ), Periodate ion (IO
₄ -), perchlorate ion (ClO ₄ -), sulfate ion (S
O ₄ ^2- ), nitrate ion (NO _3- ), phosphate ion (P
Examples include O ₄ ³ −), sulfite ion (SO ₃ ² −), and nitrite ion (NO ₂ −).

Examples of the organic anion include free organic acids such as free organic carboxylic acid and free organic sulfonic acid. Free organic acid has 1 carbon atom
-20, preferably a free organic acid having 1 to 10 carbon atoms.

Examples of the free organic carboxylic acid include, for example,
Monovalent saturated carboxylate ion, divalent saturated carboxylate ion, monovalent unsaturated carboxylate ion, divalent unsaturated carboxylate ion, hydroxycarboxylate ion, oxocarboxylate ion, aromatic carboxylate ion, etc. Is mentioned.

Examples of monovalent saturated carboxylate ions include
For example, formate ion (HCOO-), acetate ion (CH_Three
COO-), propionate ion (C_TwoH₅COO-),
Butyrate ion (C_ThreeH₇COO-), isobutyrate ion
((CH_Three)_TwoCHCOO-), valerate ion (CH_Three
(CH_Two)_ThreeCOO-), isovalerate ion ((C
H_Three)_TwoCHCH_TwoCOO-), pivalate ion ((C
H_Three)_ThreeCCOO-), octanoate ion (CH_Three(C
H_Two)₆COO-), decanoate ion (CH_Three(C
H_Two)₈COO-), laurate ion (CH_Three(CH
_Two)₁₀COO-), myristate ion (CH_Three(C
H_Two)₁₂COO-), palmitate ion (CH
_Three(CH _Two)₁₄COO-), stearate ion (C
H_Three(CH_Two)₁₆COO-), etc., having 1 to 18 carbon atoms
Examples thereof include monovalent saturated carboxylate ions.

Examples of the divalent saturated carboxylate ion include oxalate ion ((COO-) ₂ ), malonate ion (CH ₂ (COO-) ₂ ), succinate ion ((-O
OC) (CH ₂ ) ₂ (COO-)), glutarate ion ((-OOC) (CH ₂ ) ₃ (COO-)), adipate ion ((-OOC) (CH ₂ ) ₄ (COO-)) , Pimelic acid ion ((-OOC) (CH ₂ ) ₅ (COO
-)), Suberate ion ((-OOC) (CH ₂ ).
₆ (COO-)), azelaic acid ion ((-OOC)
(CH ₂ ) ₇ (COO-)), sebacate ion ((-O
OC) (CH ₂ ) ₈ (COO-)) and the like having 2 to 1 carbon atoms
And a divalent saturated carboxylate ion of 0 and the like.

As the monovalent unsaturated carboxylate ion,
For example, acrylic acid ion (CH ₂ = CHCOO-), methacrylate ion _{(CH 2 = C (CH 3} ) COO-), crotonic acid ion _{(CH 3 CH = CHCOO -)} , cis-
Crotonic acid ion _(CH 3 _CH = CHCOO-), sorbic acid ion _{(CH 3 CH = CHCH = CHCOO-} ), oleic acid ion _{(CH 3 (CH 2) 7} CH = CH (CH
_{2) 7 COO -), trans} -9- octadecenoic acid ion _{(CH 3 (CH 2) 7} CH = CH (CH 2) 7 COO
-), such as furan carboxylic acid ion _{(C 4} H 3 OCOO-) 1 monovalent unsaturated carboxylic acid ion having a carbon number of 3 to 18, such as and the like.

As the divalent unsaturated carboxylate ion,
For example, maleate ion (CH (COO-) = CHCO
O-), citraconic acid ion _{((CH 3) C (COO-} )
= CHCOO-), mesaconic acid ion ((COO-) C
(CH ₃₎ = CHCOO-), and the like divalent unsaturated carboxylic acid ion 4-5 carbon atoms such as.

Examples of the hydroxycarboxylate ion include lactate ion (CH ₃ CH (OH) COO-) and malate ion (CH (OH) (COO-) CH ₂ COO.
-), Citrate ion (CH ₂ (COO-) C (OH)
(COO-) CH ₂ COO-), glycolate ion (CH
₂ (OH) CH (OH) CH (OH) CH (OH) CH
Examples thereof include hydroxycarboxylic acid ions having 3 to 6 carbon atoms such as (OH) COO-).

Examples of the oxocarboxylate ion include pyruvate ion (CH ₃ COCOO −) and acetoacetate ion (CH ₃ COCH ₂ COO −) having 3 to 4 carbon atoms.

Examples of the aromatic carboxylate ion include benzoate ion (C ₆ H ₅ COO-), phthalate ion (C ₆ H ₄ (COO-) ₂ ), and naphthalenecarboxylate ion (C ₁₀ H ₇ COO). -), such as an aromatic carboxylic acid ion having a carbon number of 5-11 such as pyridine carboxylic acid ion _{(C 5} H ₅ NCOO-) and the like.

[0066] As the free organic sulfonic acids, for example, methyl sulfate ion _{((CH 3) SO 4 -} ), ethyl sulfate ion _{((C 2 H 5) SO} 4 -), methyl benzenesulfonate ion (CH Examples of the organic sulfonate ion having 1 to 7 carbon atoms such as ₃ C ₆ H ₄ SO _3- ).

In addition, as the organic anion represented by Z in the formula (1), other organic anions derived from amino acids, erythorbic acid, ascorbic acid, dehydroacetic acid, alcoholates, phenolates and hydroxyl groups can be mentioned. To be

These anions may be used alone or in combination of two or more. Preferably, an organic anion, more preferably a free organic acid, and more preferably a free organic carboxylic acid is used.

In addition, a represents an integer of 1 or 2, and is specifically determined depending on the types of the bis-quaternary ammonium salt compound and the anion. 1 is particularly preferable as a.

Such a bis-quaternary ammonium salt compound can be produced by a known method according to the specific compounds shown below, and 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, N'-alkylene-such as N'-hexamethylene-bis (4-carbamoyl-1-tetradecylpyridinium salt) and N, N'-hexamethylene-bis (4-carbamoyl-1-hexadecylpyridinium salt) Bis (4-carbamoyl-1-alkylpyridinium salt), for example, N,
N'-hexamethylene-bis (3-carbamoyl-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'-hexamethylene-bis (3-carbamoyl-1-octadecylpyridinium salt), etc. N,
N'-alkylene-bis (3-carbamoyl-1-alkylpyridinium salt), for example, 4,4 '-(tetramethylenedicarbonyldiamino) bis (1-octylpyridinium salt), 4,4'-(tetramethylenedi Carbonyldiamino) bis (1-decylpyridinium salt), 4,
4 '-(tetramethylenedicarbonyldiamino) bis (1-dodecylpyridinium salt), 4,4'-(tetramethylenedicarbonyldiamino) bis (1-tetradecylpyridinium salt), 4,4 '-(tetramethylenedi) 4,4 ′-(alkylenedicarbonyldiamino) bis (1-alkylpyridinium salt) such as carbonyldiamino) bis (1-hexadecylpyridinium salt), for example,
4,4 ′-(alkylenedithio) bis (1-alkylpyridinium salt) such as 4,4 ′-(hexamethylenedithio) bis (1-octylpyridinium salt), for example,
4,4 '-(p-xylyldithio) bis (1-butylpyridinium salt), 4,4'-(p-xylyldithio) bis (1-hexylpyridinium salt), 4,4 '-(p-
Xylyldithio) 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
4,4 ′-(p-xylyldithio) bis ((1-alkyl) pyridinium salt) such as -xylyldithio) bis (1-octadecylpyridinium salt), eg 3,
3,3 ′-(m-xylyldithio) bis (1-alkylpyridinium salt) such as 3 ′-(m-xylyldithio) bis (1-tetradecylpyridinium salt), for example,
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'- such as N, N '-(p-phenylene) bis (4-carbamoyl-1-octadecylpyridinium salt)
N, N '-(such as (p-phenylene) bis (4-carbamoyl-1-alkylpyridinium salt), for example, N, N'-(m-phenylene) bis (3-carbamoyl-1-dodecylpyridinium salt). m-phenylene) bis (3-carbamoyl-1-alkylpyridinium salt),
For example, 4,4 '-(p-phthalamido) bis (1-butylpyridinium salt), 4,4'-(p-phthalamido) bis (1-pentylpyridinium salt), 4,4'-
(P-phthalamido) bis (1-hexylpyridinium salt), 4,4 ′-(p-phthalamido) 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,
4,4′- such as 4 ′-(p-phthalamido) bis (1-hexadecylpyridinium salt) and 4,4 ′-(p-phthalamido) bis (1-octadecylpyridinium salt)
3,3′- such as (p-phthalamido) bis (1-alkylpyridinium salt), for example, 3,3 ′-(m-phthalamido) bis (1-octadecylpyridinium salt).
(M-phthalamido) bis (1-alkylpyridinium 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 ′
(Alkylenedicarbonyldiamino) bis (1-alkylpyridinium salt) such as-(1,3-trimethylenedicarbonyldiamino) bis (1-dodecylpyridinium salt), for example, 4,4 '-(1,8-octa Methylenedioxy) bis (1-dodecylpyridinium salt), 3,
3 '-(1,6-hexamethylenedioxy) bis (1-
(Alkylenedioxy) bis (1-alkylpyridinium salt) such as hexadodecylpyridinium salt), for example, 4,4 ′-(1,6-hexamethylenedioxydicarbonyl) bis (1-octylpyridinium salt), 3 ，
(Alkylenedioxydicarbonyl) bis (1-alkylpyridinium salt) such as 3 ′-(1,6-tetramethylenedioxydicarbonyl) bis (1-dodecylpyridinium salt), for example, 4,4 ′-(1 , 4-tetramethylenedicarbonyldioxy) bis (1-octylpyridinium salt) such as (alkylenedicarbonyldioxy) bis (1-alkylpyridinium salt),
(Alkylenedicarbonyldithioxy) bis (1-alkylpyridinium salt) such as 4,4 ′-(1,8-octamethylenedicarbonyldithioxy) bis (1-octadecylpyridinium salt), for example, 3,3′- (Phthaloyldithioxy) bis (1-alkyl) such as (p-phthaloyldioxy) bis (1-decylpyridinium salt) and 3,3 ′-(m-phthaloyldithioxy) bis (1-decylpyridinium salt) Pyridinium salt), for example, 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'-dipyridinium salt,
1-dodecyl-1 '-(6-hydroxyhexamethylene) -4,4'-dipyridinium salt, 1-dodecyl-
1 '-(8-hydroxyoctamethylene) -4,4'-
Dipyridinium salt, 1-dodecyl-1 ′-(10-hydroxydecamethylene) -4,4′-dipyridinium salt,
1-alkyl-1 '-(12-hydroxyalkylene) -4,4' such as 1-dodecyl-1 '-(12-hydroxydodecamethylene) -4,4'-dipyridinium salt
-Dipyridinium salts 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 anion represented by Z, and for example,
Examples thereof include bromide (pyridinium bromide), iodide (pyridinium iodide), and acetate (pyridinium acetate).

Of these, N, N'-hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide) (dimer 38, manufactured by Inui) is preferred.
N, N'-hexamethylenebis (4-carbamoyl-1
-Decylpyridinium acetate) (dimer 38A,
Inui), 4,4 '-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide) (Dimer 136, Inui), 4,4'-(tetramethylenedicarbonyldiamino) bis (1- Decylpyridinium acetate) (Dimer 136A, manufactured by Inui). These bis-quaternary ammonium salt compounds may be used alone or in combination of two or more.

The isothiazoline compound used in the present invention is represented by the following general formula (2) and / or the following general formula (3).

General formula (2)

[0075]

[Chemical 36] (In the formula, R6 is a hydrocarbon group or a hydrogen atom which may have a substituent, X1 and X2 are the same or different, and a hydrocarbon group (X1 and X2 are divalent hydrocarbon groups; (Including the case where a ring is formed), and a halogen atom or a hydrogen atom.) General formula (3)

[0076]

[Chemical 37] (In the formula, R7 represents a hydrocarbon group or hydrogen atom which may have a substituent, and A ring represents a benzene ring which may have a substituent.) General formula (2) and general formula In the formula (3), R6 and R
Examples of the hydrocarbon group which may have a substituent represented by 7 include those similar to the hydrocarbon group which may have a substituent which is represented by R1 and R2 described above. Hydrocarbon groups not having are preferred, among which,
Alkyl groups are preferred. The alkyl group has a carbon number of 1 to 8, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, i.
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as so-butyl, sec-butyl and tert-butyl, and an alkyl group having 8 carbon atoms such as octyl. More preferably, methyl, n-butyl and n-octyl are mentioned.

Preferable examples of R6 and R7 include an alkyl group having 1 to 8 carbon atoms and a hydrogen atom.

In the isothiazoline compound represented by the general formula (2), the hydrocarbon group represented by X1 and X2 is a hydrocarbon group which may have a substituent represented by R1 and R2. Examples thereof include those similar to the hydrogen group, preferably an alkyl group, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t.
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as ert-butyl.

X1 and X2 may be ring-formed with a divalent hydrocarbon group, and examples of such a divalent hydrocarbon group include methylene, ethylene, propylene (trimethylene) and iso-. Carbon number 1 such as propylene, butylene (tetramethylene), iso-butylene, sec-butylene, pentylene, iso-pentylene, sec-pentylene, hexylene (hexamethylene)
The divalent hydrocarbon group of 6 is mentioned. Preferable is trimethylene.

Examples of the halogen atom represented by X1 and X2 include fluorine, chlorine, bromine and iodine. Preferable is chlorine.

Preferred examples of X1 and X2 include, for example, a halogen atom and a hydrogen atom. In a preferred embodiment, for example, both X1 and X2 are hydrogen atoms, and one of X1 and X2 is a hydrogen atom. And the other is a halogen atom, and both X1 and X2 are halogen atoms. Further, a ring formed of trimethylene is also one of the preferable embodiments.

In the isothiazoline compound represented by the general formula (3), the substituent of the benzene ring represented by the A ring is a hydrocarbon group which may have a substituent represented by R1 and R2 described above. The thing similar to a substituent is mentioned. Preferably, a halogen atom, an alkyl group (eg, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t
(C1-C4 alkyl groups such as ert-butyl)
Is mentioned. These substituents may be the same or different and may be substituted by 1 to 4, preferably 1 or 2. A preferable example of the benzene ring which may have a substituent represented by ring A is a benzene ring which does not have a substituent.

Such an isothiazoline compound can be produced by a known method according to the specific compounds shown below, and specific examples thereof include 2-methyl-4-isothiazolin-3-one. , 2-ethyl-4
-Isothiazolin-3-one, 2-n-octyl-4-
Isothiazolin-3-one, 5-chloro-2-methyl-
4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-
n-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-Dichloro-2-cyclohexyl-4-isothiazolin-3-one, 2-methyl-
4,5-trimethylene-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, Nn
-Butyl-1,2-benzisothiazolin-3-one and the like can be mentioned. Of these, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and 5 are preferable. -Chloro-2
-N-octyl-4-isothiazolin-3-one, 4-
Chloro-2-n-octyl-4-isothiazoline-3-
On, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one , N-n-butyl-1,2-
Benzisothiazolin-3-one may be mentioned. These isothiazoline compounds may be used alone or in combination of two or more.

The nitroalcohol compound used in the present invention is represented by the following general formula (4).

General formula (4)

[0086]

[Chemical 38] (In the formula, R8 represents a hydrocarbon group or a hydrogen atom,
Represents a hydrocarbon group having a hydroxyl group, a halogen atom or a hydrogen atom, and X3 represents a hydrocarbon group having a hydroxyl group or a halogen atom. In the formula (4), examples of the hydrocarbon group represented by R8 include the same hydrocarbon groups as the hydrocarbon groups which may have a substituent represented by R1 and R2 described above. To be Preferably, it is an alkyl group, more preferably methyl, ethyl, n-propyl, iso-propyl, n-.
Butyl, iso-butyl, sec-butyl, tert-
Examples thereof include alkyl groups having 1 to 4 carbon atoms such as butyl.

In the formula (4), the hydrocarbon group having a hydroxyl group represented by R9 is
Examples thereof include the same hydrocarbon group as the hydrocarbon group which may have a substituent, which is represented by R1 and R2. Preferably, an alkyl group, more preferably, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and the like can be mentioned. . Further, the hydroxyl group is, for example, a hydrocarbon group with 1 to 3
It is preferable that one is substituted, and among them, one is preferably substituted.

The hydrocarbon group having such a hydroxyl group is preferably hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl or the like, and preferably hydroxymethyl.

Examples of the halogen atom represented by R9 include those similar to the halogen atom represented by X1 and X2 described above, and preferably chlorine and bromine.

In the formula (4), examples of the hydrocarbon group having a hydroxyl group represented by X3 include the same as the hydrocarbon group having a hydroxyl group represented by R9. Preferred are hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl and the like, and more preferred is hydroxymethyl. The halogen atom represented by X3 is R
Examples thereof include those similar to the halogen atom represented by 9, and chlorine and bromine are preferable.

In a preferred embodiment of the general formula (4), R is
8 is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R9 is an alkyl group having 1 to 4 carbon atoms having a hydroxyl group, a bromine atom or a hydrogen atom, and X3 is a carbon number having a hydroxyl group. 1 to 4 is an alkyl group, a bromine atom or a chlorine atom, R8 is a methyl or hydrogen atom, R9 is hydroxyethyl, hydroxymethyl, a bromine atom or a hydrogen atom, and X3 is hydroxy. The embodiment in which it is a methyl, bromine atom or chlorine atom is more preferable.

Such a nitro alcohol compound is
It can be produced by a known method according to the following specific compounds, and specific examples thereof include 2-
Bromo-2-nitropropane-1,3-diol, 2-
Bromo-2-nitrobutane-1,3-diol, 3-bromo-3-nitropentane-2,4-diol, 2,2
-Dibromo-2-nitro-1-ethanol, 2-nitro-1,3-propanediol, tris (hydroxymethyl) nitromethane, 3,3-dibromo-3-nitro-2
-Propanol, 2-chloro-2-nitroethanol,
2-chloro-2-nitro-1,3-propanediol,
3-chloro-3-nitro-2-propanol etc. are mentioned. Of these, 2-bromo-2- is preferable.
Examples include nitropropane-1,3-diol and 2,2-dibromo-2-nitro-1-ethanol. These nitro alcohol compounds may be used alone or in combination of two or more.

The dithiol compound used in the present invention is represented by the following general formula (5).

General formula (5)

[0095]

[Chemical Formula 39] (In the formula, X4 and X5 are the same or different and represent a halogen atom or a hydrogen atom.) In the formula of the general formula (5), the halogen atom represented by X4 and X5 is the same as the above X1 and X2. The same halogen atom as shown can be mentioned, and chlorine and bromine are preferable.

In a preferred embodiment of the general formula (5), for example, X4 and X5 are both bromine atom, X4 and X5.
5 are both chlorine atoms, one of X4 and X5 is a bromine atom, the other is a chlorine atom, and one of X4 and X5 is a bromine atom and the other is a hydrogen atom, and one of X4 and X5. An embodiment in which one is a chlorine atom and the other is a hydrogen atom can be mentioned.

Such a dithiol compound can be produced by a known method according to the following specific compounds, and specific examples thereof include 4,5-dichloro-1,2-dithiol. -3-one, 4,5-dibromo-1,2-dithiol-3-one, 4-chloro-
1,2-dithiol-3-one, 4-bromo-1,2-
Examples thereof include dithiol-3-one. Of these, 4,5-dichloro-1,2-dithiol-3-one is preferable. These dithiol compounds may be used alone or in combination of two or more.

The thiophene compound used in the present invention is represented by the following general formula (6).

General formula (6)

[0100]

[Chemical 40] (In the formula, X6, X7, X8 and X9 are the same or different and represent a hydrocarbon group which may have a substituent, a halogen atom or a hydrogen atom.) In the formula of the general formula (6), As the hydrocarbon group which may have a substituent represented by X6, X7, X8 and X9,
The same as the above-mentioned hydrocarbon group which may have a substituent represented by R1 and R2 can be mentioned. Hydrocarbon groups having no substituents are preferable, and among them, alkyl groups are preferable. The alkyl group is preferably
Methyl, ethyl, n-propyl, iso-propyl, n
-Butyl, iso-butyl, sec-butyl, tert
And alkyl groups having 1 to 4 carbon atoms such as butyl.

Examples of the halogen atom represented by X6, X7, X8 and X9 are the same as the halogen atom represented by X1 and X2 described above, preferably chlorine.

As a preferred embodiment of the general formula (6), X is
6, X7, X8 and X9 are all halogen atoms, X
6, X7 and X8 are halogen atoms, X9 is a hydrogen atom, X6
And X7 are halogen atoms and X8 and X9 are hydrogen atoms. Of these, X6, X7, X8
And X9 are all halogen atoms, especially X6,
An embodiment in which all of X7, X8 and X9 are chlorine atoms is preferable.

Such a thiophene-based compound can be produced by a known method according to the following specific compounds, and specific examples thereof include, for example, 3,3,3.
4,4-tetrachlorotetrahydrothiophene-1,1
-Dioxide, 3,3,4,4-tetrabromotetrahydrothiophene-1,1-dioxide, 3,4-dichlorotetrahydrothiophene-1,1-dioxide, 3,
3,4-trichlorotetrahydrothiophene-1,1-
Dioxide, 3,3,4-tribromotetrahydrothiophene-1,1-dioxide and the like can be mentioned. Of these, preferably 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide, 3,3,4,4
-Tetrachlorotetrahydrothiophene-1,1-dioxide. These thiophene compounds may be used alone or in combination of two or more.

The haloacetylene compound used in the present invention is represented by the following general formula (7).

General formula (7)

[0106]

[Chemical 41] (In the formula, R10 and R11 are the same or different and each represents a hydrocarbon group or a hydrogen atom which may have a substituent, X10 represents a halogen atom, and z represents an integer of 0 or 1.) In the formula of formula (7), the hydrocarbon group which may have a substituent represented by R10 and R11 includes the hydrocarbon group which may have a substituent represented by R1 and R2 described above. The same thing is mentioned. Hydrocarbon groups having no substituents are preferable, and among them, alkyl groups are preferable. The alkyl group is preferably methyl,
Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, pentyl, is
1- to 10-carbons such as o-pentyl, sec-pentyl, hexyl, heptyl, n-octyl, isooctyl, 2-ethylhexyl, nonyl, decyl and isodecyl
Alkyl groups of More preferably, n-butyl is mentioned.

In the formula of the general formula (7), the halogen atom represented by X10 is the same as the halogen atom represented by X1 and X2 described above, and preferably,
Examples include iodine.

As a preferred embodiment of the general formula (7), R is
10 and R11 are both hydrogen atoms, R10 and R1
One of 1 is a hydrogen atom and the other one has 1 to 1 carbon atoms
The alkyl group of 0 or R10 and R11 are both a C1-C10 alkyl group, and X10 is iodine. More preferably, one of R10 and R11 is a hydrogen atom, the other is an alkyl group having 1 to 10 carbon atoms, and X10 is iodine. In particular, one of R10 and R11 is hydrogen. An atom and the other is n-butyl, X
A mode in which 10 is iodine can be mentioned.

Further, z represents an integer of 0 or 1, and when z is 0, the haloacetylene compound becomes an acid amide derivative, and when z is 1, the haloacetylene compound becomes a carbamate derivative. Among these, carbamate derivatives of haloacetylene compounds in which z is 1 are preferable.

Such a haloacetylene-based compound can be produced by a known method according to the following specific compounds. Specific examples thereof include the acid of the haloacetylene-based compound when z is 0. Examples of the amide derivative include 3-chloropropiolic acid amide and N-methyl-3.
-Chloropropiolic acid amide, N-ethyl-3-chloropropiolic acid amide, N-propyl-3-chloropropiolic acid amide, N-butyl-3-chloropropiolic acid amide, N-hexyl-3-chloro (N-substituted-) 3-chloropropiolic acid amide such as propiolic acid amide, N-octyl-3-chloropropiolic acid amide, N-cyclohexyl-3-chloropropiolic acid amide, for example, 3-bromopropyiic acid amide All acid amide, N
-Methyl-3-bromopropiolic acid amide, N-ethyl-3-bromopropiolic acid amide, N-propyl-
3-Bromopropiolic acid amide, N-butyl-3-bromopropiolic acid amide, N-hexyl-3-bromopropiolic acid amide, N-octyl-3-bromopropiolic acid amide, N-cyclohexyl-3- (N-Substituted-) 3-bromopropiolic acid amide such as bromopropiolic acid amide, for example, 3-iodopropiolic acid amide, N-methyl-3-iodopropiolic acid amide, N-ethyl-3-iodo Propiolic acid amide, N
-Propyl-3-iodopropiolic acid amide, N-butyl-3-iodopropiolic acid amide, N-hexyl-3-iodopropiolic acid amide, N-octyl-3
-Iodopropiolic acid amide, N-cyclohexyl-
(N-substituted-) such as 3-iodopropiolic acid amide
3-iodopropiolic acid amide and the like can be mentioned. Preferred is (N-substituted-) 3-iodopropiolic acid amide, and more preferred is N-butyl-3-iodopropiolic acid amide.

Further, as a carbamate derivative of a haloacetylene compound when z is 1, for example, 3-iodo-2-propynylmethyl carbamate, 3-iodo-2
-Propynyl ethyl carbamate, 3-iodo-2-propynyl propyl carbamate, 3-iodo-2-propynyl butyl carbamate, 3-iodo-2-propynyl hexyl carbamate, 3-iodo-2-propynyl octyl carbamate, 3-iodo-2 And 3-iodo-2-propynylalkylcarbamates such as propynylcyclohexylcarbamate. Of these, preferably, 3-iodo-2-propynylbutyl carbamate is used. These haloacetylene compounds may be used alone or in combination of two or more.

The phthalimide compound used in the present invention is represented by the following general formula (8).

General formula (8)

[0114]

[Chemical 42] (In the formula, both X11 and X12 represent a halogen atom, X13 represents a hydrocarbon group having a halogen atom or a halogen atom, and ring B represents a cyclohexene ring or a benzene ring.) In the formula of the general formula (8) , X11, X12 and X13 include the above-mentioned X1 and X2.
The same as the halogen atom represented by are mentioned, and preferably fluorine and chlorine are mentioned.

The hydrocarbon group of the hydrocarbon group having a halogen atom represented by X13 is the same as the hydrocarbon group of the hydrocarbon group which may have a substituent represented by R1 and R2. There are things. Preferably, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as ert-butyl, and more preferably, methyl. Also,
Examples of the halogen atom include those similar to the halogen atom represented by X1 and X2 described above, and preferably include fluorine and chlorine. Halogen atom is
For example, the hydrocarbon group is preferably substituted with 1 to 3, and among them, 2 is preferably substituted.

Examples of such a hydrocarbon group having a halogen atom include trihalomethyl, dihalomethyl, monohalomethyl, etc., preferably dihalomethyl, and more preferably dichloromethyl.

In a preferred embodiment of general formula (8), ring B is a cyclohexene ring, and X11 and X12
Are both chlorine atoms, X13 is dichloromethyl, a fluorine atom or a chlorine atom, or ring B is a benzene ring, X11 and X12 are both chlorine atoms, and X13 is a fluorine atom. Alternatively, an embodiment in which it is a chlorine atom can be mentioned.

Such a phthalimide compound can be produced by a known method according to the following specific compounds, and specific examples thereof include N-1,
1,2,2-tetrachloroethylthio-tetrahydrophthalimide (Captafol), N-trichloromethylthio-tetrahydrophthalimide (Captan),
N-dichlorofluoromethylthiophthalimide (Flu
orfolpet), N-trichloromethylthiophthalimide (Folpet) and the like. Of these, N-dichlorofluoromethylthiophthalimide (Fluorfolpet) is preferable. These phthalimide compounds may be used alone or in combination of two or more.

The haloalkylthio compound used in the present invention is represented by the following general formula (9).

General formula (9)

[0121]

[Chemical 43] (In the formula, R12 is a hydrocarbon group which may have a substituent or -N (Ra) (Rb) (Ra and Rb are the same or different and may be a hydrocarbon group which may have a substituent). Hydrogen group), X14 and X15 are both halogen atoms, X16 is a hydrocarbon group or halogen atom having a halogen atom, and Y3 is —SO ₂ — or —CONH—.
And C ring represents a benzene ring which may have a substituent. In the formula of the general formula (9), the hydrocarbon group which may have a substituent represented by R12, Ra and Rb may have a substituent which is represented by the above R1 and R2. The same thing as a hydrocarbon group is mentioned. Hydrocarbon groups having no substituents are preferable, and among them, alkyl groups are preferable. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, and the like. Preferred is methyl.

Preferred examples of R12 include, for example, an alkyl group having 1 to 4 carbon atoms or --NRR '(R, R'.
They are the same or different, an alkyl group having 1 to 4 carbon atoms), more preferably, methyl and -N _{(CH 3) 2}
Is mentioned.

In the formula of the general formula (9), X14 and X15
Examples of the halogen atom represented by are the same as the halogen atom represented by X1 and X2 described above,
Preferable is chlorine.

In the formula (9), the hydrocarbon group of the halogen-containing hydrocarbon group represented by X16 is
The same hydrocarbon group as the above-mentioned hydrocarbon group having a halogen atom represented by X13 can be used. Preferred are trihalomethyl, dihalomethyl, monohalomethyl and the like, more preferred is trihalomethyl, and especially dichlorofluoromethyl is preferred.

In the haloalkylthio compound represented by the general formula (9), the substituent of the benzene ring represented by C ring is a hydrocarbon group which may have a substituent represented by R1 and R2 described above. And the same substituents as those mentioned above. Preferably, a halogen atom, an alkyl group (eg, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t
(C1-C4 alkyl groups such as ert-butyl)
Is mentioned. These substituents may be the same or different and may be substituted by 1 to 4, preferably 1 or 2. Preferred examples of the benzene ring which may have a substituent represented by ring C include a benzene ring having no substituent, an alkyl-substituted benzene, and a halogen-substituted benzene.

As a preferred embodiment of the general formula (9), Y
3, -SO ₂ - and is, R12 is an alkyl group or -NRR 1 to 4 carbon atoms '(R, R' are the same or different, an alkyl group having 1 to 4 carbon atoms), and X14
And X15 are both chlorine atoms, X16 is dichlorofluoromethyl or a fluorine atom, and the C ring is a benzene ring or an alkyl-substituted benzene, or Y3 is -CONH- and R12 is
An alkyl group having 1 to 4 carbon atoms, X14 and X15
Are chlorine atoms, X16 is a fluorine atom, and C ring is a halogen-substituted benzene.

Such a haloalkylthio compound is
It can be produced by a known method according to the following specific compounds, and specific examples thereof include N-
Methylsulfonyl-N-phenyl- (1,1-dichloro-2,2-dichloro-2-fluoro-) ethanesulfamide, N-methyl-N'-3,4-dichlorophenyl-
N'-dichlorofluoromethylthiourea, N-dimethylaminosulfonyl-N-tolyl-dichlorofluoromethanesulfamide (Tolylfluanide), N
-Dimethylaminosulfonyl-N-phenyl-dichlorofluoromethanesulfamide (Dichlofluan)
ide) and the like. Of these, N-dimethylaminosulfonyl-N-tolyl-dichlorofluoromethanesulfamide (Tolylflua) is preferable.
Nide), N-dimethylaminosulfonyl-N-phenyl-dichlorofluoromethanesulfamide (Dich)
lofluanide). These haloalkylthio compounds may be used alone or in combination of two or more.

The pyrithione compound used in the present invention is represented by the following general formula (10).

General formula (10)

[0130]

[Chemical 44] (In the formula, M represents a metal, and n represents an integer of 1 to 4.) In the formula of the general formula (10), examples of the metal represented by M include sodium, zinc, copper, nickel, cobalt, and manganese. 1, iron, tin, titanium or magnesium, etc.
A tetravalent metal can be used. Further, n is preferably 1 to 3. As such a metal, sodium (monovalent), zinc (divalent), copper (divalent), nickel (1) is preferable.
Valent), cobalt (divalent), manganese (divalent), iron (3)
Value).

Such a pyrithione compound can be produced by a known method according to the following specific compounds, and specific examples thereof include sodium pyrithione and zinc pyrithione. These pyrithione compounds may be used alone or in combination of two or more.

The phenylurea compound used in the present invention is represented by the following general formula (11).

General formula (11)

[0134]

[Chemical formula 45] (In the formula, R13 and R14 are the same or different and each represents a hydrocarbon group or a hydrogen atom which may have a substituent which may be bonded to an adjacent nitrogen atom via an oxygen atom, X17 and X18 are the same or different and represent a halogen atom or a hydrogen atom.) In the formula of the general formula (11), a substituent which may be bonded to an adjacent nitrogen atom represented by R13 and R14 via an oxygen atom. The hydrocarbon group which may have a substituent and which may have a substituent is the same as the hydrocarbon group which may have a substituent and is represented by R1 and R2 described above. And a hydrocarbon group having no substituent is preferred. That is, R13 and R
The hydrocarbon group which may have a substituent which may be bonded to an adjacent nitrogen atom represented by 14 through an oxygen atom is preferably an alkyl group having 1 to 8 carbon atoms or 1 carbon atom. To alkenyl groups having 1 to 8 carbon atoms, alkynyl groups having 1 to 8 carbon atoms and alkoxy groups having 1 to 8 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, pentyl, iso-pentyl, sec-pentyl, Hexyl, heptyl, n-octyl, isooctyl, 2-ethylhexyl and the like can be mentioned, and more preferably, methyl can be mentioned.

Examples of the alkenyl group having 1 to 8 carbon atoms include vinyl, allyl, methallyl, isopropenyl, 1
-Propenyl, 2-propenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, butenyl, pentenyl, hexenyl, heptynyl, octenyl and the like can be mentioned, and more preferable are propenyl and isopropenyl.

Examples of the alkynyl group having 1 to 8 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, octenyl and the like, more preferably propynyl and butynyl.

Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and te.
Examples thereof include rt-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy and octyloxy, and more preferably methoxy.

In the formula (11), X17 and X1
Examples of the halogen atom represented by 8 include those similar to the halogen atom represented by X1 and X2 described above, and preferably chlorine.

As a preferred embodiment of the general formula (11),
R13 and R14 are both C1-8 alkyl groups, both C1-8 alkenyl groups, or one is a C1-8 alkyl group and the other is a C1-8 alkenyl group, carbon An embodiment is an alkynyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and both X17 and X18 are chlorine atoms, or one is a chlorine atom and the other is a hydrogen atom.

Such a phenylurea compound can be produced by a known method according to the specific compounds shown below, and specific examples thereof include 3-
(3,4-Dichlorophenyl) -1,1-dimethylurea, 3- (4-monochlorophenyl) -1,1-dimethylurea, 3- (4-monochlorophenyl) -1-methoxy-1-methylurea, 3- (4-monochlorophenyl) -1-butynyl-1-methylurea, 3- (3,4
-Dichlorophenyl) -1-methoxy-1-methylurea, 3- (3,4-dichlorophenyl) -1-methyl-
1-propenyl urea, 3- (3,4-dichlorophenyl) -1-isopropenyl-1-propynyl urea and the like can be mentioned. Of these, preferably, 3- (3,
4-dichlorophenyl) -1,1-dimethylurea may be mentioned. These phenylurea compounds may be used alone or in combination of two or more.

The triazine compound used in the present invention is represented by the following general formula (12).

General formula (12)

[0144]

[Chemical formula 46] (In the formula, R15, R16, R17 and R18 are each a hydrocarbon group which may have a substituent or a hydrogen atom,
19 represents an alkylthio group or a halogen atom. In the formula of the general formula (12), the hydrocarbon group which may have a substituent represented by R15, R16, R17 and R18 has a substituent represented by the above R1 and R2. The same as the good hydrocarbon group may be mentioned,
A hydrocarbon group having no substituent is preferred.

As the hydrocarbon group which may have a substituent represented by R15 and R16, a hydrocarbon group which does not have a substituent is preferable, and among them, an alkyl group is preferable. The alkyl group is preferably methyl,
Examples thereof include alkyl groups having 1 to 4 carbon atoms such as ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.

The hydrocarbon group which may have a substituent represented by R17 and R18 is preferably an alkyl group which may have a substituent or a cycloalkyl which may have a substituent. Groups.

The alkyl group represented by R17 and R18, which may have a substituent, is preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or sec. -Butyl,
Examples thereof include an alkyl group having 1 to 5 carbon atoms such as pentyl, iso-pentyl and sec-pentyl. In addition, examples of the substituent include the same ones as described above.

The cycloalkyl group of the cycloalkyl group represented by R17 and R18 which may have a substituent preferably has 3 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
-6 cycloalkyl groups. In addition, examples of the substituent include the same ones as described above.

In the formula (12), the alkylthio group represented by X19 is, for example, an alkylthio group having 1 to 4 carbon atoms such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio and isobutylthio. Is mentioned. Examples of the halogen atom represented by X19 include those similar to the halogen atom represented by X1 and X2 described above, and preferably chlorine.

As a preferred embodiment of the general formula (12),
R15 and R16 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R17 and R18 are unsubstituted or substituted with an alkoxy group having 1 to 4 carbon atoms and having 1 to 5 carbon atoms. Or a cycloalkyl group having 3 to 6 carbon atoms, which is unsubstituted or substituted with an alkoxy group having 1 to 4 carbon atoms, and X19 is a halogen atom or 1 to 4 carbon atoms.
And an alkylthio group of. this house,
Particularly, an embodiment in which the cycloalkyl group having 3 to 6 carbon atoms is a cyclopropyl group and X19 is chlorine, or methylthio or ethylthio is preferable.

Such a triazine compound can be produced by a known method according to the following specific compounds. Specific examples thereof include 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2-chloro-4,6-diethylamino-s-triazine and 2-chloro-4-ethyl. Amino-6-isopropylamino-s-triazine, 2-methylthio-4-ethylamino-6- (1,2-dimethylpropylamino) -s-triazine and the like can be mentioned. Of these, more preferred is 2-methylthio-4-t.
-Butylamino-6-cyclopropylamino-s-triazine. These triazine compounds may be used alone or in combination of two or more.

The triazine compound may be used as it is as a base, or may be a salt with an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid, or, for example, acetic acid, propionic acid, citric acid, It may be used as a salt with an organic acid such as paratoluenesulfonic acid.

The guanidine compound used in the present invention has the following general formula (13) and / or the following general formula (1
4).

General formula (13)

[0155]

[Chemical 47] (In formula, W shows a salt, m shows the integer of 1-30, p shows the integer of 2-8.) General formula (14).

[0156]

[Chemical 48] (In the formula, D ring represents a benzene ring which may have a substituent, and t represents an integer of 2 to 8.) In the formula of the general formula (13), the salt represented by W is, for example, , Hydrochloride, hydrobromide, sulfate, nitrate, and other inorganic acid salts such as acetate, gluconate, trichloroacetate, trifluoroacetate, methanesulfonate, p-toluenesulfonate, etc. And organic acid salts thereof.
Preferred are inorganic acid salts, and more preferred are hydrochlorides. In addition, m is an integer of 1 to 30, preferably
The integer of 5-20 is mentioned, p is the integer of 2-8, Preferably it is 4 or 6, More preferably, 6 is mentioned.

In the formula of the general formula (14), the substituent of the benzene ring represented by ring D is the same as the substituent of the hydrocarbon group which may have a substituent represented by R1 and R2. The following are listed. Preferably, a halogen atom, an alkyl group (for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,
1 to 4 carbon atoms such as sec-butyl and tert-butyl
Alkyl groups, etc.). These substituents are
The same or different one may be substituted with 1 to 4, preferably 1 or 2. A preferred embodiment of the benzene ring which may have a substituent represented by ring D is halogen-substituted benzene, more preferably chlorophenyl. Moreover, t is an integer of 2 to 8, preferably 4 or 6, and more preferably 6.

The guanidine-based compound represented by the general formula (14) may be a salt like the guanidine-based compound represented by the general formula (13). Examples of such a salt include the above-mentioned salts. The same salts as the salts of W in the general formula (13) can be mentioned.

Such a guanidine compound can be produced by a known method according to the following specific compounds. Specific examples thereof include polyhexamethylene biguanidine hydrochloride and 1,6-di- (4′-
Chlorophenyldiguanide) -hexane hydrochloride, 1,6
-Di- (4'-chlorophenyldiguanide) -hexane gluconate and the like can be mentioned. These guanidine compounds may be used alone or in combination of two or more.

The triazole compound used in the present invention has the following general formula (15) and / or the following general formula (1)
6).

General formula (15)

[0162]

[Chemical 49] (In the formula, R 19, R 20 and R 21 are the same or different and each represents a hydrocarbon group or hydrogen atom which may have a substituent, and F 1 represents an aryl group which may have a substituent or a substituent. An aralkyl group which may have a group,
q shows the integer of 1-3. ) General formula (16)

[0163]

[Chemical 50] (In the formula, R22 and R23 are the same or different and each represents a hydrocarbon group or hydrogen atom which may have a substituent, and F2 represents an aryl group or a substituent which may have a substituent. An aralkyl group which may have, q is 1
Indicates an integer of ˜3. In the general formula (15), the hydrocarbon group of the hydrocarbon group optionally represented by R 19, R 20 and R 21 has a substituent represented by R 1 and R 2 described above. The same as the good hydrocarbon group may be mentioned,
A hydrocarbon group having no substituent is preferred. Of these, an alkyl group and a cycloalkyl group are preferable. Examples of the alkyl group represented by R19, R20 and R21 include methyl, ethyl, n-propyl and iso-.
An alkyl group having 1 to 4 carbon atoms such as propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl is preferable, and methyl is particularly preferable. Also, R1
As the cycloalkyl group represented by 9, R20 and R21, cyclopropyl is preferable.

Preferred examples of R19, R20 and R21 include a hydrogen atom, an alkyl group and a cycloalkyl group, and preferred examples include R19 and R21.
A mode in which 20 and R21 are both hydrogen atoms, R19, R20 and R21 are both alkyl groups, and R19, R20 and R21 are both cycloalkyl groups, for example,
Any two of R19, R20 and R21 are alkyl groups, and the rest are cycloalkyl groups or hydrogen atoms,
Any two of R19, R20 and R21 are cycloalkyl groups, and the rest are alkyl groups or hydrogen atoms,
An embodiment in which any two of R19, R20 and R21 are hydrogen atoms and the rest are cycloalkyl groups or alkyl groups, for example, any one of R19, R20 and R21 is an alkyl group, and any one of them is An example is a cycloalkyl group in which the rest are hydrogen atoms. Of these embodiments, R19, R20 and R21
Wherein both are alkyl groups, and R19 and R2
One of 0 and R21 is an alkyl group,
An embodiment in which any one of them is a cycloalkyl group and the rest are hydrogen atoms is more preferable.

The aryl group of the aryl group which may have a substituent represented by F1 includes, for example, phenyl, tolyl, xylyl, biphenyl, naphthyl, anthryl, phenanthryl, azulenyl and the like having 6 to 6 carbon atoms.
14 aryl groups can be mentioned. In addition, examples of the aralkyl group of the aralkyl group which may have a substituent represented by F1 include benzyl, 1-phenylethyl, and 2
-Phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl, 4-phenylbutyl, diphenylmethyl and the like having 7 to 13 carbon atoms.
The aralkyl group of is mentioned. Preferred is 1-phenylethyl. Further, as the substituent of the aryl group which may have a substituent or the aralkyl group which may have a substituent, which is represented by F1, the above R 1 can be used.
And a hydrocarbon group which may have a substituent represented by R2 and the same as the substituent are exemplified, and a halogen atom is preferable. These substituents may be the same or different and may be substituted by 1 to 5, preferably 1 to 3.

Of these, the most preferred examples of the optionally substituted aryl group represented by F1 or the optionally substituted aralkyl group are halogen-substituted phenyl and halogen-substituted 1-phenyl. Examples include ethyl.

In the triazole compound represented by the general formula (15), n is preferably 1.

Further, in the triazole compound represented by the general formula (16), the hydrocarbon group which may have a substituent represented by R22 and R23 is a substituent represented by R1 and R2 described above. The same as the hydrocarbon group which may have are mentioned, and the hydrocarbon group which does not have a substituent is mentioned preferably. Of these, alkyl groups are preferred. More preferably, methyl,
Examples thereof include alkyl groups having 1 to 4 carbon atoms such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. R22 and R
Preferred examples of 23 include a hydrogen atom and an alkyl group. In a preferred embodiment, for example, R22 and R23 are both hydrogen atoms, and among R22 and R23,
One of which is a hydrogen atom and the other is an alkyl group, R
An embodiment in which both 22 and R23 are alkyl groups can be mentioned.

The aryl group optionally represented by F2 or the aralkyl group optionally substituted may be an aryl group optionally substituted by F1. Examples of the aralkyl group which may have a substituent include the same ones as described above, preferably an aryl group which may have a substituent, and more preferably a halogen-substituted phenyl. To be

In the triazole compound represented by the general formula (16), n is preferably 1.

Such a triazole compound can be produced by a known method according to the specific compounds shown below. As a specific example, for example, α−
[2- (4-chlorophenyl) ethyl] -α- (1,1
-Dimethylethyl) -1H-1,2,4-triazole-1-ethanol (conventional name: tebuconazole), 1-
[[2- (2,4-Dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1
H-1,2,4-triazole (conventional name: propiconazole), 1-[[2- (2,4-dichlorophenyl)-
1,3-Dioxolan-2-yl] methyl] -1H-
1,2,4-triazole (conventional name: azaconazole), α- (4-chlorophenyl) -α- (1-cyclopropylethyl) -1H-1,2,4-triazole-
1-Ethanol (conventional name: cyproconazole) etc. are mentioned. More preferably, α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl)-
1H-1,2,4-triazole-1-ethanol (conventional name: tebuconazole). These triazole compounds may be used alone or in combination of two or more.

The benzimidazole compound used in the present invention is represented by the following general formula (17).

General formula (17)

[0174]

[Chemical 51] (In the formula, R24 represents a hydrocarbon group or a hydrogen atom which may have a substituent, and E represents —NHCOOR25 (R2
5 represents a hydrocarbon group which may have a substituent. )
Represents a carbamate group or a thiazolyl group. In the general formula (17), the hydrocarbon group of the hydrocarbon group represented by R24, which may have a substituent, is the above-mentioned R.
Examples of the hydrocarbon group which may have a substituent represented by 1 and R2 include a hydrocarbon group which does not have a substituent. Of these, alkyl groups are preferred. The alkyl group is preferably methyl, ethyl, n-propyl, iso-propyl, n-.
Butyl, iso-butyl, sec-butyl, tert-
Examples thereof include alkyl groups having 1 to 4 carbon atoms such as butyl, with methyl being particularly preferable.

When R24 is a hydrocarbon group which may have a substituent, the benzimidazole ring may have a substituent at any of 4-position, 5-position, 6-position or 7-position. There may be mentioned an embodiment in which an optionally substituted hydrocarbon group is substituted. Further, as a mode in which R24 is a hydrogen atom, any of 4-position, 5-position, 6-position or 7-position of the benzimidazole ring is substituted with a hydrocarbon group which may have a substituent. A non-existent mode, that is, a mode in which R24 is deleted from the general formula (17) can be mentioned. R24
The most preferable embodiment of is a hydrogen atom, that is, an embodiment in which R24 is deleted from the general formula (17).

In the carbamate group represented by -NHCOOR25 represented by E, the hydrocarbon group which may have a substituent represented by R25 includes the substituents represented by R1 and R2 described above. The same as the hydrocarbon group which may have is mentioned, and the hydrocarbon group which does not have a substituent is mentioned preferably. Of these, alkyl groups are preferred. The alkyl group is preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl,
Examples thereof include alkyl groups having 1 to 8 carbon atoms such as pentyl, iso-pentyl, sec-pentyl, hexyl, heptyl, n-octyl, isooctyl and 2-ethylhexyl. More preferably, methyl and ethyl are mentioned.

Examples of the thiazolyl group represented by E include 2-thiazolyl, 4-thiazolyl and 5-thiazolyl. Preferred is 4-thiazolyl.

Such a benzimidazole compound can be produced by a known method according to the specific compounds shown below, and specific examples thereof include E = -N.
In the case of the carbamate group represented by HCOOR25, methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate and the like can be mentioned. When E is a thiazolyl group, for example, 2- (4-thiazolyl) benzimidazole and the like can be mentioned. Of these, methyl 2-benzimidazole carbamate is preferable. These benzimidazole compounds may be used alone or in combination of two or more.

The microbial control agent of the present invention comprises a bis-quaternary ammonium salt compound, an isothiazoline compound,
Nitroalcohol compounds, dithiol compounds, thiophene compounds, haloacetylene compounds, phthalimide compounds, haloalkylthio compounds, pyrithione compounds, phenylurea compounds, triazine compounds, guanidine compounds, triazole compounds, benzimidazole It can be obtained by blending at least one type of compound (hereinafter collectively referred to as active ingredient for combined use).

The combination compounds may be used alone or in combination of two or more kinds. For example, a bis quaternary ammonium salt compound and 1
Combination of two components with one combination compound, combination of three components of bis quaternary ammonium salt compound and two combination compounds, and further four components of bis quaternary ammonium salt compound and three or more combination compounds Depending on the purpose and application, such as the combinations described above, the bis-quaternary ammonium salt compound may be used as an essential active ingredient, and the combination compounds may be appropriately added alone or in combination of two or more.

Particularly preferred combinations include, for example, bis quaternary ammonium salt compounds and isothiazoline compounds, bis quaternary ammonium salt compounds and nitro alcohol compounds, bis quaternary ammonium salt compounds and dithiol compounds, bis quaternary ammonium salts. Compounds and thiophene compounds, bis quaternary ammonium salt compounds and haloacetylene compounds, bis quaternary ammonium salt compounds and triazine compounds, bis quaternary ammonium salt compounds and guanidine compounds, bis quaternary ammonium salt compounds and triazole compounds The combination of

Further, a bis quaternary ammonium salt compound,
The proportion of at least one of the combined active ingredients to be combined is:
For example, the total amount of active ingredients used in combination is 1 to 9000 parts by weight, preferably 3 to 8000 parts by weight, based on 100 parts by weight of the bis-quaternary ammonium salt compound. Also,
The compounding ratio of each combined active ingredient is 5 to 5000 parts by weight, preferably 10 to 1000 parts by weight of the isothiazoline compound with respect to 100 parts by weight of the bis-quaternary ammonium salt compound.
10 to 1000 parts by weight of nitro alcohol compound
0 parts by weight, preferably 100 to 5000 parts by weight, the dithiol compound is 5 to 5000 parts by weight, preferably
10 to 1000 parts by weight, 5 to 5 thiophene compound
000 parts by weight, preferably 10 to 1000 parts by weight, haloacetylene compound is 5 to 5000 parts by weight, preferably 10 to 1000 parts by weight, phthalimide compound is 5 to 5000 parts by weight, preferably 10 to 100 parts by weight. 1000
5 to 5000 parts by weight, preferably 10 to 1000 parts by weight, and 5 to 5000 parts by weight, preferably 10 to 1000 parts by weight of pyrithione compound.
1000 parts by weight, phenylurea compound is 5 to 50
00 parts by weight, preferably 10 to 1000 parts by weight, the triazine compound is 5 to 5000 parts by weight, preferably
10 to 1000 parts by weight, 5 to 5 parts of guanidine compound
000 parts by weight, preferably 10 to 1000 parts by weight, the triazole compound is 5 to 5000 parts by weight, preferably 10 to 1000 parts by weight, the benzimidazole compound is 5 to 5000 parts by weight, preferably 10 to 1000 parts by weight. 100
0 parts by weight.

The microbial control agent of the present invention thus obtained exhibits an excellent control effect on at least one of bacteria, fungi, yeasts and algae, and is therefore suitably used as a control agent for these.

In the microbial control agent of the present invention, a bis-quaternary ammonium salt compound and at least one active ingredient for each combination may be blended in advance and formulated into a formulation, In addition, the bis quaternary ammonium salt compound and at least one of the combined active ingredients may be individually added to the application target to act in the application target.

When the microbial control agent of the present invention is formulated, a known method can be used without particular limitation. For example, a liquid formulation (water suspension and (Including oil), paste, powder,
It may be formulated into various known dosage forms such as granules and microcapsules. Further, it may be prepared as an inclusion compound, and further prepared by supporting it on montmorillonite (such as smectites) such as layered silicate, or by adsorbing it on clay, silica, white carbon, talc or the like. Good.

Of these, for example, in order to formulate as a liquid preparation, a bis quaternary ammonium salt compound and at least one active ingredient for each combination are dissolved or dispersed in a solvent in the above-mentioned mixing ratio as appropriate. Good. More specifically,
For example, in 100% by weight of the liquid preparation, the solvent is 1 to 99.8% by weight, the bis-quaternary ammonium salt compound is 0.1 to 95% by weight, and the total amount of each combined active ingredient is 0.1 to 95% by weight. It may be mixed and dissolved or dispersed in the respective ranges. The solvent used is not particularly limited as long as it is a solvent capable of dissolving or dispersing the bis quaternary ammonium salt compound and the respective active ingredients for combined use.

Examples of such a solvent include water such as methanol, ethanol, n-propanol, and i.
Alcoholic solvents such as so-propanol, n-butanol, tert-butanol, 3-methyl-3-methoxybutanol, such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, Glycol-based solvents such as 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tripropylene glycol monomethyl ether,
For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as propylene carbonate, for example, dioxane, tetrahydrofuran, ether solvents such as ethyl ether, for example, ethyl acetate,
Ester solvents such as butyl acetate, isobutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate, dimethyl succinate, for example, benzene, toluene, xylene, methylnaphthalene, dimethylnaphthalene. Aromatic solvents such as isopropylnaphthalene, diisopropylnaphthalene, ethylbiphenyl, diethylbiphenyl and solvent naphtha, for example, carbon tetrachloride, chloroform, halogenated hydrocarbon solvents such as methylene chloride, for example, dimethylformamide, dimethylacetamide,
Examples thereof include polar solvents such as dimethyl sulfoxide, acetonitrile and N-methylpyrrolidone.

Further, an industrially used aliphatic petroleum solvent or aromatic petroleum solvent may be used. Examples of the aliphatic petroleum solvent include mineral spirits. As the aromatic petroleum solvent, commercially available products such as MSP (distillation range (° C) 90 to 120,
Specific gravity (15/4 ° C) 0.820 or more, mixed aniline point (° C) 26 or less, aromatic content (volume%) 70 or more), Superzole 100 (distillation range (° C) 95 to 111, specific gravity (15/4) ℃) 0.825, mixed aniline point (℃) 2
6.0, aromatic content (volume%) 75 or more), pegazole ARO-80 (distillation range (° C) 104 to 123, specific gravity (15/4 ° C) 0.832, mixed aniline point (° C) 2
6, aromatic content (volume%) 75.9), Swazol 10
0 (distillation range (° C) 106 to 116, specific gravity (15/4
C) 0.835, mixed aniline point (C) 24.6, aromatic content (volume%) 76.4), Swazol 200 (distillation range (C) 132 to 144, specific gravity (15/4 C) 0.8.
44, mixed aniline point (° C) 23.8, aromatic content (volume%) 80.9), MHS (distillation range (° C) 140-1)
70, specific gravity (15/4 ° C.) 0.86 to 0.88, mixed aniline point (° C.) 11 to 12, aromatic content (volume%) 98
Above), high arom 2S (distillation range (° C) 152 to 18)
7, specific gravity (15/4 ° C.) 0.816, mixed aniline point (° C.) 47 or less, aromatic content (volume%) 45 to 55),
Swazol 310 (distillation range (° C) 153-177, specific gravity (15/4 ° C) 0.817, mixed aniline point (° C) 4
3.6, aromatic content (volume%) 51.0), Superzole 150 (distillation range (° C) 153-197, specific gravity (1
5/4 ° C.) 0.815, mixed aniline point (° C.) 21.
5, aromatic content (volume%) 50 or more), Shoishi Hysol (distillation range (° C) 153-198, specific gravity (15.6 / 1)
5.6 ° C) 0.818, aromatic content (volume%) 55),
HAWS (distillation range (° C) 154-190, specific gravity (15
/ 4 ° C) 0.822, aromatic content (volume%) 50), Superzol 1500 (distillation range (° C) 155-17
1, specific gravity (15/4 ° C) 0.869, mixed aniline point (° C) 14.6, aromatic content (volume%) 98 or more), Nisseki Hysol 100 (distillation range (° C) 155 to 180,
Specific gravity (15/4 ° C.) 0.870 to 0.880, mixed aniline point (° C.) 15 or less, aromatic content (volume%) 99.0
Above), Vegasol R-100 (distillation range (° C) 156
˜174, specific gravity (15/4 ° C.) 0.874, mixed aniline point (° C.) 14, aromatic content (volume%) 96.4), Solvesso 100 (distillation range (° C.) 158 to 177, specific gravity (15 / 4 ℃) 0.870, mixed aniline point (℃) 1
4, aromatic content (volume%) 98.0), MSS (distillation range (° C) 158 to 180, specific gravity (15.6 / 15.6)
C) 0.86-0.89, mixed aniline point (C) 13-
14, aromatic content (volume%) 98 or more), SHELLS
OL A (distillation range (° C) 160 to 182, specific gravity (15
/ 4 ° C) 0.873, aromatic content (volume%) 98), Swazol 1000 (distillation range (° C) 162 to 176, specific gravity (15/4 ° C) 0.878, mixed aniline point (° C) 1
2.7, aromatic content (volume%) 99.7), Idemitsu Ipsol 100 (distillation range (° C) 162 to 179, specific gravity (1
5/4 ° C.) 0.875, mixed aniline point (° C.) 13.
5, aromatic content (volume%) 99.5 or more), Shoishi Tokusol (distillation range (° C) 162-180, specific gravity (15 /
4 ° C.) 0.881, mixed aniline point (° C.) 12.6, aromatic content (volume%) 99.99), Swazol 1500
(Distillation range (° C) 180-207 Specific gravity (15/4 ° C)
0.886, mixed aniline point (° C) 16.5, aromatic content (volume%) 98.8), Nisseki Hysol 150 (distillation range (° C) 182 to 216, specific gravity (15/4 ° C) 0.8)
87 to 0.904, mixed aniline point (° C) 17 or less, aromatic content (volume%) 99.0 or more), Superzole 1
800 (distillation range (° C) 183-208, specific gravity (15 /
4 ° C.) 0.889, mixed alinine point (° C.) 15.7, aromatic content (volume%) 99 or more), Solvesso 150 (distillation range (° C.) 185-211, specific gravity (15/4 ° C.) 0.
896, mixed aniline point (° C) 18.3, aromatic content (volume%) 97.3), Idemitsu Ipsol 150 (distillation range (° C) 186 to 205, specific gravity (15.6 / 15.6).
℃) 0.895, mixed aniline point (℃) 15.2, aromatic content (volume%) 99.5 or more), SHELLSOL
AB (distillation range (° C) 187 to 213, specific gravity (15/4
C.) 0.894, aromatic content (volume%) 99.5), pegazole R160 (distillation range (C) 191-212, specific gravity (15/4 C) 0.890, mixed aniline point (C) 1
8, aromatic content (volume%) 97.2), Swazol 18
00 (distillation range (° C) 197 to 237, specific gravity (15/4
C) 0.940, mixed aniline point (C) 14.0, aromatic content (volume%) 99.6).

Of these, water, alcohol solvents, glycol solvents, polar solvents and the like are preferable. These solvents may be used alone or in combination of two or more kinds.

Further, the microbial control agent of the present invention may be a known additive, for example, other algae and / or fungicide, a surfactant, an antioxidant, a light stabilizer, etc., depending on its purpose and use. May be added.

Examples of the other algae and / or fungicides include quaternary compounds such as hexadecyltrimethylammonium bromide, benzalkonium chloride, di-n-decyl-dimethylammonium chloride and 1-hexadecylpyridinium chloride. Ammonium salt compounds,
For example, diiodomethyl-p-toluyl sulfone, p-
Organic iodine compounds such as chlorophenyl-3-iodopropargylformal, for example, thiocarbamate compounds such as tetramethylthiuram disulfide, and nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile, for example , 2, 3, 5, 6-
Pyridine compounds such as tetrachloro-4- (methylsulfonyl) pyridine, for example, benzothiazole compounds such as 2- (4-thiocyanomethylthio) benzothiazole, for example, 3-benzo [b] thien-2-yl- 5,6-dihydro-1,4,2-oxathiazine-4
And oxathiazine compounds such as oxide.

These other algae and / or fungicides may be used alone or in combination of two or more. Further, the blending ratio of these is appropriately determined depending on the dosage form, purpose and use.

Examples of the surface active agent include known surface active agents such as soaps, nonionic surface active agents, anionic surface active agents, cationic surface active agents, amphoteric surface active agents, polymeric surface active agents, and the like. An activator can be used, and preferably, a nonionic surfactant and an anionic surfactant are used.

Examples of nonionic surfactants include:
Polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, alkylalkanolamide, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid Examples thereof include esters and glycerin fatty acid esters.

More specifically, as polyoxyethylene alkyl ether and polyoxyethylene alkyl allyl ether, for example, polyoxyethylene lauryl ether (Emulgen (manufactured by Kao Corporation, the same applies hereinafter) 104
P, Emulgen 105, Emulgen 106, Emulgen 108, Emulgen 109P, Emulgen 120, Emulgen 123P, Emulgen 147, Emulgen 130
K), for example, polyoxyethylene cetyl ether (Emulgen 210P, Emulgen 220), for example, polyoxyethylene stearyl ether (Emulgen 306
P, Emulgen 320P), for example, polyoxyethylene oleyl ether (Emulgen 404, Emulgen 4
08, Emulgen 409P, Emulgen 420, Emulgen 430), for example, polyoxyethylene higher alcohol ether (Emulgen 705, Emulgen 707,
Emulgen 709), for example, polyoxyethylene octyl phenyl ether (Emulgen 810, Emulgen 840S), for example, polyoxyethylene nonyl phenyl ether (Emulgen 903, Emulgen 904, Emulgen 905, Emulgen 906, Emulgen 90).
9, Emulgen 910, Emulgen PI-20T, Emulgen 911, Emulgen 913, Emulgen 920,
Emulgen 930, Emulgen 931, Emulgen 93
5, Emulgen 950, Emulgen 985) and the like.

As the polyoxyethylene derivative and sorbitan fatty acid ester, for example, polyoxyethylene derivative (Emulgen A-60, Emulgen A-9
0, Emulgen A-500, Emulgen B-66, Emulgen L-40), for example, sorbitan monolaurate (Leodol (Kao Corporation, the same applies hereinafter) SP-L10),
For example, sorbitan monopalmitate (Leodoll SP
-P10), for example sorbitan monostearate (Reodol SP-S10), for example sorbitan tristearate (Reodol SP-S30), for example sorbitan monooleate (Reodol SP-O10), for example sorbitan trioleate (Reodol). SP-O3
0), for example, sorbitan monolaurate (Reodol Super SP-L10), for example sorbitan monostearate (Reodol Super SP-S10), for example sorbitan monostearate (Reodol AS-1.
0), for example, sorbitan monooleate (Reodol AO-10), for example, sorbitan sesquioleate (Reodol AO-15), for example, sorbitan monolaurate (Emazole (Kao, hereinafter the same) L-10).
(F)), for example sorbitan monopalmitate (Emazole P-10 (F)), for example sorbitan monostearate (Emazole S-10 (F)), for example sorbitan monooleate (Emazole O-10 (F). )),
For example, sorbitan monolaurate (Emazole Super L-10 (F)), for example, sorbitan monostearate (Emazole Super S-10 (F)), for example,
Sorbitan sesquioleate (Emazole O-15
R), for example, sorbitan distearate (Emazole S-20) and the like.

Examples of the polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and alkylalkanolamide include, for example, polyethylene glycol monolaurate (Emanone (manufactured by Kao Corporation, the same applies hereinafter) 1112), for example, polyethylene glycol monostearate ( Emanone 3199), for example polyethylene glycol distearate (Emanone 329
9), for example, polyethylene glycol distearate (Emanone 3299R), for example, polyethylene glycol monooleate (Emanone 4110), for example, polyoxyethylene alkylamine (Amate (manufactured by Kao, hereinafter the same) 105, Amate 320), For example, polyoxyethylene hydrogenated castor oil (Emanon CH
-25, Emanone CH-40, Emanone CH-60
(K), Emanone CH-80), for example, alkyl alkanolamide (Aminone (manufactured by Kao Corporation, the same applies hereinafter)
PK-02S, Aminone L-02) and the like.

Examples of polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid ester include, for example, polyoxyethylene sorbitan monolaurate (Reodol TW-L120), for example, polyoxyethylene sorbitan monolaurate ( Leo Doll TW-L106),
For example, polyoxyethylene sorbitan monopalmitate (Reodol TW-P120), for example, polyoxyethylene sorbitan monostearate (Reodol TW
-S120), for example polyoxyethylene sorbitan monostearate (Reodol TW-S106), for example polyoxyethylene sorbitan tristearate (Reodol TW-S320), for example polyoxyethylene sorbitan monooleate (Reodol TW-O).
120), for example polyoxyethylene sorbitan monooleate (Reodol TW-O106), for example polyoxyethylene sorbitan trioleate (Reodol TW-O320), for example polyoxyethylene sorbitan monolaurate (Reodol Super TW-L1).
20), for example polyoxyethylene sorbitan monostearate (Reodol Super TW-S120), for example polyoxyethylene sorbitan monooleate (Reodol Super TW-O120), for example polyoxyethylene sorbitan monooleate (Emazole O −
105R), for example, polyoxyethylene sorbitol tetraoleate (Reodol 430, Rhedol 44
0, rheodol 460), for example glycerol monostearate (Reodol MS-50), for example glycerol monostearate (Reodol MS-60), for example glycerol monooleate (Reodol MO-).
60), for example self-emulsifying glycerol monostearate (Reodol MS-165), for example glycerol monooleate (Emazole MO-50), for example
Molecularly distilled monoglyceride stearin system (EXCEL (manufactured by Kao Corporation, the same applies hereinafter) T-95), for example, molecularly distilled monoglyceride vegetable stearin system (EXCEL VS-9
5) For example, molecularly distilled monoglyceride vegetable olein system (Exel O-95R), for example, medium purity monoglyceride stearin system (Exel 150), for example, medium purity monoglyceride stearine olein system (Excel 200), for example, medium purity monoglyceride. Oleine-based (Exel 300), for example, medium-purity monoglyceride stearin-based (Exel 84), for example, medium-purity monoglyceride olein-stearin-based (Exel 12)
2) For example, medium-purity monoglyceride self-emulsifying stearin type (Excel P-40S), for example, medium-purity monoglyceride olein stearin type (Excel P-4).
0) and the like.

Examples of anionic surfactants include:
Examples thereof include alkylbenzene sulfonic acid metal salts, alkylnaphthalene sulfonic acid metal salts, polycarboxylic acid type surfactants, dialkyl sulfosuccinic acid ester metal salts, polyoxyethylene distyrenated phenyl ether sulfate ammonium salts, and lignin sulfonic acid metal salts. Examples of these metal salts include sodium salt, potassium salt, magnesium salt and the like.

As the antioxidant, for example, 2,
6-di-t-butyl-4-methylphenol, 2,2 '
-Phenolic antioxidants such as methylenebis [4-methyl-6-t-butylphenol], for example, amine antioxidants such as alkyldiphenylamine and N, N'-di-s-butyl-p-phenylenediamine. Can be mentioned.

These surfactants and antioxidants are
For example, in the case of a liquid agent, 0.1 to 5 parts by weight is added to 100 parts by weight of the liquid agent.

Examples of the light stabilizer include hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.

For example, in the case of a liquid agent, such a light stabilizer is added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the liquid agent.

The microbial control agent of the present invention thus obtained has excellent antibacterial, antifungal, antiseptic and antialgal action.
As a control agent against bacteria, fungi, yeasts, algae, etc., a synergistic effect of a bis quaternary ammonium salt compound and a combined active ingredient can be exhibited.

Therefore, for example, various industrial waters such as a pulp and paper mill and a cooling water circulation process, an oil agent for metal processing such as cutting oil, casein, starch paste, glue, coated paper, coating liquid for paper, surface size Effectively used in the control of harmful microorganisms such as agents, paints, adhesives, synthetic rubber latex, inks, polyvinyl alcohol films, vinyl chloride films, resin products, cement admixtures, sealants, joint products, and other industrial products. be able to.

More specifically, for example, slime control agents for paper pulp mills, antiseptics for oils for metalworking, antiseptic agents for paints, antifungal agents for resin emulsions, antiseptics for cement admixtures, It is preferably used as an industrial harmful microbial control agent such as an antiseptic / antifungal agent for ink, an antiseptic / antifungal agent for dampening water, an antiseptic / antifungal agent for cement water reducing agents, a plant life-prolonging agent, and a wood preservative.

The amount of the microbial control agent of the present invention to be added may be appropriately determined depending on the application target thereof.
It can be used as a concentration of 1 to 8000 mg (total active ingredient) / kg (product), preferably 5 to 5000 mg (total active ingredient) / kg (product).

The microbial control agent of the present invention has a pH of
3 to 13, preferably 4 to 12 can be used, and further, for example, SO ₂ ²⁻ , S
Its effect even in the presence of a reducing agent such as O ₃ ²⁻ , HSO ₂ ⁻ , HSO ₃ ⁻ , S ₂ O ₃ ²⁻ , preferably SO ₃ ²⁻ , HSO ₃ ⁻ , S ₂ O ₃ ^2−. Can be effectively expressed. The concentration of the reducing agent in this case is preferably, for example, 1 to 10000 ppm in the product.

[0209]

EXAMPLES The present invention will be described more specifically with reference to the following examples.

The abbreviations of the active ingredients used in the following examples are shown below.

HMDP-Br: N, N'-hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide) HMDP-Ac: N, N'-hexamethylenebis (4-
Carbamoyl-1-decylpyridinium acetate) MIT: 2-methyl-4-isothiazolin-3-one MITs: 2-methyl-4-isothiazolin-3-one 6% by weight and 5-chloro-2-methyl-4-isothiazolin Mixture with 20% by weight of 3-one OIT: 2-n-octyl-4-isothiazoline-3-
ON BIT: 1,2-benzisothiazolin-3-one DBNE: 2,2-dibromo-2-nitro-1-ethanol BNPD: 2-bromo-2-nitropropane-1,3-
Diol IPBC: 3-Iodo-2-propynylbutyl carbamate A3: N-dichlorofluoromethylthiophthalimide A4s: N-dimethylaminosulfonyl-N-phenyl-dichlorofluoromethanesulfamide ZPT: Zinc pyrithione DCMU: 3- (3,4- Dichlorophenyl) -1,1
-Dimethylurea Irg1071: 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine IB: polyhexamethylene biguanidine hydrochloride CH: 1,6-di- (4'-chlorophenyldiguanide ) -Hexane hydrochloride tebuconazole: α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,
2,4-triazole-1-ethanol MBC: methyl 2-benzimidazole carbamate TeCS: 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide DCDT: 4,5-dichloro-1,2-dithiol -3
-One, propiconazole: 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolane-
2-yl] methyl] -1H-1,2,4-triazole (1) Formulation Example Formulation 1 (5 wt% DBNE solution) Dibunilol A-75 (DBNE: 75 wt%, manufactured by KAI KASEI Co., Ltd.) 6.67 g Methyl carbitol (diethylene glycol monomethyl ether, the same applies hereinafter) 93.
Add 33 g and stir at room temperature to dissolve
00 g of formulation was obtained.

Formulation 2 (5% by weight BNPD solution) 5.1 g of Myaside AS (BNPD: 98% by weight, manufactured by Nagase & Co., Ltd.) was added to 94.9 g of methyl carbitol.
100 g of formulation was obtained by stirring and dissolving at room temperature.

Formulation 3 (5% by weight MITs solution) 19.23 g of Caisson LX SF25 (MITs: 26% by weight, manufactured by Rohm and Haas Co.) was added to 80.77 g of methyl carbitol, and dissolved by stirring at room temperature. , 100 g of formulation was obtained.

Formulation 4 (5% by weight BIT solution) 6.25 g of Proxel Press Paste D (BIT: 80% by weight, manufactured by Avicia) was added to methylcarbitol 93.7.
Add 5 g and stir at room temperature to dissolve
0 g of formulation was obtained.

Formulation 5 (5% by weight MIT solution) 10 g of Codec 50C (MIT: 50% by weight, manufactured by Rohm and Haas) was added to 90 g of methyl carbitol, and dissolved by stirring at room temperature to obtain 100 g of the formulation. Obtained.

Formulation 6 (5 wt% HMDP-Br solution) 5.05 g of dimer 38 (HMDP-Br: 99 wt%, manufactured by Inui) was added to 94.95 g of propylene glycol, and dissolved by stirring at room temperature. , 100 g of formulation was obtained.

Preparation 7 (5% by weight A3 solution) 5.1 g of Preventol A3 (A3: 98% by weight, manufactured by Bayer) was added to 94.9 g of methyl carbitol.
100 g of formulation was obtained by stirring and dissolving at room temperature.

Formulation 8 (5% by weight A4s solution) 5.1 g of Preventol A4s (A4s: 98% by weight, manufactured by Bayer) was added to 94.9 g of methyl carbitol, and dissolved by stirring at room temperature to give 100 g. A formulation of

Formulation 9 (5 wt% ZPT solution) 5.1 g of ZPT (ZPT: 98 wt., Manufactured by Yoshitomi Fine Chemical Co., Ltd.) was added to 94.9 g of N-methylpyrrolidone, and dissolved by stirring at room temperature to give 100 g of 100 g. A formulation was obtained.

Formulation 10 (5 wt% DCMU solution) 5.1 g of Preventol A6 (DCMU: 98 wt%, manufactured by Bayer) was added to 94.9 g of methyl carbitol, and dissolved by stirring at room temperature to give 100 g. A formulation of

Formulation 11 (5 wt% Irg1071 solution) Irgalol 1071 (Irg1071: 98 wt%,
Ciba Specialty Chemical Co., Ltd. 5.1 g was added to methyl carbitol 94.9 g and dissolved by stirring at room temperature to obtain 100 g of a preparation.

Formulation 12 (5% by weight IB solution) Proxel IB (IB: 20% by weight, manufactured by Abyssia) 2
5 g was added to 75 g of water and dissolved by stirring at room temperature to obtain 100 g of the preparation.

Formulation 13 (2 wt% HMDP-Br + 3 wt% BIT solution) 40 g of Formulation 6 and 60 g of Formulation 4 were mixed to obtain a formulation.

Formulation 14 (2.5 wt% HMDP-Br +
2.5 wt% ZPT solution) 50 g of Formulation 6 and 50 g of Formulation 9 were mixed to obtain a formulation.

Formulation 15 (2.5 wt% HMDP-Br +
2.5 wt% A3 solution) 50 g of Formulation 6 and 50 g of Formulation 7 were mixed to obtain a formulation.

Formulation 16 (2.5 wt% HMDP-Br +
2.5 wt% A4s solution) 50 g of Formulation 6 and 50 g of Formulation 8 were mixed to obtain a formulation.

Formulation 17 (1 wt% HMDP-Br + 4 wt% DCMU solution) 20 g of Formulation 6 and 80 g of Formulation 10 were mixed to obtain a formulation.

Formulation 18 (1.5 wt% HMDP-Br +
3.5 wt% Irg1071 solution) 30 g of Formulation 6 and 70 g of Formulation 11 were mixed to obtain a formulation.

Formulation 19 (1.5 wt% HMDP-Br +
3.5 wt% IB solution) 1.51 g of dimer 38 (HMDP-Br: 99 wt%, manufactured by Inui) and Proxel IB (IB: 20 wt%, manufactured by Avicia) 17.5 g of propylene glycol 80. In addition to 99 g, 100 g of a formulation was obtained by stirring and dissolving at room temperature.

Formulation 20 (5% by weight IPBC solution) 5.1 g of Troysan Polyphase P-100 (IPBC: 98% by weight, manufactured by Troy Chemical Co.) was added to 94.9 g of methyl carbitol and dissolved by stirring at room temperature. By doing so, 100 g of the preparation was obtained.

Formulation 21 (5% by weight OIT solution) 5.1 g of Sonnen 0/100 (OIT: 98% by weight, manufactured by Chemiclea) was added to 94.9 g of methyl carbitol, and dissolved by stirring at room temperature. 100 g of formulation was obtained.

Formulation 22 (5% by weight MBC solution) 5.1 g of MBC (MBC: 98% by weight, manufactured by Yoshitomi Fine Chemical Co., Ltd.) and 0.5 g of concentrated hydrochloric acid were added to 94.4 g of methyl carbitol and stirred at room temperature. Then, 100 g of the preparation was obtained by dissolving.

Formulation 23 (5% by weight tebuconazole solution) 5.1 g of tebuconazole (tebuconazole: 98% by weight, manufactured by Bayer) was added to 94.9 g of methylcarbitol, and dissolved by stirring at room temperature to prepare 100 g of the formulation. Got

Formulation 24 (2 wt% HMDP-Br + 3 wt% IPBC solution) 40 g of Formulation 6 and 60 g of Formulation 20 were mixed to obtain a formulation.

Formulation 25 (2 wt% HMDP-Br + 3 wt% OIT solution) 40 g of Formulation 6 and 60 g of Formulation 21 were mixed to obtain a formulation.

Formulation 26 (1.5 wt% HMDP-Br +
3.5 wt% MBC solution) 30 g of Formulation 6 and 70 g of Formulation 22 were mixed to obtain a formulation.

Formulation 27 (1.5 wt% HMDP-Br +
3.5 wt% tebuconazole solution) 30 g of Formulation 6 and 70 g of Formulation 23 were mixed to obtain a formulation.

Formulation 28 (2.5 wt% HMDP-Br +
2.5 wt% TeCS solution) 50 g of Formulation 6 and 12.5 g of Sulacarb (TeCS: 20 wt%, Takeda Pharmaceutical Co., Ltd.) are added to 37.5 g of propylene glycol, and dissolved by stirring at room temperature. Gave 100 g of the formulation.

Formulation 29 (2.5 wt% HMDP-Br +
2.5 wt% DCDT solution) 50 g of Formulation 6 and 2.5 g of RYH-86 (DCDT: 100 wt%, manufactured by Yoshitomi Fine Chemical Co., Ltd.) are added to 47.5 g of propylene glycol, and dissolved by stirring at room temperature. This gave 100 g of formulation.

Formulation 30 (2.5 wt% HMDP-Br +
2.5 wt% propiconazole solution) 50 g of Formulation 6 and 2.5 g of propiconazole (propiconazole: 100 wt%, manufactured by Janssen) are added to 47.5 g of methyl carbitol and stirred at room temperature. Then, 100 g of the preparation was obtained by dissolving.

Formulation 31 (5 wt% HMDP-Ac solution) 5.05 g of dimer 38A (HMDP-Ac: 99 wt%, manufactured by Inui) and 94.95 g of propylene glycol.
In addition to 100g by stirring and dissolving at room temperature
A formulation of

Formulation 32 (2.5 wt% HMDP-Ac +
2.5 wt% MIT solution) 50 g of the formulation 31 and 50 g of the formulation 5 were mixed to obtain a formulation.

Formulation 33 (10 wt% HMDP-Ac solution) 10.1 g of dimer 38A (HMDP-Ac: 99 wt%, manufactured by Inui) was added to 89.9 g of propylene glycol, and dissolved by stirring at room temperature. , 100 g of formulation was obtained.

Formulation 34 (5 wt% HMDP-Ac + 5 wt% IB solution) 50 g of Formulation 33 and 25 g of Proxel IB (IB: 20 wt%, Abyssia) are added to 25 g of water and dissolved by stirring at room temperature. This gave 100 g of formulation.

Formulation 35 (5 wt% HMDP-Ac + 5 wt% CH solution) 50 g of Formulation 33 and chlorohexidine hydrochloride (CH: 9)
5.1 g (9% by weight, manufactured by Mutual Pharmaceutical Co., Ltd.) was added to 44.9 g of methyl carbitol, and dissolved by stirring at room temperature to obtain 100 g of a preparation.

Formulation 36 (10 wt% IB solution) Proxel IB (IB: 20 wt%, Abyssia) 5
0 g was added to 50 g of water and dissolved by stirring at room temperature to obtain 100 g of a preparation.

Formulation 37 (10% by weight CH solution) 10.1 g of chlorohexidine hydrochloride (CH: 99% by weight, manufactured by Mutual Pharmaceutical Co., Ltd.) was added to 89.9 g of methyl carbitol, and dissolved by stirring at room temperature. , 100 g of formulation was obtained.

(2) Antibacterial test Predetermined as the active ingredient concentration by the binary dilution method, the formulation 6 is an essential component (component A) and the formulations 1 to 5 are combined components (B component) in a glucose-broth liquid medium. Was added so as to have a concentration of. Furthermore, pre-cultured cells, namely Serratia marcescens (Serrat
ia marcescens: IFO 3735), E. coli (IFO
3044), Pseudomonas aeruginosa (Pseudo)
monas aeruginosa: IFO 3080), 10 ³ cf
It was adjusted to u / mL and added to this liquid medium. Then, after static culture at 37 ° C. for 24 hours, the binary minimum inhibitory concentration (TDMIC) was determined by the presence or absence of growth by a turbidimeter (OD630 nm), and the synergistic index FICin
dex (Fractional concentrat
ion index). The results are shown in Table 1.

The FIC index was calculated by the following formula.

FICindex = a / a₀+ B / b₀ a₀: Single MIC of component A, b₀: Single component MIC of B component a: MIC of A component when A component + B component are used together b: MIC of B component when A component + B component are used together Then, the calculated FICindex has the following effects.
Show.

[0251] FICindex> 1 antagonism FICindex = 1 Additive action FICindex <1 synergistic action

[0252]

[Table 1] (2) The algae control test formulations 6, 10 to 12, and 17 to 19 were subjected to the multiple dilution method using Allen agar medium, and the algae shown in Table 2 were used.
Cultivated under light irradiation at ℃ for 2 weeks, the minimum inhibitory concentration (MI
C: μg / mL) was determined. The results are shown in Table 2.

[0253]

[Table 2] (3) Hello test broth (GB medium) agar medium, 1% by weight of the precultured culture solution (staphylococcus aureus (IFO 3061) adjusted to OD 660 nm: 0.2) to the agar medium. It mixed at the density which becomes.

Formulations 6, 4, 7-9, 21, 13-1
Acetone solution of 6, 25 (active ingredient concentration 100 ppm,
500 ppm) was prepared, the filter paper was immersed in this acetone solution for 2 hours, and then the filter paper was air dried for 24 hours.

The agar medium was transferred to a Petri dish, and the filter paper (3 cm) prepared above was placed in the center of the Petri dish agar medium.
(φ, circle) was placed, static culture was performed at 32 ° C. for 2 days, and the inhibition circle (mm) was measured. The results are shown in Table 3. In addition,
Table 3 also shows the results without addition of each formulation.
It is also shown as a control.

[0256]

[Table 3] (4) Antifungal test 1) Formulations 6, 20, 22 and 2 were applied to paints having the compositions shown in Table 4.
4, 26 and 27 were added at a concentration such that the added amount was 1% by weight.

2) No. A fixed amount of each of the obtained coating materials was applied to both sides of 2 filter papers (3 cm × 3 cm), and dried at room temperature for 24 hours to form a coating film, and a test piece was prepared.

3) A test piece was attached to the center of an agar plate obtained by pouring autoclave-sterilized glucose agar medium into a Petri dish having a diameter of 9 cm to coagulate.

4) Aspergillus niger (IFO 63
41), Cladsporium Cladsporioides (IF
O 6348), Penicillium sitonalim (IFO 6
352), Aureo Passilium pull lance (IFO
6353), Gliocladium virens (IFO 6
The mixture of 5 kinds of bacteria of 355) was sprayed on the test piece, and after static culture at 28 ° C. for 4 weeks, the following criteria were used for judgment. The results are shown in Table 5.

[0260]

[Table 4] (Mill base) Dispersant: polycarboxylic acid sodium salt (trade name: Orotan 850, manufactured by Rohm and Haas) Wetting agent: alkyl ether sulfate (trade name: Triton CF-10, manufactured by Union Carbide) Defoamer : Mixture of mineral oil and polyethylene glycol type nonionic surfactant (trade name: Nopco 8043-L, manufactured by San Nopco) Titanium white: rutile type titanium oxide (trade name: TITANI
X JR-900, manufactured by Teika) (let down) Emulsion: acrylic / styrene emulsion (trade name: Ultrasol C-62, manufactured by Ganz Kasei Co., preservative-free product) Film forming aid: 2,2 4-Trimethyl-1,3-pentanediol monoisobutyrate (trade name: CS-12, manufactured by Chisso Corporation) Defoaming agent: Mixture of mineral oil and polyethylene glycol type nonionic surfactant (Product side: Nopco 8034- L, manufactured by San Nopco Co., Ltd. Thickener: hydroxyethyl cellulose (trade name: SP-
2% by weight aqueous solution of 600, manufactured by Daicel)

[0261]

[Table 5] The judgment of Table 5 is based on the following criteria.

-: No hyphal growth is observed in the inoculated part of the sample or test piece.

+: In the inoculated part of the sample or test piece, mycelial growth is observed in an area of less than 1/3.

++: In the inoculated part of the sample or test piece, mycelial growth is observed in an area of 1/3 or more and less than 2/3.

+++: In the inoculated part of the sample or test piece, mycelial growth is observed in an area of 2/3 or more.

(5) Minimum bactericidal concentration test Escherichia coli (K12W3110) pre-cultured was adjusted to 0.001 (OD660 nm) with sterile water,
A bacterial solution was obtained. Each of the microbial control agents prepared in Formulations 33 to 37 was prepared to be an aqueous solution having various concentrations, and 0.5 mL of each aqueous solution was mixed with 0.5 mL of the bacterial solution,
After contacting with a water bath shaker at 1 ° C for 1 minute, the cells were inoculated into NB (nutrient pros) medium. Each medium,
After static culture at 37 ° C. for 24 hours, the presence or absence of proliferation was visually determined to determine the minimum bactericidal concentration (MBC). The results are shown in Table 6
Shown in.

[0267]

[Table 6]

INDUSTRIAL APPLICABILITY As described above, the microbial control agent of the present invention has excellent antibacterial, antifungal, antiseptic, antialgal action, etc. as a quaternary bis control agent against bacteria, fungi, yeast, algae, etc. A synergistic effect between the ammonium salt compound and the active ingredient for combined use can be exhibited. Therefore, for example, various industrial water such as pulp and paper mills, cooling water circulation process, oil for metal processing such as cutting oil, casein, starch paste, glue, coated paper, coating liquid for paper, surface sizing agent, paint , Adhesive, synthetic rubber latex, ink, polyvinyl alcohol film, vinyl chloride film, resin product, cement admixture,
It can be effectively used for controlling harmful microorganisms such as various industrial products such as sealing agents and jointing agents.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) A01N 43/10 A01N 43/10 Z 43/26 43/26 43/38 43/38 43/653 43/653 B C 43/68 43/68 43/80 102 43/80 102 47/12 47/12 Z 101 101 47/30 47/30 Z 47/44 47/44 55/02 55/02 B C02F 1/50 510 C02F 1/50 510A 510D 520 520K 532 532C 532D 532H 532J 532L ZAB ZAB (72) Inventor Shoji Tanaka No. 17-85, Jusohon-cho, Yodogawa-ku, Osaka-shi, Osaka 72, Takeda Pharmaceutical Co., Ltd. ) Inventor Shigeka Matsuhisa 2-12-10 Nihonbashi, Chuo-ku, Tokyo F-term in the Living Environment Company, Takeda Pharmaceutical Co., Ltd. (reference) 4H011 AA01 AA03 BA06 BB04 BB06 BB0 7 BB08 BB09 BB10 BB11 BB13 BB14 BB16 DA13 DD01 DD05 DF04

Claims (17)

[Claims] 1. A bis-quaternary ammonium salt compound represented by the following general formula (1), an isothiazoline compound represented by the following general formula (2) and / or the following general formula (3), and the following general formula (4): A nitro alcohol compound represented by the following formula, a dithiol compound represented by the following general formula (5), a thiophene compound represented by the following general formula (6), a haloacetylene compound represented by the following general formula (7), and the following general formula A phthalimide compound represented by the formula (8), a haloalkylthio compound represented by the following general formula (9), a pyrithione compound represented by the following general formula (10), and a phenylurea compound represented by the following general formula (11). Compound, triazine-based compound represented by the following general formula (12), guanidine-based compound represented by the following general formula (13) and / or general formula (14) Compounds represented by the following general formula (15) and / or the following general formula (1
A triazole compound represented by the following general formula (1)
7. A microbial control agent, which comprises at least one compound selected from the group consisting of benzimidazole compounds represented by 7). 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, R 3 and R 4
Are the same or different, a hydrocarbon group which may have a substituent, an alkoxy group which may have a substituent,
A hydroxyl group, an amino group or a hydrogen atom, R5 is
A hydrocarbon group which may have a substituent or a carbon-carbon single bond, Y1 is -NRnCO-, -CONRn.
-, -NRnCS- (Rn represents a hydrocarbon group which may have a substituent or a hydrogen atom), -COO.
-, -COS-, -O-, -S- or a carbon-carbon single bond, Y2 is -CONRn-, -NRnCO-,-.
CSNRn- (Rn represents a hydrocarbon group which may have a substituent or a hydrogen atom), -OOC-,-.
SOC-, -O-, -S- or a carbon-carbon single bond, Z is an anion, and a is an integer of 1 or 2. ) General formula (2) (In the formula, R6 is a hydrocarbon group or a hydrogen atom which may have a substituent, X1 and X2 are the same or different, and a hydrocarbon group (X1 and X2 are divalent hydrocarbon groups; And a halogen atom or a hydrogen atom.) General formula (3) (In the formula, R7 represents a hydrocarbon group or hydrogen atom which may have a substituent, and A ring represents a benzene ring which may have a substituent.) General formula (4) ] (In the formula, R8 represents a hydrocarbon group or a hydrogen atom,
Represents a hydrocarbon group having a hydroxyl group, a halogen atom or a hydrogen atom, and X3 represents a hydrocarbon group having a hydroxyl group or a halogen atom. ) General formula (5) (In the formula, X4 and X5 are the same or different and represent a halogen atom or a hydrogen atom.) General formula (6) (In the formula, X6, X7, X8 and X9 are the same or different and each represents a hydrocarbon group which may have a substituent, a halogen atom or a hydrogen atom.) General formula (7) (In the formula, R10 and R11 are the same or different and each represents a hydrocarbon group or a hydrogen atom which may have a substituent, X10 represents a halogen atom, and z represents an integer of 0 or 1.) Formula (8) (In the formula, both X11 and X12 represent a halogen atom, X13 represents a hydrocarbon group having a halogen atom or a halogen atom, and ring B represents a cyclohexene ring or a benzene ring.) General formula (9) ] (In the formula, R12 is a hydrocarbon group which may have a substituent or -N (Ra) (Rb) (Ra and Rb are the same or different and may be a hydrocarbon group which may have a substituent). Hydrogen group), X14 and X15 are both halogen atoms, X16 is a hydrocarbon group or halogen atom having a halogen atom, and Y3 is —SO ₂ — or —CONH—.
And C ring represents a benzene ring which may have a substituent. ) General formula (10): (In the formula, M represents a metal, and n represents an integer of 1 to 4.) General formula (11) (In the formula, R13 and R14 are the same or different and each represents a hydrocarbon group or a hydrogen atom which may have a substituent which may be bonded to an adjacent nitrogen atom via an oxygen atom, X17 and X18 are the same or different and each represents a halogen atom or a hydrogen atom.) General formula (12) (In the formula, R15, R16, R17 and R18 are each a hydrocarbon group which may have a substituent or a hydrogen atom,
19 represents an alkylthio group or a halogen atom. ) General formula (13): (In the formula, W is a salt, m is an integer of 1 to 30, and p is an integer of 2 to 8.) General formula (14) (In the formula, D ring represents a benzene ring which may have a substituent, and t represents an integer of 2 to 8.) General formula (15) (In the formula, R 19, R 20 and R 21 are the same or different and each represents a hydrocarbon group or hydrogen atom which may have a substituent, and F 1 represents an aryl group which may have a substituent or a substituent. An aralkyl group which may have a group,
q shows the integer of 1-3. ) General formula (16): (In the formula, R22 and R23 are the same or different and each represents a hydrocarbon group or hydrogen atom which may have a substituent, and F2 represents an aryl group or a substituent which may have a substituent. An aralkyl group which may have, q is 1
Indicates an integer of ˜3. ) General formula (17): (In the formula, R24 represents a hydrocarbon group or a hydrogen atom which may have a substituent, and E represents —NHCOOR25 (R2
5 represents a hydrocarbon group which may have a substituent. )
Represents a carbamate group or a thiazolyl group. ) 2. In the formula of the bis-quaternary ammonium salt compound represented by the general formula (1), R1 and R2 are each a carbon number of 1 to 1.
An alkyl group having 18 carbon atoms or a hydroxyalkyl group having 1 to 18 carbon atoms, R3 and R4 are hydrogen atoms,
R5 is a C2-C18 alkylene group, a phenylene group, a xylylene group, or a carbon-carbon single bond, The microorganism control agent of Claim 1 characterized by the above-mentioned. 3. R6 and R7 in the formula of the isothiazoline compounds represented by the general formulas (2) and (3).
Is an alkyl group having 1 to 8 carbon atoms or a hydrogen atom,
The microbial control agent according to claim 1 or 2, wherein X1 and X2 are both hydrogen atoms, one is a hydrogen atom, and the other is a chlorine atom or both are chlorine atoms. 4. In the formula of the nitroalcohol compound represented by the general formula (4), R8 is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and R9 is 1 to 4 carbon atoms having a hydroxyl group. Is an alkyl group, a bromine atom or a hydrogen atom, and X3 has a hydroxyl group and has 1 to 4 carbon atoms.
The microbial control agent according to any one of claims 1 to 3, which is an alkyl group, a bromine atom, or a chlorine atom. 5. A dithiol compound represented by the general formula (5), wherein X4 and X5 are both chlorine or bromine, one is hydrogen and the other is chlorine or bromine. The microorganism control agent according to any one of claims 1 to 4. 6. In the formula of the thiophene compound represented by the general formula (6), X6, X7, X8 and X9 are all chlorine atoms, or any three of them are chlorine atoms and one is a hydrogen atom. The microbial control agent according to any one of claims 1 to 5, characterized in that: 7. In the formula of the haloacetylene compound represented by the general formula (7), one of R10 and R11 is a hydrogen atom and the other is an alkyl group having 1 to 10 carbon atoms, and X10
Is an iodine atom, The microbial control agent in any one of Claims 1-6 characterized by the above-mentioned. 8. In the formula of the phthalimide compound represented by the general formula (8), X11 and X12 are both chlorine atoms, and X13 is a C1-4 alkyl having a chlorine atom and / or a fluorine atom. Group, chlorine atom or fluorine atom, The microbial control agent in any one of Claims 1-7 characterized by the above-mentioned. 9. In the formula of the haloalkylthio compound represented by the general formula (9), R12 is an alkyl group having 1 to 4 carbon atoms or -N (Ra) (Rb) (Ra and Rb are both carbon numbers. 1-4 alkyl group), X14 and X15 are both chlorine atoms, and X16 is a C1-4 alkyl group having a chlorine atom and / or a fluorine atom, a chlorine atom or a fluorine atom, The microbial control agent according to any one of claims 1 to 8, wherein the C ring is benzene, alkyl-substituted benzene, or halogen-substituted benzene. 10. A pyrithione compound represented by the general formula (10), wherein M is sodium, zinc, copper, nickel, cobalt, manganese, or iron.
The microbial control agent according to any one of claims 1 to 9. 11. A phenylurea-based compound represented by the general formula (11), wherein R13 and R14 have 1 carbon atoms.
To an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an alkynyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, wherein X17 and X18 are chlorine atoms or hydrogen atoms. The microorganism control agent according to any one of claims 1 to 10. 12. In the formula of the triazine compound represented by the general formula (12), R15 and R16 have 1 to 4 carbon atoms.
An alkyl group or a hydrogen atom of R17 and R1
8 is an alkyl group having 1 to 5 carbon atoms which may be substituted by an alkoxy group having 1 to 4 carbon atoms, or 1 to 8 carbon atoms
A cycloalkyl group having 3 to 6 carbon atoms which may be substituted by an alkoxy group having 4 carbon atoms, and X19 has 1 carbon atom.
The microbial control agent according to any one of claims 1 to 11, which is an alkylthio group or a halogen atom. 13. The guanidine compound represented by the general formula (13), wherein W is an inorganic acid salt and p is 6, wherein the guanidine compound is represented by the general formula (13). Microbial control agent. 14. In the formula of the guanidine compound represented by the general formula (14), D ring is chlorophenyl and t is 6
The microbial control agent according to any one of claims 1 to 13, wherein 15. In the formula of the triazole-based compound represented by the general formula (15), R 19, R 20 and R 21 are a hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, and F 1
Is a halogen-substituted phenyl or a halogen-substituted phenylalkyl, The microbial control agent according to any one of claims 1 to 14, wherein 16. In the formula of the triazole-based compound represented by the general formula (16), one of R22 and R23 is a hydrogen atom and the other is a hydrocarbon group having 1 to 4 carbon atoms, or both are hydrogen atoms, F2 is halogen-substituted phenyl, The microorganism control agent in any one of Claims 1-15 characterized by the above-mentioned. 17. A benzimidazole compound represented by the general formula (17), wherein R24 is a hydrogen atom and E
Is -NHCOOR25 (R25 is a C1-C8 alkyl group) or a thiazolyl group, The microbial control agent in any one of Claims 1-16 characterized by the above-mentioned.