JP5518595B2 - Industrial antiseptic and antifouling composition - Google Patents

Description

  The present invention relates to an industrial antiseptic and antifouling composition containing oxyclozanide.

  Various industrial waters such as pulp and paper mills, cooling water circulation process, coated paper, paper coating liquids, paints, adhesives, synthetic rubber latex, printing inks, plastic products, cement admixtures, sealing agents, etc. Various antiseptic and antifouling agents are used in products for the purpose of controlling harmful microorganisms. For example, in the case of water-based paints, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-hydroxymethyl Aminoethanol, 2-bromo-2-nitro-1,3-propanediol and the like are widely used (Non-Patent Document 1).

  However, for the purpose of industrial antiseptic and antifouling, it is desired to have a broad antibacterial spectrum for various microorganisms present in the environment and to exhibit antibacterial activity at a lower concentration.

  On the other hand, oxyclozanide is used as an animal parasite control agent (Patent Document 1), but antiseptic and antifouling effects on microorganisms are not known.

JP-A-48-75718

TECHNO-COSMOS 2003 Mar. Vol. 16 pp. 32-37

  Therefore, an object of the present invention is to obtain a new industrial antiseptic and antifouling composition having a broader antibacterial spectrum and better antibacterial activity.

  As a result of intensive studies to solve the above problems, the present inventors have found antibacterial and antifungal activities for oxyclozanide used as an animal drug. Furthermore, it has been found that by using oxyclozanide and a specific antibacterial compound in combination, the antibacterial spectrum is broadened and a synergistic improvement in antibacterial activity is obtained, and the present invention has been completed.

That is, the present invention relates to the following [1] to [11].
[1] An industrial antiseptic and antifouling composition containing oxyclozanide.

[2] Oxyclozanide, isothiazoline compound represented by formula (1), benzisothiazoline compound represented by formula (2), benzimidazole compound represented by formula (3), haloacetylene represented by formula (4) Industrial antiseptic and antifouling containing one or more compounds selected from the group consisting of a compound based on tetrahydrothiophene dioxide represented by formula (5) and salts thereof, and pyrithione and metal salts thereof Composition.

[Wherein, R ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. Show. ]

[Wherein, ring A ₁ represents an optionally substituted benzene ring, and Y represents a hydrogen atom or an optionally substituted hydrocarbon group. ]

[In the formula, A ₂ ring represents an optionally substituted benzene ring, and Z represents —NHCOOR ₄ (wherein R ₄ represents a hydrogen atom or an alkyl group) or a substituted group. A good 5-membered or 6-membered nitrogen-containing heterocyclic group is shown. ]

[Wherein, X represents a halogen atom, R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an optionally substituted hydrocarbon group, and m represents an integer of 0 or 1. ]

[Wherein Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same or different and each represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. ]

[3] The isothiazoline-based compound is 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazoline-3- ON, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one and 4,5-dichloro-2-n-octyl-4- The industrial antiseptic / antifouling composition according to the above [2], which is one or more selected from the group consisting of isothiazolin-3-one.
[4] The isothiazoline-based compound is selected from 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-n-octyl-4-isothiazolin-3-one The industrial antiseptic / antifouling composition according to the above [2], which is one or more selected from the group consisting of:
[5] The benzoisothiazoline-based compound is one or two selected from the group consisting of 1,2-benzisothiazolin-3-one and Nn-butyl-1,2-benzisothiazolin-3-one The industrial antiseptic and antifouling composition according to [2] above.
[6] The above, wherein the benzimidazole compound is one or more selected from the group consisting of methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate and 2- (4-thiazolyl) benzimidazole. 2] Industrial antiseptic and antifouling composition.
[7] The industrial antiseptic / antifouling composition according to the above [2], wherein the haloacetylene compound is 3-iodo-2-propynyl N-butylcarbamate.
[8] The industrial antiseptic / antifouling composition according to the above [2], wherein the tetrahydrothiophene dioxide compound is 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide.
[9] The industrial antiseptic / preventive agent according to the above [2], wherein the metal salt of pyrithione is one or more selected from the group consisting of an alkali metal salt of pyrithione and a divalent metal salt of pyrithione. Soil composition.
[10] The industrial antiseptic / antifouling composition according to the above [9], wherein the alkali metal salt of pyrithione is sodium pyrithione.
[11] The industrial antiseptic / antifouling composition according to the above [9], wherein the divalent metal salt of pyrithione is one or two selected from the group consisting of zinc pyrithione and copper pyrithione.

  According to the present invention, an industrial antiseptic and antifouling composition comprising oxyclozanide and having antibacterial activity against various microorganisms present in the environment can be obtained. In addition, by using a specific antibacterial compound in combination, the antibacterial spectrum is expanded and the antibacterial activity is synergistically improved, so that it can be used in various modes and can be used for a wide range of industrial applications. An antiseptic / antifouling composition can be obtained.

Oxyclozanide (2,2′-dihydroxy-3,3 ′, 5,5 ′, 6-pentachlorobenzanilide) is a compound represented by the following formula (6), and as an animal parasite control agent, bovine Used to combat adult liver fluke ( Fasciola sp.). This time, for the first time, it was found to have antimicrobial activity. As described later, bacteria such as Bacillus subtilis , Staphylococcus aureus , Cladosporium cladosporioides , Reobashidiumu pullulans (Aureobasidium pullulans) molds such as to have antimicrobial activity.

  In the industrial antiseptic / antifouling composition of the present invention, the oxyclozanide may be a commercially available product or may be one produced according to a known technique, but it is convenient to use a commercially available product. In order to give a good antiseptic / antifouling effect to microorganisms such as bacteria and fungi in the environment, the industrial antiseptic / antifouling composition of the present invention has an amount of 0. It is preferable to contain 1 to 40 weight%, and it is more preferable to contain 1 to 40 weight%.

  In the industrial antiseptic / antifouling composition of the present invention, in addition to the above oxyclozanide, isothiazoline compounds, benzisothiazoline compounds, benzimidazole compounds, haloacetylene compounds, tetrahydrothiophene dioxide compounds, and salts thereof And one or more antibacterial compounds selected from the group consisting of pyrithione and metal salts thereof may be used in combination. By using the antibacterial compound in combination, the antibacterial spectrum is expanded and the antibacterial activity is synergistically improved.

  The isothiazoline-based compound is represented by the following formula (1).

[Wherein, R ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. Show. ]

In the formula (1), the hydrocarbon group of the “optionally substituted hydrocarbon group” represented by R ₁ is preferably a hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon group having 1 to 14 carbon atoms. Are more preferable, and 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, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 1-methylbutyl, 1-ethylpropyl, 1,1- Dimethylpropyl, n-hexyl, isohexyl, 1-ethyl-1-methylpropyl, 2-ethylbutyl, n-heptyl, isoheptyl, 2,2-dimethylpentyl, n-octyl, isooctyl, 1-methylheptyl, 1-ethylhexyl, C1-C10 alkyl groups such as 1-propylpentyl, 1,1-dimethylhexyl, 1-ethyl-1-methylpentyl, 1,1-diethylbutyl, 2-ethylhexyl, nonyl, decyl, preferably carbon number 1-8 alkyl groups are mentioned.

  Examples of the alkenyl group include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 1-pentenyl, Examples thereof include alkenyl groups having 2 to 6 carbon atoms such as 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, and 5-hexenyl.

  Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, Examples thereof include alkynyl groups having 2 to 6 carbon atoms such as 2-hexynyl, 3-hexynyl, 4-hexynyl and 5-hexynyl.

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

  Examples of the aryl group include aryl groups having 6 to 14 carbon atoms such as phenyl, naphthyl, anthracenyl, phenanthrenyl and the like.

  Examples of the aralkyl group include aralkyl groups having 7 to 14 carbon atoms such as benzyl, phenylethyl, naphthylmethyl and the like.

  Substituents of the above-mentioned “optionally substituted hydrocarbon group” include hydroxyl groups; halogen atoms of chlorine, fluorine, bromine and iodine; cyano groups; amino groups; carboxyl groups; acetyl, propanoyl, butanoyl, hexanoyl, etc. An acyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; an aryloxy group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms such as phenoxy and naphthyloxy An aralkyloxy group having 7 to 14 carbon atoms such as benzyloxy and phenylethyloxy; an alkylthio group having 1 to 4 carbon atoms such as methylthio, ethylthio, propylthio and butylthio; an arylthio group having 6 to 20 carbon atoms such as phenylthio and the like; Can be mentioned. The said substituent of the said hydrocarbon group may be the same or different, and 1-5 pieces, Preferably 1-3 may be substituted.

As the “optionally substituted hydrocarbon group” represented by R ₁ , an unsubstituted hydrocarbon group is preferable, and among them, an alkyl group or a cycloalkyl group is preferable. As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like, and n -8 carbon atoms such as octyl, isooctyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1,1-dimethylhexyl, 1-ethyl-1-methylpentyl, 1,1-diethylbutyl, 2-ethylhexyl Are more preferable, and methyl, ethyl, n-butyl, and n-octyl are more preferable. As the cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and cyclohexyl is more preferable.

In the present invention, in the above formula (1), the group represented by R ₁ is preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. More preferably, alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-octyl, isooctyl, 1-methylheptyl, 1-ethylhexyl. More preferable are alkyl groups having 8 carbon atoms such as 1-propylpentyl, 1,1-dimethylhexyl, 1-ethyl-1-methylpentyl, 1,1-diethylbutyl, 2-ethylhexyl, methyl, ethyl, n- Butyl and n-octyl are particularly preferred.

In formula (1), examples of the halogen atom represented by R ₂ or R ₃ include fluorine, chlorine, bromine and iodine atoms, and among these, a chlorine atom is preferred.

The “optionally substituted hydrocarbon group” represented by R ₂ or R ₃ is the same as the “optionally substituted hydrocarbon group” described above for the group represented by R ₁ , but A substituted hydrocarbon group is preferable, and an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like is particularly preferable.

In the present invention, in the above formula (1), the groups represented by R ₂ and R ₃ are the same or different and each is preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom or a chlorine atom.

  Specific examples of the isothiazoline-based compound that can be used in the present invention include 2-methyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, and 2-n-octyl-4-isothiazoline-3- ON, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazoline-3- ON, 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 etc. are mentioned. Of these, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 5- Chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one and 4,5-dichloro-2-n-octyl-4-isothiazoline-3- On is preferred, with 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-n-octyl-4-isothiazolin-3-one being particularly preferred.

  In the present invention, as the isothiazoline-based compound, one or more can be selected from the group consisting of the above compounds.

  The benzoisothiazoline compound is represented by the following formula (2).

[Wherein, ring A ₁ represents an optionally substituted benzene ring, and Y represents a hydrogen atom or an optionally substituted hydrocarbon group. ]

In the formula (2), as the substituent of the “optionally substituted benzene ring” represented by A ₁ ring, a hydroxyl group; a halogen atom of chlorine, fluorine, bromine and iodine; a cyano group; an amino group; a carboxyl group; C1-C10 acyl groups such as butanoyl, octanoyl, decanoyl; C1-C4 alkoxy groups such as methoxy, ethoxy, propoxy, butoxy; C6-C20 such as phenoxy, naphthyloxy, preferably carbon numbers An aryloxy group having 6 to 10 carbon atoms; an aralkyloxy group having 7 to 14 carbon atoms such as benzyloxy and phenylethyloxy; an alkylthio group having 1 to 4 carbon atoms such as methylthio, ethylthio, propylthio and butylthio; 6 carbon atoms such as phenylthio To 20 arylthio groups, etc., including halogen atoms and methyl, ethyl, An alkyl group having 1 to 4 carbon atoms such as pill and butyl is preferable. These substituents may be the same or different, and 1 to 4, preferably 1 or 2 may be substituted on the benzene ring. The “optionally substituted benzene ring” represented by A ₁ ring is preferably an unsubstituted benzene ring.

In the formula (2), examples of the “optionally substituted hydrocarbon group” represented by Y include the same as the “optionally substituted hydrocarbon group” represented by R ₁ described above. An unsubstituted hydrocarbon group is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms (particularly n-butyl) is particularly preferred.

  In the present invention, in the formula (2), the group represented by Y is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (particularly n-butyl). Particularly preferred.

  Preferable specific examples of the benzoisothiazoline compound include 1,2-benzisothiazoline-3-one, Nn-butyl-1,2-benzisothiazoline-3-one, and the like.

  In the present invention, as the benzoisothiazoline-based compound, one or more kinds selected from the group consisting of the above compounds can be selected and used.

  The benzimidazole compound is represented by the following formula (3).

[In the formula, A ₂ ring represents an optionally substituted benzene ring, and Z represents —NHCOOR ₄ (wherein R ₄ represents a hydrogen atom or an alkyl group) or a substituted group. A good 5-membered or 6-membered nitrogen-containing heterocyclic group is shown. ]

In the above formula (3), as may be included in the "which may be substituted benzene ring" substituent represented by A ₂ ring and may be the same as the substituents of A ₁ ring above , Halogen atoms, and alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl. These substituents may be the same or different, 1 to 4 to the benzene ring represented by A ₂ ring, preferably may include one or two. As the benzene ring which may be substituted represented by A ₂ ring, a benzene ring is preferably unsubstituted.

In the group represented by —NHCOOR ₄ represented by Z in the above formula (3), examples of the alkyl group represented by R ₄ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert -Alkyl groups having 1 to 8 carbon atoms such as butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl, and among them, 1 to C carbon atoms such as methyl, ethyl, n-propyl and the like. The alkyl group of 3 is particularly preferred.

  In the formula (3), the optionally substituted 5- or 6-membered nitrogen-containing heterocyclic group represented by Z contains 1 to 4 nitrogen atoms as ring constituent atoms, or 1 to 1 A 5-membered or 6-membered monocyclic heterocyclic group containing, as a ring-constituting atom, one nitrogen atom selected from an oxygen atom and a sulfur atom in addition to two nitrogen atoms; Examples thereof include a condensed heterocyclic group in which a benzene ring or a 5-membered ring is condensed to a nitrogen-containing heterocyclic ring. The 5- or 6-membered nitrogen-containing monocyclic heterocyclic group includes pyridyl groups such as 2-pyridyl, 3-pyridyl and 4-pyridyl; thiazolyl groups such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl; 3 -Isothiazolyl groups such as isothiazolyl, 4-isothiazolyl and 5-isothiazolyl; imidazolyl groups such as 1-imidazolyl, 2-imidazolyl, 4-imidazolyl and 5-imidazolyl; pyrrolyl groups such as 1-pyrrolyl, 2-pyrrolyl and 3-pyrrolyl A pyrrolinyl group such as 2-pyrrolinyl and 3-pyrrolinyl; a furazanyl group; a pyrrolidinyl group such as 1-pyrrolidinyl, 2-pyrrolidinyl and 3-pyrrolidinyl; an imidazolidinyl group such as 2-imidazolidinyl, 4-imidazolidinyl and 5-imidazolidinyl; Pyrazolidinyl groups such as pyrazolidinyl; 5-pyrazoli A pyrazolyl group such as 2-oxazolyl, 4-oxazolyl and 5-oxazolyl; an isoxazolyl group such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl; a tetrazolyl group such as 1H-tetrazolyl and 2H-tetrazolyl; 2 -Pyrimidinyl groups such as pyrimidinyl, 4-pyrimidinyl and 5-pyrimidinyl; pyridazinyl groups such as 3-pyridazinyl and 4-pyridazinyl; pyrazinyl groups such as 2-pyrazinyl and 3-pyrazinyl; 1,2-thiazin-3-yl, 1 , 2-thiazin-4-yl, 1,3-thiazin-2-yl, 1,3-thiazin-4-yl, 1,4-thiazin-2-yl, 1,4-thiazin-3-yl, etc. Thiazinyl group; piperazinyl group such as 1-piperazinyl, 2-piperazinyl, 3-piperazinyl 1,2,3-thiadiazin-4-yl, 1,2,3-thiadiazin-5-yl, 1,2,3-thiadiazin-6-yl, 1,2,4-thiadiazin-3-yl, 1, Thiadiazinyl groups such as 3,4-thiadiazin-2-yl; 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadi Oxadiazolyl groups such as azol-5-yl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl; 1,2,3-thiadiazol-4-yl, A thiadiazolyl group such as 1,2,3-thiadiazol-5-yl; a triazolyl group such as 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl; 2-thiomorpholinyl, 3- Thiomorpholinyl, 4-thiomorpholine Thiomorpholinyl groups such as linyl, 5-thiomorpholinyl, 6-thiomorpholinyl; morpholinyl groups such as 2-morpholinyl, 3-morpholinyl, 4-morpholinyl, 5-morpholinyl, 6-morpholinyl; oxoimidazoles such as 2-oxoimidazolinyl Dinyl group; 1,2,4-triazine-3,5-dione-1-yl, 1,2,4-triazine-3,5-dione-2-yl, 1,2,4-triazine-3, A dioxotriazinyl group such as 5-dione-4-yl; a piperidyl group such as 1-piperidyl, 2-piperidyl, 3-piperidyl, 4-piperidyl; Examples of the condensed heterocyclic group include quinolyl groups such as 2-quinolyl, 3-quinolyl and 4-quinolyl; isoquinolyl groups such as 3-isoquinolyl and 4-isoquinolyl; indolyl groups such as 2-indolyl and 3-indolyl; Isoindolyl groups such as isoindol-3-yl; quinolidinyl groups such as 8-quinolidinyl; purinyl groups such as 1H-purin-6-yl and 3H-purin-6-yl; cinnolinyl groups such as 3-cinnolinyl and 5-cinnolinyl An indazolyl group such as 3-indazolyl; a pteridinyl group such as 2-pteridinyl; a phthalazinyl group such as 4-phthalazinyl; a quinazolinyl group such as 2-quinazolinyl and 4-quinazolinyl; a quinoxalinyl group such as 2-quinoxalinyl and 3-quinoxalinyl; -An indolizinyl group such as indolizinyl; Benzooxazinyl groups such as zooxazin-2-yl; phenothiazinyl groups such as 2-phenothiazinyl and 3-phenothiazinyl; phenazinyl groups such as 2-phenazinyl and 3-phenazinyl; 2-phenoxazinyl, 3-phenoxazinyl, 4- Examples include phenoxazinyl groups such as phenoxazinyl. Of the above heterocyclic groups, a 5-membered nitrogen-containing heterocyclic group is preferable, and a thiazolyl group is particularly preferable.

  Examples of the substituent of the heterocyclic ring include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; methoxy, ethoxy, n-propoxy Alkoxy groups having 1 to 4 carbon atoms such as isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy; halogen atoms such as fluorine, chlorine, bromine; hydroxyl groups; amino groups; nitro groups; mercapto groups Can be mentioned.

  The optionally substituted 5-membered or 6-membered nitrogen-containing heterocyclic group is preferably an unsubstituted 5-membered or 6-membered nitrogen-containing heterocyclic group, and is an unsubstituted 5-membered nitrogen-containing heterocyclic group. A cyclic group is more preferable, and a thiazolyl group is particularly preferable.

In the present invention, in the formula (3), the group represented by Z is a group represented by -NHCOOR ₄ (wherein R ₄ is an alkyl group having 1 to 8 carbon atoms) or an unsubstituted 5-membered group. Alternatively, a 6-membered nitrogen-containing heterocyclic group is preferable, and a group represented by -NHCOOR ₄ (wherein R ₄ is an alkyl group having 1 to 3 carbon atoms) or an unsubstituted 5-membered nitrogen-containing heterocyclic group is A group represented by -NHCOOR ₄ (wherein R ₄ is an alkyl group having 1 to 3 carbon atoms) or a thiazolyl group is particularly preferable.

  Preferable specific examples of the benzimidazole compound include methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate, 2- (4-thiazolyl) benzimidazole and the like.

  In this invention, as a benzimidazole type compound, it can select and use 1 type (s) or 2 or more types from the group which consists of said compound.

  The haloacetylene compound is represented by the following formula (4).

[Wherein, X represents a halogen atom, R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an optionally substituted hydrocarbon group, and m represents an integer of 0 or 1. ]

  In the formula (4), examples of the halogen atom represented by X include fluorine, chlorine, bromine and iodine atoms, and an iodine atom is particularly preferable.

In the formula (4), the “optionally substituted hydrocarbon group” represented by R ₅ or R ₆ is the same as the “optionally substituted hydrocarbon group” represented by R ₁ described above. Is mentioned. Among them, an unsubstituted hydrocarbon group is preferable, an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms is more preferable, an alkyl group having 1 to 10 carbon atoms is further preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. Alkyl groups are even more preferred, and n-butyl is particularly preferred.

One of R ₅ and R _{6 is} a hydrocarbon group which may be substituted, the other is preferably a hydrogen atom, and one of R ₅ and R ₆ is an alkyl group having 1 to 10 carbon atoms. More preferably, the other is a hydrogen atom, one of R ₅ and R ₆ is an alkyl group having 1 to 4 carbon atoms (particularly n-butyl), and the other is particularly preferably a hydrogen atom.

  In formula (4), m represents an integer of 0 or 1, when m is 0, the haloacetylene compound is an acid amide derivative, and when m is 1, the haloacetylene compound is a carbamate derivative. Of these, carbamate derivatives of haloacetylene compounds in which m is 1 are preferred.

  Specific examples of haloacetylene compounds include 3-chloropropiolic acid amide, N-methyl-3-chloropropiolic acid amide, N-ethyl as acid amide derivatives of haloacetylene compounds when m is 0. -3-chloropropiolic amide, N-propyl-3-chloropropiolic amide, N-butyl-3-chloropropiolic amide, N-hexyl-3-chloropropiolic amide, N-octyl-3 (N-substituted-) 3-chloropropiolic amides such as chloropropiolic amide, N-cyclohexyl-3-chloropropiolic amide; 3-bromopropiolic amide, N-methyl-3-bromopropi All acid amide, N-ethyl-3-bromopropiolic acid amide, N-propyl-3-bromopropiolic acid N-butyl-3-bromopropiolic acid amide, N-hexyl-3-bromopropiolic acid amide, N-octyl-3-bromopropiolic acid amide, N-cyclohexyl-3-bromopropiolic acid amide, etc. (N-substituted-) 3-bromopropiolic amides; 3-iodopropiolic amides, N-methyl-3-iodopropiolic amides, N-ethyl-3-iodopropiolic amides, N-propyl -3-iodopropiolic amide, N-butyl-3-iodopropiolic amide, N-hexyl-3-iodopropiolic amide, N-octyl-3-iodopropiolic amide, N-cyclohexyl-3 -(N-substituted-) 3-iodopropiolic amides such as iodopropiolic amide. Of these, (N-substituted-) 3-iodopropiolic acid amide is preferable, and N-butyl-3-iodopropiolic acid amide is more preferable.

  Further, as a carbamate derivative of a haloacetylene compound when m is 1, 3-iodo-2-propynyl N-methylcarbamate, 3-iodo-2-propynyl N-ethylcarbamate, 3-iodo-2-propynyl N -Propyl carbamate, 3-iodo-2-propynyl N-butyl carbamate, 3-iodo-2-propynyl N-hexyl carbamate, 3-iodo-2-propynyl N-octyl carbamate, 3-iodo-2-propynyl N-cyclohexyl Examples thereof include 3-iodo-2-propynyl N-alkyl carbamate such as carbamate, among which 3-iodo-2-propynyl N-butyl carbamate is preferable.

  In this invention, as a haloacetylene type compound, 1 type (s) or 2 or more types can be selected and used from the group which consists of said compound.

  The tetrahydrothiophene dioxide compound is represented by the following formula (5).

[Wherein Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same or different and each represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. ]

In formula (5), examples of the halogen atom represented by Y ₁ , Y ₂ , Y ₃ or Y ₄ include fluorine, chlorine, bromine and iodine atoms, with a chlorine atom being particularly preferred. In addition, as the “optionally substituted hydrocarbon group” represented by Y ₁ , Y ₂ , Y ₃ or Y ₄ , the “optionally substituted hydrocarbon group” represented by R ₁ described above The same thing is mentioned, Especially, C1-C4 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, are preferable.

As Y ₁ , Y ₂ , Y ₃ and Y ₄ , all of Y ₁ , Y ₂ , Y ₃ and Y ₄ are halogen atoms, or Y ₁ , Y ₂ and Y ₃ are halogen atoms and Y ₄ is It is preferably a hydrogen atom, or Y ₁ and Y ₄ are halogen atoms and Y ₂ and Y ₃ are preferably hydrogen atoms, and all of Y ₁ , Y ₂ , Y ₃ and Y ₄ are halogen atoms. More preferably, all of Y ₁ , Y ₂ , Y ₃ and Y ₄ are particularly preferably chlorine.

  Specific examples of the tetrahydrothiophene dioxide compound include 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 Of these, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide is particularly preferred.

  In the present invention, the tetrahydrothiophene dioxide-based compound can be used by selecting one or more from the group consisting of the above compounds.

  The above-mentioned isothiazoline compounds, benzisothiazoline compounds, benzimidazole compounds, haloacetylene compounds and tetrahydrothiophene dioxide compounds may be used as salts with acids in the case of basic compounds. In some cases, it may be used as a salt with a base.

  Salts with acids include salts with inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid; formic acid, acetic acid, trifluoroacetic acid, phthalic acid, fumaric acid, oxalic acid, tartaric acid, maleic acid, Examples include salts with organic acids such as citric acid, succinic acid, malic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

  As a salt with a base, a salt with an alkali metal such as sodium or potassium; a salt with an alkaline earth metal such as magnesium or calcium; an ammonium salt; a trimethylamine, triethylamine, pyridine, picoline, ethanolamine, diethanolamine or triethanolamine And salts with organic amines such as ethylenediamine, 1,6-hexamethylenediamine, tert-butylamine, cyclohexylamine, benzylamine, dicyclohexylamine, N, N-dibenzylethylenediamine, and the like.

  Isothiazoline compounds, benzisothiazoline compounds, benzimidazole compounds, haloacetylene compounds, tetrahydrothiophene dioxide compounds, and salts thereof may be commercially available products, or those prepared according to known techniques may be used. However, it is convenient to use a commercially available product.

  Pyrithione (1-hydroxy-1,2-dihydropyridine-2-thione) is represented by the following formula (7).

  In the antiseptic / antifouling composition of the present invention, one or more of pyrithione and a metal salt thereof can be selected and used, but a metal salt is preferably used from the viewpoint of excellent antibacterial activity. As the metal salt of pyrithione, an alkali metal salt and a divalent metal salt are preferably used.

  The alkali metal salt of pyrithione is represented, for example, by the following formula (8).

[Wherein M ₁ represents an alkali metal. ]

Examples of the alkali metal salt of pyrithione include sodium pyrithione (M ₁ = Na in the above formula (8)).

  Moreover, the divalent metal salt of pyrithione is represented by the following formula (9), for example.

[Wherein M ₂ represents a divalent metal. ]

The divalent metal represented by M ₂ in the formula (9) is preferably a Group 11 metal such as zinc capable of forming a complex with pyrithione or a transition metal. Preferable examples of the divalent metal salt of pyrithione include zinc pyrithione (M ₂ = Zn) and copper pyrithione (M ₂ = Cu).

  Commercially available products may be used as the pyrithione and the metal salts thereof, or those manufactured according to known techniques may be used, but it is convenient to use commercially available products.

  When one or more selected from the above antibacterial compounds are used in combination, in order to impart a broader antibacterial spectrum and sufficient antibacterial activity to the industrial antiseptic and antifouling composition of the present invention, The content ratio of one or two or more selected from the above antibacterial compounds (the total amount of each compound when two or more compounds are used) may be 9: 1 to 1: 9 (weight ratio). Preferably, 8: 2 to 2: 8 (weight ratio) is more preferable. Further, although depending on the dosage form, application object, use environment, etc., the content of oxyclozanide is preferably 0.1% by weight to 40% by weight, and more preferably 1% by weight to 40% by weight. As content of 1 type (s) or 2 or more types selected from the antibacterial compounds (when 2 or more types are used, the total amount of each compound) is preferably 0.1% by weight to 40% by weight, and preferably 1% by weight to 40%. Weight percent is more preferred.

  The industrial antiseptic / antifouling composition of the present invention is dissolved in a solvent, or suspended or dispersed using a surfactant or a dissolution aid, etc., as a liquid agent, a suspending agent or a dispersing agent, or a surfactant. It can be emulsified with an agent and provided as an emulsion. In addition, surfactants and solid carriers can be added to provide wettable powders, flowable powders, powders, and the like.

  Examples of the solvent that can be used in the present invention include water; lower alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1, 3-butanediol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether (methyl carbitol), ethylene glycol monoethyl ether (ethyl carbitol), ethylene glycol monobutyl ether (butyl carbitol), Polyhydric alcohols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; acetone, methyl ethyl ketone, methyl alcohol Ketones such as butyl ketone and propylene carbonate; ethers such as dioxane, tetrahydrofuran and ethyl ether; ethyl acetate, butyl acetate, isobutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate Esters such as dimethyl succinate; aromatic solvents such as benzene, toluene, xylene, methylnaphthalene, dimethylnaphthalene, isopropylnaphthalene, diisopropylnaphthalene, ethylbiphenyl, diethylbiphenyl, solvent naphtha; carbon tetrachloride, chloroform, methylene chloride Halogenated hydrocarbon solvents such as: polar organic solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone, etc. Is mentioned. These solvents may be used alone or in combination of two or more. Of these solvents, water, lower alcohols and polyhydric alcohols are preferably used.

  Examples of the surfactant that can be used in the present invention include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethienonyl phenyl ether, polyoxyethylene polyoxypropylene glycol; Examples include anionic surfactants such as ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate esters, lignin sulfonates, and naphthalene sulfonate formalin condensates. . These may be used alone or in combination of two or more.

  Examples of the dissolution aid that can be used in the present invention include carboxylic acids such as capric acid and adipic acid; esters such as diisopropyl adipate, diisopropyl sebacate, isopropyl myristate, and isopropyl palmitate; higher grades such as octyldodecanol and oleyl alcohol. Examples of alcohols include amines such as monoethanolamine and diethanolamine, and these may be used alone or in combination of two or more.

  Examples of solid carriers that can be used in the present invention include minerals such as kaolin clay, attapulgite clay, bentonite, montmorillonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, and natural substances such as corn cob flour and walnut shell flour. Organic substances; synthetic organic substances such as urea; salts such as calcium carbonate and ammonium sulfate; fine powders or granules of synthetic inorganic substances such as synthetic hydrous silicon oxide.

  The industrial antiseptic / antifouling composition of the present invention is preferably prepared at 5 to 40 ° C. Mixing with a solvent or the like is preferably carried out by treatment for about 0.5 to 5 hours. Surfactant, solubilizer and solid carrier are mixed in an amount of about 0.1% to 10% by weight, 0.1% to 10% by weight and 30% to 95% by weight, respectively, based on the total amount of the composition. can do.

  In the antiseptic and antifouling composition for industrial use according to the present invention, in addition to other antibacterial and antifungal agents, algaeproofing agents, etc., as long as they do not affect the antibacterial activity, stability, safety, etc. of the composition, Additives generally used in the formulation, such as a pH adjuster, an antioxidant, a light stabilizer, and an antifoaming agent, can be added.

Industrial antiseptic / antifouling compositions containing oxyclozanide alone have good antibacterial activity against bacteria and molds. As will be described later, bacteria exhibit particularly good antibacterial activity against Gram-positive cocci such as Staphylococcus aureus , Bacillus subtilis resident in the environment, etc. , Especially good antibacterial activity against the genus Mucor, genus Cladosporium, genus Aureobasidium, genus Alternaria, etc. Show.

In the industrial antiseptic and antifouling composition containing oxyclozanide and one or more selected from the above antibacterial compounds, the antibacterial spectrum is further expanded. The bacteria Escherichia coli (Escherichia coli), Pseudomonas aeruginosa (Pseudomonas aeruginosa), Serratia (Serratia), Legionella (Legionella) genera such as gram-negative bacilli; cereus (Bacillus cereus), Clostridium (Clostridium) grams of the genus such as positive rods; against such Branhamella bacteria (Branhamella catarrhalis) gram-negative cocci, such as is observed good antibacterial activity. The fungi, Rhizopus (Rhizopus) genus (Rhizopus) Zygomycetes such as; Aspergillus (Aspergillus) genus (Aspergillus), Penicillium (Penicillium) genus (Penicillium), Acremonium (Acremonium) genus Fusarium (Fusarium) genus, Guriokura Diumu (Gliocladium) genus Trichoderma (Trichoderma) Deuteromycetes genera like; Chaetomium (Chaetomium) genus Yurochiumu (Eurotium) genus Neurospora (Neurospora) genus Ascomycetes such as (N. crassa) to such widely antimicrobial Has activity. Furthermore, Schizosaccharomyces (Schizosaccharomyces) genus, proto Mrs (Protomyces) genus taphrina (Taphrina) HaraIkuko ascomycete such genera and the like; end Mrs (Endomyces) Shinseiko ascomycete such genera and the like; Saccharomyces (Saccharomyces) genus like half of Ascomycetes; Candida (Candida) incomplete type of ascomycete yeasts genera and the like; Philo Basi di Ella (Filobasidiella) atypical Basidiomycetes genus like; Rhodotorula (Rhodotorula) genus Trichosporon (Trichosporon) genus Suporoboromisesu (Sporobolomyces ) incomplete type Basidiomycetes yeast genera and the like; Rhodosporidium di um (Rhodosporidium) genus scan poly Dio Bors (Sporidiobolus) genus, such as xanthogen Philo Mrs (Xanthophyllomyces) Basidiomycetes yeast genera such as, with respect to yeasts Also, antibacterial activity is observed.

Further, the antiseptic and antifouling composition of the present invention comprises cyanobacteria ( Cyanophyceae ), green algae ( Chlorophyceae ), green worms ( Euglenophyceae ), axle algae ( Charophyceae ), golden algae ( Chrysophyceae ), yellow green algae ( Xanthophyceae ), Since microbacteria such as diatoms ( Bacillariophyceae ) can exhibit a wide and good inhibitory action, an anti-algae effect is also expected.

  Therefore, the industrial antiseptic and antifouling composition of the present invention can be applied to various industrial waters such as paper pulp mills, cooling water circulation processes, coated papers, paper coating liquids, paints, adhesives, synthetic rubber latex, printing It can be effectively used for controlling harmful microorganisms in various industrial products such as inks, plastic products, cement admixtures, and sealing agents. More specifically, antibacterial and antifungal agents such as slime control agents for paper pulp mills and cooling water circulation processes, antibacterial and antifungal agents for paper products and resin products, paints, synthetic rubber latex, resins, inks, silicone sealants, etc. It is useful as such.

  The antiseptic and antifouling composition for industrial use of the present invention can be appropriately selected depending on the application target, the type of microorganism to be controlled (bacteria, mold, yeast, algae, etc.) and the control period. For example, when used as a slime control agent, the total amount of antibacterial components per kg of product is 0.1 mg to 500 mg, preferably 0.5 mg to 100 mg. When used as a preservative, 1 kg of product. As a total amount of antibacterial components per 1 kg to 5,000 mg, preferably 10 mg to 1,000 mg, when used as an antifungal / yeast agent or an algal control agent, the total amount of antibacterial components per kg of product What is necessary is just to add so that it may become 10 mg-50,000 mg, Preferably, it is 100 mg-10,000 mg.

  Hereinafter, the present invention will be described in detail with reference to examples.

[Example 1]
Oxyclozanide (2,2′-dihydroxy-3,3 ′, 5,5 ′, 6-pentachlorobenzanilide; manufactured by Wako Pure Chemical Industries, Ltd.) was added to methyl carbitol so as to be 10% by weight, The mixture was prepared by stirring and mixing at room temperature for 30 minutes to obtain an industrial antiseptic / antifouling composition as a white suspension.

About Example 1, Example 2-28 mentioned later, and Comparative Examples 1-9, antibacterial activity was evaluated by the method shown below. In other words, as test bacteria, Bacillus subtilis IFO3513, Staphylococcus aureus IFO12732, Escherichia coli IFO3972, Pseudomonas aeruginosa IFO3080, Serratia marcescens IFO3735 in the fungi Aspergillus niger (Aspergillus niger IFO6341), blue mold (Penicillium citrinum IFO6352), Cladosporium class dos polio Lee Death (Cladosporium cladosporioides IFO6348), Out Leo Basi di Umm pullulans (Aureobasidium pullulans IFO6353), Alternaria species (Alternaria sp. ), Mucor Supinessensu (Mucor spinescens IFO6071), glyceryl okra di um Birensu (Gliocladium virens IFO6355), the yeasts Rhodotorula rubra (Rhodotorula rubra IFO0907), using a Saccharomyces cerevisiae (Saccharomyces cerevisiae IFO0209), in the case of bacteria, the real Glucose broth agar medium (pH 6.0) to which each of the industrial antiseptic and antifouling compositions of Examples and Comparative Examples was added was inoculated with a bacterial suspension for inoculation using a microplanter (manufactured by Sakuma Seisakusho). Cultured at 33 ° C. for 18 hours. In the case of molds and yeasts, a mold spore suspension or inoculation was carried out on a glucose broth agar medium (pH 6.0) to which the industrial antiseptic and antifouling compositions of Examples and Comparative Examples were added, respectively. The yeast suspension was inoculated, cultured at 33 ° C. for 18 hours, and further cultured at 28 ° C. for 2 days. After the cultivation, the growth of each bacterium was observed to determine the minimum inhibitory concentration (MIC) (μg / mL). The results for the industrial antiseptic / antifouling composition of Example 1 are shown in Table 1.

As is clear from Table 1, the industrial antiseptic and antifouling composition of Example 1 was 2 μg / mL and 3.9 μg / mL for Bacillus subtilis and Staphylococcus aureus , respectively. The MIC was excellent, and an excellent antibacterial activity was recognized. In addition, it shows an MIC of 125 μg / mL or less for Cladosporium cladosporioides , Aureobasidium pullulans , Alternaria sp. And Mucor spinescens . Good antibacterial activity was observed.

[Examples 2 to 28]
The composition of the industrial antiseptic / antifouling composition of Examples 2 to 28 of the present invention is shown in Table 2, and the composition of the industrial antiseptic / antifouling composition of Comparative Examples 1 to 9 is shown in Table 3. In preparing the compositions of the following examples and comparative examples, the same oxyclozanide manufactured by Wako Pure Chemical Industries, Ltd. was used.

  Examples of the isothiazoline-based compound include “ZONEN-MT” (containing 50% by weight of 2-methyl-4-isothiazolin-3-one, manufactured by Chemicrea Co., Ltd.), “Caisson LX1400” (2-methyl-4-isothiazoline-3-one And 14% by weight of a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one, manufactured by Rohm and Haas), “Caisson 893T” (2-n-octyl-4-isothiazolin-3-one 99. 5% by weight contained, manufactured by Rohm and Haas).

  As the benzoisothiazoline compound, “BIT” (containing 1,2-benzisothiazolin-3-one 80% by weight, manufactured by Dow Chemical Company) was used.

  As the benzimidazole compound, “Coatside” (containing 10% by weight of methyl 2-benzimidazole carbamate hydrochloride, manufactured by Nippon Enviro Chemicals Co., Ltd.) was used.

  As the haloacetylene compound, “IPBC” (containing 99.4% by weight of 3-iodo-2-propynyl N-butylcarbamate, manufactured by Focus) was used.

  As the tetrahydrothiophene dioxide compound, a 20% by weight diethylene glycol monomethyl ether solution (manufactured by Nippon Enviro Chemicals Co., Ltd.) of slab curve (3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide) was used.

  Further, as the metal salt of pyrithione, “Suraoff 28” (containing 40% by weight of sodium pyrithione, manufactured by Nippon Enviro Chemicals Co., Ltd.) and “Suraoff 95” (containing 50% by weight of zinc pyrithione, manufactured by Nippon Enviro Chemicals Co., Ltd.) were used. .

  The antiseptic and antifouling compositions for industrial use of Examples and Comparative Examples were prepared by adding each antibacterial compound to methyl carbitol according to the compositions shown in Tables 2 and 3 and stirring and mixing at room temperature for 30 minutes. Obtained as a white suspension or solution.

  Evaluation of antibacterial activity when oxyclozanide is used in combination with the above-mentioned predetermined antibacterial compound (Examples 2 to 28) is as follows: oxyclozanide, isothiazoline compound, benzisothiazoline compound, benzimidazole compound, haloacetylene compound, tetrahydrothiophene di From the MIC values when the oxide compounds and the metal salts of pyrithione were used alone (Example 1 and Comparative Examples 1 to 9), the theoretical values of MICs for the antiseptic and antifouling compositions of each of the above examples were as follows: Was calculated, and the actually measured MIC values were compared with them. When the measured value of MIC is smaller than the calculated value of the theoretical value, that is, when “measured value / calculated value” is smaller than 1, the antibacterial activity is greater than the algebraic sum when each of the above components is used alone. Therefore, it was evaluated that a synergistic effect was observed.

Theoretical value of MIC = C _A × x / 100 + C _B × y / 100
C _A ; MIC value when oxyclozanide is used alone (Example 1) C _B ; isothiazoline compound, benzisothiazoline compound, benzimidazole compound, haloacetylene compound, tetrahydrothiophene dioxide compound and metal of pyrithione MIC value x when each salt is used alone (Comparative Examples 1 to 9) x: proportion (% by weight) of oxyclozanide in the antibacterial component
y: Ratio of the isothiazoline compound, benzisothiazoline compound, benzimidazole compound, haloacetylene compound, tetrahydrothiophene dioxide compound or metal salt of pyrithione in the antibacterial component (% by weight)

  The evaluation results of the antibacterial activity are shown in Tables 4 to 12. “100/0”, “75/25”, “50/50”, “25/75” and “0/100” in each table are oxyclozanide, isothiazoline compound, benzoisothiazoline compound, benzimidazole The compounding weight ratio with a compound, a haloacetylene compound, a tetrahydrothiophene dioxide compound or a metal salt of pyrithione is shown. In addition, in each table below, for oxyclozanide and each of the above antibacterial compounds, when used at the above weight ratio, only test bacteria having an MIC value of less than 1000 μg / mL in at least one weight ratio are obtained. Indicated.

  Table 4 shows an industry containing oxyclozanide and 2-methyl-4-isothiazolin-3-one as isothiazoline-based compounds in weight ratios of 100: 0, 75:25, 50:50, 25:75 and 0: 100. The evaluation result about the antiseptic / antifouling composition for use (Examples 1 to 4 and Comparative Example 1) is shown.

As is apparent from Table 4, the industrial antiseptic and antifouling compositions of Examples 2 to 4 are effective antibacterial activity against bacteria and molds other than Aspergillus niger and Penicillium citrinum. showed that. For the composition of Example 4, except for the case of Cladosporium cladosporioides , the actual / calculated value of MIC was 1 for the bacteria and molds that showed antibacterial activity. The synergistic improvement of the antibacterial activity was recognized as compared with the case where oxyclozanide and 2-methyl-4-isothiazolin-3-one were each used alone (Example 1 and Comparative Example 1). In the composition of Example 4, a MIC value of 250 μg / mL was obtained for Gliocladium virens , and a synergistic improvement in antibacterial activity was observed.

  Table 5 shows a mixture of oxyclozanide and 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one as isothiazoline-based compounds at 100: 0, 75:25, The evaluation result about the industrial antiseptic / antifouling compositions (Examples 1, 5 to 7 and Comparative Example 2) contained in the weight ratios of 50:50, 25:75 and 0: 100 is shown.

As apparent from Table 5, the compositions of Examples 5 to 7 were found to have effective antibacterial activity against all test bacteria. In Examples 5 and about 6 compositions Mucor Supinessensu (Mucor spinescens), the composition of Example 7 except where against Staphylococcus aureus (Staphylococcus aureus), the MIC for each bacteria, molds and yeasts tested When the measured value / calculated value is smaller than 1, and oxyclozanide and a mixture of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one are used alone (Examples) Compared to 1 and Comparative Example 2), a synergistic improvement in antibacterial activity was observed.

  Table 6 contains oxyclozanide and 2-n-octyl-4-isothiazolin-3-one as isothiazoline-based compounds in weight ratios of 100: 0, 75:25, 50:50, 25:75 and 0: 100 The evaluation result about the industrial antiseptic / antifouling composition (Examples 1, 8 to 10 and Comparative Example 3) is shown.

As is apparent from Table 6, the compositions of Examples 8-10 have effective antibacterial activity against Bacillus subtilis and Staphylococcus aureus , and the molds and yeasts tested. Indicated. Except for the case of Mucor spinescens , the measured / calculated value of MIC is less than 1 for the test bacteria with antibacterial activity, and oxyclozanide and 2-n-octyl-4-isothiazoline-3 -A synergistic improvement in antibacterial activity was observed as compared to the cases where ON was used alone (Example 1 and Comparative Example 3).

  Table 7 shows an industrial product containing oxyclozanide and 1,2-benzisothiazolin-3-one as a benzoisothiazoline compound in a weight ratio of 100: 0, 75:25, 50:50, 25:75 and 0: 100. The evaluation result about antiseptic | preservation antifouling composition (Example 1, 11-13, and Comparative Example 4) is shown.

As is clear from Table 7, the compositions of Examples 11-13 showed effective antibacterial activity against the tested bacteria, molds and yeasts. Also, for the composition of Example 11, Aspergillus niger and Gliocladium virens , for the composition of Example 13, Bacillus subtilis and Cladosporium ( Cladosporium) Except for the case of cladosporioides ), the measured / calculated value of MIC is less than 1 for each tested bacteria, mold and yeast, and oxyclozanide and 1,2-benzisothiazolin-3-one are used alone (implementation) Compared to Example 1 and Comparative Example 4), a synergistic improvement in antibacterial activity was observed.

  Table 8 shows industrial preservatives containing oxyclozanide and methyl 2-benzimidazole carbamate hydrochloride as benzimidazole compounds in weight ratios of 100: 0, 75:25, 50:50, 25:75 and 0: 100. -The evaluation result about antifouling composition (Examples 1, 14-16, and comparative example 5) is shown.

As is apparent from Table 8, the compositions of Examples 14-16 are effective against Bacillus subtilis and Staphylococcus aureus , all molds tested, and Rhodotorula rubra. It showed antibacterial activity. In addition, for the test bacteria that showed antibacterial activity, the measured / calculated value of MIC was smaller than 1, and when oxyclozanide and methyl 2-benzimidazole carbamate hydrochloride were each used alone (Example 1 and comparison) Compared with Example 5), a synergistic improvement in antibacterial activity was observed.

  Table 9 contains oxyclozanide and 3-iodo-2-propynyl N-butylcarbamate as haloacetylene compounds in weight ratios of 100: 0, 75:25, 50:50, 25:75 and 0: 100. The evaluation result about the industrial antiseptic / antifouling composition (Examples 1, 17 to 19 and Comparative Example 6) is shown.

As can be seen from Table 9, the compositions of Examples 17-19 show antibacterial activity against Bacillus subtilis and Staphylococcus aureus , as well as all of the molds and yeasts tested. It was. Except for the case of Mucor spinescens , the measured / calculated value of MIC was less than 1 for the test bacteria with antibacterial activity, and oxyclozanide and 3-iodo-2-propynyl N-butylcarbamate were added. A synergistic improvement in antibacterial activity was observed compared to the cases where each was used alone (Example 1 and Comparative Example 6).

  Table 10 shows 100%, 75:25, 50:50, 25 of Sura curve (3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide) as an oxyclozanide and a tetrahydrothiophene dioxide-based compound. : The evaluation result about the antiseptic | preservation antifouling composition (Examples 20, 20-22, and comparative example 7) contained in the weight ratio of 75 and 0: 100 is shown.

As is apparent from Table 10, the compositions of Examples 20-22 exhibited antimicrobial activity against all fungi tested. Further, Staphylococcus aureus (Staphylococcus aureus) for the compositions of Examples 20 to 22, Au Leo Basi di um pullulans (Aureobasidium pullulans) and Mucor Supinessensu (Mucor spinescens), Alternaria sp for the compositions of Examples 20 and 21 (Alternaria sp.), Cladosporium cladosporioides for the compositions of Examples 20 and 22, and Bacillus subtilis for the composition of Example 22 As compared with the case where oxyclozanide and sura curve were used alone (Example 1 and Comparative Example 7), the synergistic improvement in antibacterial activity was observed for the yeast and yeast, where the measured / calculated value of MIC was less than 1. .

  Table 11 shows an industrial antiseptic and antifouling composition containing oxyclozanide and sodium pyrithione as metal salts of pyrithione in weight ratios of 100: 0, 75:25, 50:50, 25:75 and 0: 100 ( The evaluation result about Example 1,23-25 and comparative example 8) is shown.

As is clear from Table 11, the compositions of Examples 23 to 25 showed effective antibacterial activity against test bacteria other than Serratia marcescens . Moreover, about the composition of Examples 23-25, Staphylococcus aureus and Cladosporium cladosporioides ( Cladosporium cladosporioides ), about the composition of Example 23, Escherichia coli , Pseudomonas aeruginosa ( Pseudomonas aeruginosa ) ) And Alternaria sp., And the compositions of Examples 24 and 25, except for the case against Mucor spinescens , the measured / calculated values of MIC were measured for test bacteria with antibacterial activity. A synergistic improvement in antibacterial activity was observed as compared to the case where oxyclozanide and sodium pyrithione were each used alone (Example 1 and Comparative Example 8).

  Table 12 shows an industrial antiseptic and antifouling composition containing zinc pyrithione in a weight ratio of 100: 0, 75:25, 50:50, 25:75 and 0: 100 as oxyclozanide and a metal salt of pyrithione (implementation) The evaluation result about Example 1,26-28 and comparative example 9) is shown.

As is clear from Table 12, the compositions of Examples 26 to 28 showed effective antibacterial activity against all test bacteria. In addition, Staphylococcus aureus for the compositions of Examples 26 to 28, Serratia marcescens for the compositions of Examples 26 and 27, and Cladosporium cladosporioides (Composition of Example 26). Except for Cladosporium cladosporioides ) and Alternaria sp., And the composition of Example 27 against Mucor spinescens , the measured / calculated values of MIC for the mold, bacteria and yeast tested A synergistic improvement in antibacterial activity was observed as compared to the case where oxyclozanide and zinc pyrithione were each used alone (Example 1 and Comparative Example 9).

As described above, in the antiseptic / antifouling composition of the examples of the present invention, oxyclozanide contains bacteria such as Bacillus subtilis and Staphylococcus aureus , Cladosporium cladospouleides ( Cladosporium cladosporioides ), Aureobasidium pullulans , Alternaria sp. And Mucor spinescens, etc., were found to have antibacterial activity. Further, by using a predetermined antibacterial compound in combination, the antibacterial activity increased synergistically, and a wide range of synergistic improvements in the antibacterial activity was observed for bacteria, fungi and fungi of yeast.

  According to the present invention, there is provided an industrial antiseptic and antifouling composition that can be used for a wide range of industrial applications such as industrial water and the control of harmful microorganisms in various industrial products, and in which each of these applications has synergistically improved antibacterial activity. Can be provided.

Claims (11)

  An industrial antiseptic and antifouling composition containing oxyclozanide. Oxyclozanide, an isothiazoline compound represented by formula (1), a benzisothiazoline compound represented by formula (2), a benzimidazole compound represented by formula (3), a haloacetylene compound represented by formula (4), An industrial antiseptic / antifouling composition comprising one or more selected from the group consisting of tetrahydrothiophene dioxide compounds represented by formula (5) and salts thereof, and pyrithione and metal salts thereof.

[Wherein, R ₁ represents a hydrogen atom or an optionally substituted hydrocarbon group, and R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. Show. ]

[Wherein, ring A ₁ represents an optionally substituted benzene ring, and Y represents a hydrogen atom or an optionally substituted hydrocarbon group. ]

[In the formula, A ₂ ring represents an optionally substituted benzene ring, and Z represents —NHCOOR ₄ (wherein R ₄ represents a hydrogen atom or an alkyl group) or a substituted group. A good 5-membered or 6-membered nitrogen-containing heterocyclic group is shown. ]

[Wherein, X represents a halogen atom, R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an optionally substituted hydrocarbon group, and m represents an integer of 0 or 1. ]

[Wherein Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same or different and each represents a hydrogen atom, a halogen atom or an optionally substituted hydrocarbon group. ]   Isothiazoline-based compounds are 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 5 -Chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one and 4,5-dichloro-2-n-octyl-4-isothiazoline-3 The industrial antiseptic / antifouling composition according to claim 2, wherein the composition is one or more selected from the group consisting of ON.   The isothiazoline-based compound is selected from the group consisting of 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-n-octyl-4-isothiazolin-3-one The industrial antiseptic / antifouling composition according to claim 2, which is one or more selected.   The benzoisothiazoline-based compound is one or two selected from the group consisting of 1,2-benzisothiazolin-3-one and Nn-butyl-1,2-benzisothiazolin-3-one. 2. Industrial antiseptic and antifouling composition according to 2.   The benzimidazole compound is one or more selected from the group consisting of methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate, and 2- (4-thiazolyl) benzimidazole. Industrial antiseptic and antifouling composition.   The industrial antiseptic / antifouling composition according to claim 2, wherein the haloacetylene compound is 3-iodo-2-propynyl N-butylcarbamate.   The industrial antiseptic / antifouling composition according to claim 2, wherein the tetrahydrothiophene dioxide compound is 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide.   The industrial antiseptic / antifouling composition according to claim 2, wherein the metal salt of pyrithione is one or more selected from the group consisting of an alkali metal salt of pyrithione and a divalent metal salt of pyrithione.   The industrial antiseptic / antifouling composition according to claim 9, wherein the alkali metal salt of pyrithione is sodium pyrithione.   The industrial antiseptic / antifouling composition according to claim 9, wherein the divalent metal salt of pyrithione is one or two selected from the group consisting of zinc pyrithione and copper pyrithione.