JP4549775B2 - Microbial control agent - Google Patents

Description

  The present invention relates to a microbial control agent, and more particularly to a microbial control agent useful for wood and industrial applications.

  Conventionally, for example, various industrial products such as wood, wood product pulp, fiber, paint, adhesive, leather, paper processed products, electronic parts, wall coverings, harmful microorganisms such as bacteria, mold, yeast, algae, etc. Are prone to breeding, causing a decline in productivity, quality, and odor. Therefore, in order to sterilize such harmful microorganisms, microbial control agents having antiseptic and antifungal properties are widely used.

As such a microorganism control agent, for example, haloacetylene compounds such as 3-iodo-2-propynylmethylcarbamate are known (for example, see Patent Document 1).
Japanese Patent Laid-Open No. 10-182318

However, this haloacetylene-based compound has selectivity in the antibacterial spectrum and generally has an excellent antifungal effect, but has an insufficient antiseptic effect. Therefore, even when a haloacetylene compound is applied to an industrial product or its raw material, a microorganism (mainly a bacterium) that is not effective or hardly effective may grow and propagate.
Therefore, it has been attempted to broaden the antibacterial spectrum or increase the control effect by combining a haloacetylene compound and another microbial control agent, but even if two or more types of microbial control agents are combined, In many cases, only one type of control effect is exhibited or only an additive effect can be obtained.

In recent years, it has been desired to reduce the amount of a microorganism control agent containing a halogen atom from the viewpoint of reducing the burden on the environment.
Accordingly, an object of the present invention is to provide a novel microbial control agent that has high control performance, has a wide antibacterial spectrum, and can reduce the burden on the environment in order to solve the above problems.

As a result of intensive studies to achieve and solve the above object, when 3-iodo-2-propynylbutylcarbamate and an organic salt of a quaternary ammonium compound represented by the following general formula (2) are used in combination We found that an excellent synergistic effect was obtained, that the microbial control performance was enhanced compared to when each compound was used alone, and that a microbial control agent with a broad antibacterial spectrum was obtained, and further studies were repeated. As a result, the present invention has been completed.

That is, the present invention
(1) A microbial control agent comprising 3-iodo-2-propynylbutylcarbamate and an organic salt of a quaternary ammonium compound represented by the following general formula (2) :

One general formula (2):

(In the formula, R ³ represents an alkyl group having 12 to 16 carbon atoms. Y ₁ represents an organic anion.)
(2 ) The microorganism control according to (1 ) above, wherein in the general formula (2), the organic anion represented by Y ₁ is a free organic carboxylate ion having 1 to 4 carbon atoms. Agent,
( 3 ) The organic salt of the quaternary ammonium compound represented by the general formula (2) is N-lauryl-N-benzyl-N, N-dimethylammonium propionate, (1) Or the microorganism control agent according to (2) ,
( 4 ) The weight ratio of 3-iodo-2-propynylbutylcarbamate and the organic salt of the quaternary ammonium compound represented by the general formula (2) is in the range of 1:19 to 19: 1. The microorganism control agent according to any one of (1) to ( 3 ) above,
( 5 ) Furthermore, the microorganism control agent in any one of said (1)-( 4 ) characterized by containing a river extract.
( 6 ) The microorganism control agent according to any one of (1) to ( 4 ), further comprising a extract of extract of hakoshi,
Is to provide.

According to the microorganism control agent of the present invention, as an active ingredient, 3-iodo-2-propynylbutylcarbamate and an organic salt of a quaternary ammonium compound represented by the above general formula (2) are used in combination. By the synergistic effect, a sufficient control effect against harmful microorganisms can be exhibited, and a wide antibacterial spectrum can be obtained.
Further, according to the microorganism control agent of the present invention, the quaternary ammonium compound represented by the general formula (2) contains very little halogen atom. Combined with the fact that a sufficient control effect can be obtained even with a small amount, the halogen content of the entire microbial control agent can be reduced, and the burden on the environment can be reduced.

The microorganism control agent of the present invention contains 3-iodo-2-propynylbutylcarbamate and an organic salt of a quaternary ammonium compound represented by the above general formula (2) .

3-iodo-2-propynyl butyl carbamate, Ru can be prepared by methods publicly known.

The organic salt of the quaternary ammonium compound used in the present invention is represented by the following general formula (2).
General formula (2):

(In the formula, R ³ represents an alkyl group having 12 to 16 carbon atoms. Y ₁ represents an organic anion.)
In the general formula (2), the alkyl group of 12 to 16 carbon atoms represented by ^{R 3,} if example embodiment, dodecyl, tetradecyl, alkyl group having 12 to 16 carbon atoms, such as hexadecyl. Preferably, dodecyl is used.
In the general formula (2), the organic anion represented by Y ₁ forms a salt of an organic salt of a quaternary ammonium compound, for example, free organic carboxylic acid, free organic sulfonic acid, etc. Organic acids and the like. As a free organic acid, it is C1-C20, Preferably, C1-C10 free organic acid is mentioned.

Examples of the free organic carboxylic acid include a monovalent saturated carboxylic acid ion, a divalent saturated carboxylic acid ion, a monovalent unsaturated carboxylic acid ion, a divalent unsaturated carboxylic acid ion, a hydroxycarboxylic acid ion, and an oxocarboxylic acid. Acid ion, aromatic carboxylate ion, etc. are mentioned.
Examples of monovalent saturated carboxylate ions include formate ion (HCOO ⁻ ), acetate ion (CH ₃ COO ⁻ ), propionate ion (C ₂ H ₅ COO ⁻ ), butyrate ion (CH ₃ (CH ₂ ) ₂ ). COO ⁻ ), isobutyrate ion ((CH ₃ ) ₂ CHCOO ⁻ ), valerate ion (CH ₃ (CH ₂ ) ₃ COO ⁻ ), isovalerate ion ((CH ₃ ) ₂ CHCH ₂ COO ⁻ ), pivalic acid Ion ((CH ₃ ) ₃ CCOO ⁻ ), octanoic acid ion (CH ₃ (CH ₂ ) ₆ COO ⁻ ), decanoic acid ion (CH ₃ (CH ₂ ) ₈ COO ⁻ ), lauric acid ion (CH ₃ (CH ₂ ) ₁₀ COO ⁻ ), myristic acid ion (CH ₃ (CH ₂ ) ₁₂ COO ⁻ ), palmitic acid ion (CH ₃ (CH ₂ ) ₁₄ COO ⁻ ), stearic acid ion (CH ₃ (CH ₂ ) ₁₆ COO ⁻ ) Such as carbon Examples thereof include monovalent saturated carboxylate ions of formulas 1 to 18.

Examples of the divalent saturated carboxylic acid ion, for example, oxalate ((COO ^-) _2), malonic acid ion _{^{(CH 2 (COO -) 2}} ), succinate ions _{^{(- OOC (CH 2) 2}} COO -) , glutaric acid ion _{^{(- OOC (CH 2) 3}} COO -), adipic acid ion _{^{(- OOC (CH 2) 4}} COO -), pimelic acid ion _{^{(- OOC (CH 2) 5}} COO -), suberic acid ion ( _{^{- OOC (CH 2) 6 COO}} -), azelaic acid ion _{^{(- OOC (CH 2) 7}} COO -), sebacic acid ion _{^{(- OOC (CH 2) 8}} COO -) 2 divalent 2-10 carbon atoms such as And saturated carboxylate ions.

Examples of monovalent unsaturated carboxylate ions include acrylic acid ions (CH ₂ ═CHCOO ⁻ ), methacrylic acid ions (CH ₂ ═C (CH ₃ ) COO ⁻ ), and crotonic acid ions (CH ₃ CH═CHCOO ^−). ), Isocrotonic 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 ⁻ ), furan carboxylate ion (C ₄ H ₃ OCOO ⁻ ), etc. And unsaturated carboxylate ions.

Examples of the divalent unsaturated carboxylate ion include maleate ion (CH (COO ⁻ ) ═CHCOO ⁻ ), fumarate ion (CH (COO ⁻ ) = CHCOO ⁻ ), citraconic acid ion (CH ₃ C (COO)). ^-) = CHCOO ^-), mesaconic acid ion _{^{(- OCOC (CH 3) =}} CHCOO -) and the like divalent unsaturated carboxylic acid ion 4-5 carbon atoms such as.

Examples of hydroxycarboxylate ions include lactate ions (CH ₃ CH (OH) COO ⁻ ), malate ions (CH (OH) (COO ⁻ ) CH ₂ COO ⁻ ), and citrate ions (CH ₂ (COO ⁻ )). C (OH) (COO ⁻ ) CH ₂ COO ⁻ ), glycolic acid ions (CH ₂ (OH) CH (OH) CH (OH) CH (OH) CH (OH) COO ⁻ ), etc. Examples thereof include hydroxycarboxylic acid ions.

Examples of the oxocarboxylate ion include C3-C4 oxocarboxylate ions such as pyruvate ion (CH ₃ COCOO ⁻ ) and acetoacetate ion (CH ₃ COCH ₂ COO ⁻ ).
Examples of the aromatic carboxylate ion include benzoate ion (C ₆ H ₅ COO ⁻ ), phthalate ion (C ₆ H ₄ (COO ⁻ ) ₂ ), naphthalene carboxylate ion (C ₁₀ H ₇ COO ⁻ ), Examples thereof include aromatic carboxylate ions having 5 to 11 carbon atoms such as pyridinecarboxylate ion (C ₅ H ₅ NCOO ⁻ ).

Examples of the free organic sulfonic acid include methyl sulfate ion ((CH ₃ ) SO ₄ ⁻ ), ethyl sulfate ion ((C ₂ H ₅ ) SO ₄ ⁻ ), methylbenzene sulfonate ion (CH ₃ C _6). Examples thereof include organic sulfonate ions having 1 to 7 carbon atoms such as H ₄ SO ₃ ⁻ ).
Further, in the general formula (2), examples of the organic anion represented by Y ₁ include organic anions derived from amino acids, erythorbic acid, ascorbic acid, dehydroacetic acid, alcoholates, phenolates, and hydroxyl groups, in addition to those described above. .

In the general formula (2), the organic anion represented by Y ₁ is particularly preferably a monovalent saturated carboxylate ion among those described above.
A preferred embodiment of the general formula (2) includes, for example, an embodiment in which R ³ is dodecyl and Y ₁ is a monovalent saturated carboxylate ion, and more preferably, R ³ is dodecyl and Y ₁ is propion. The aspect which is an acid ion is mentioned.

The organic salt of the quaternary ammonium compound represented by the general formula (2) can be produced by a known method according to the following specific compounds. Specific examples thereof include, for example, laurylbenzyldimethylammonium Examples thereof include alkyl carboxylates. Preferably, lauryl benzyldimethylammonium propionate is used.
The weight ratio of 3-iodo-2-propynylbutylcarbamate and the organic salt of the quaternary ammonium compound represented by the above general formula (2) is not particularly limited, but is preferably 1:19 to 19: 1, more preferably 1: 9 to 9: 1.

In addition, the microorganism control agent of the present invention may further contain a river extract. By containing the extract of the river, the control effect against bacteria and mold can be increased.
The river extract is an extract extracted from a plant belonging to the river species. The river species include river (Pipe methisticum), wild species (Pipe witchmannii) and the like. Kawa is a herb belonging to the genus Pepperaceae, which is an evergreen herbaceous shrub of 1.5 to 3 m, leaves that alternate, leaf shape is heart-shaped, and length is 10 to 20 cm. Depending on the region, Kawa is called Kava, Kawakawa, Kavakawa, Yangona, Shakao, etc.

As a river extract, the compound shown by following General formula (3) shall be included, for example.
General formula (3):

(Wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁹ are the same or different and are a hydrogen atom, hydroxy or alkoxy having 1 to 4 carbon atoms, and R ⁵ and R ⁶ are linked to each other. Te _{-O- (CH 2) n -O- (} n is an integer of 1 to 3) may be a group represented by, R ⁸ is alkoxy of 1 to 4 carbon atoms, Z is -CH = CH —, —CH ₂ —CH ₂ — or epoxyethylene, and a bond

Represents a single bond or a double bond. )
In the general formula (3), examples of the alkoxy having 1 to 4 carbon atoms represented by R ^{4 to} R ⁹ include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy and the like. . Examples of the group represented by —O— (CH ₂ ) _n —O— (n is an integer of 1 to 3) formed by linking R ⁵ and R ⁶ include —O—CH ₂ —O— and —O. - (CH _{2) 2} -O-, and the like. As epoxy ethylene represented by Z,

The group shown by these is mentioned.
Of the compounds represented by the general formula (3), compounds represented by the following general formula (4) and the following general formula (5) are preferable.
General formula (4):

Wherein R ¹¹ is hydroxy or alkoxy having 1 to 4 carbon atoms, R ¹⁰ and R ¹² are a hydrogen atom, hydroxy or alkoxy having 1 to 4 carbon atoms, and R ¹¹ and R ¹² are linked to each other. -O- (CH ₂ ) _n —O— (n is an integer of 1 or 2), R ¹³ is a hydrogen atom or an alkoxy having 1 to 4 carbon atoms, and R ¹⁴ is (C1-C4 alkoxy, Z is as defined above.)
In the general formula (4), examples of the alkoxy having 1 to 4 carbon atoms represented by R ^{10 to} R ¹⁴ include the same as those described above, and —O formed by connecting R ¹¹ and R ^12. Examples of the group represented by — (CH ₂ ) _n —O— (n is an integer of 1 or 2) include —O—CH ₂ —O— and —O— (CH ₂ ) ₂ —O—.

  General formula (5):

Wherein R ¹⁵ and R ¹⁶ are a hydrogen atom, hydroxy or alkoxy having 1 to 4 carbon atoms, R ¹⁷ is a hydrogen atom or hydroxy, and R ¹⁶ and R ¹⁷ are connected to each other to form —O— ( CH ₂ ) _n —O— (n is an integer of 1 or 2), R ¹⁹ is a hydrogen atom or hydroxy, R ¹⁸ is alkoxy having 1 to 4 carbon atoms, Z Is as defined above.)
In the general formula (5), examples of the alkoxy having 1 to 4 carbon atoms represented by R ¹⁵ , R ¹⁶ and R ¹⁸ include the same ones as described above, and R ¹⁶ and R ¹⁷ are connected to each other. Examples of the group represented by —O— (CH ₂ ) _n —O— (n is an integer of 1 or 2) include —O—CH ₂ —O— and —O— (CH ₂ ) ₂ —O—. Can be mentioned.

Furthermore, among the compounds represented by the general formula (5), a compound represented by the following general formula (6) is particularly preferable.
General formula (6):

(Wherein R ²⁰ and R ²¹ are hydrogen atoms or methylenedioxy linked to each other, and Z is as defined above.)
Specific examples of the compound represented by the general formula (3) include, for example, cavine or cavine, 7,8-dihydrocavine or 7,8-dihydrocabine, yangonin, 5,6,7,8-tetrahydroyangonin. , Methysticin, 7,8-dihydromethysine, cis-5-hydroxycaine or cis-5-hydroxycabine, 11-methoxy-12-hydroxy-5,6-dehydrocavine or 11-methoxy-12-hydroxy-5 , 6-dehydrocabine, 7,8-dihydroyangonine, 5,6-dihydroyangonine, 11-methoxyyangonin, 10-methoxyyangonin, 11-hydroxyyangonin, 5,6-dehydromethycin, 12 -Benzyloxy-11-methoxy-dehydrocaine or 12-benzylo Ci-11-methoxy-dehydrocabine, 11-benzyloxy-12-methoxy-dehydrocabine or 11-benzyloxy-12-methoxy-dehydrocabine, 12-benzyloxydehydrocavine, 12-benzyloxydehydrocabine, isocaine or isocabine 5,6-dehydrocabine or 5,6-dehydrocabine, isomethicine and the like. These compounds may be used alone or in combination of two or more.

  When extracting from a plant belonging to the river species, extraction is performed from the stem, root or leaf of the plant belonging to the river species. In detail, the extract of river can be obtained by extracting a plant belonging to the species of Kawa and extracting the solvent of the extract. In the extraction treatment, for example, a plant belonging to the species of Kawa is treated with cutting, drying, pulverization, etc., if necessary, and then using an appropriate extraction solvent at room temperature or under heating at normal pressure or under pressure ( Extraction is performed under pressure in an autoclave or a pressure pan, and then, if necessary, filtered, and then concentrated so that the extraction solvent is distilled off. Plants belonging to the river species may be used alone or in combination of two or more.

  Examples of the extraction solvent include water such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-octanol, 2-butyl-octanol, and lauryl. Alcohols such as alcohols, monohydric alcohols such as cyclohexanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin and the like, such as ethyl ether, propyl ether, isopropyl ether, dimethoxyethane, cyclic Ethers such as ethers (eg, dioxane, tetrahydrofuran, etc.), mono- or dialkylene glycol monoalkyl ethers (eg, ethylene glycol monomethyl ether), eg, aceto , Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, for example, esters such as ethyl acetate, butyl acetate and n-butyl laurate, for example, halogen carbonization such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane Hydrogen, for example, aliphatic hydrocarbons such as hexane and octane, for example, alicyclic hydrocarbons such as cyclohexane and cycloheptane, for example, aromatic hydrocarbons such as benzene, toluene and xylene, for example, acetonitrile Nitriles such as carboxylic acids such as formic acid, acetic acid and oleic acid, and aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide and pyridine. These solvents may be used alone or in combination of two or more. Preferably, alcohols and ketones are used.

The amount of the extraction solvent used may be in a range that does not impair the extraction efficiency and the extraction operation, and is, for example, 50 to 10,000 parts by weight, preferably 100 to 2000 parts by weight with respect to 100 parts by weight of the extraction target. The extraction temperature is, for example, 0 to 150 ° C, preferably 10 to 120 ° C.
As a method for extracting a river extract from a Kawa seed plant, it can be carried out by methods described in Japanese Patent No. 3306054 and Japanese Patent Application Laid-Open No. 2003-267802. The compound represented by the general formula (3) can be produced by the method described in Japanese Patent Application Laid-Open No. 2003-252708.

The above-described extract of kava (including the compound represented by the general formula (3)) is an organic salt of 3-iodo-2-propynylbutylcarbamate and a quaternary ammonium compound represented by the following general formula (2). For example, 2.5 to 500 parts by weight, preferably 5 to 250 parts by weight, are contained with respect to 100 parts by weight in total.
Moreover, in the microorganism control agent of this invention, a cabbage extract can be further contained. By including the extract of boxworm, the control effect can be increased against bacteria and mold.

  The extract of extract is an extract extracted from a plant belonging to the seedling species. Scotch species include natural charcony corylfolinin, various coumarin-like substances (including mainly psoralen and isopsoalen), and the like. The cabbage is a dried product of mature fruits, seeds, etc. of prosthetic fat (Psoralea corifoia L.), which is an annual plant of Leguminosae. In the present invention, an extract extracted from this Is used.

  More specifically, the extract of the extract of koshikoshi can be obtained by extracting a plant belonging to the species of kokoshi and distilling off the solvent of the extract. In the extraction treatment, for example, a plant belonging to the seedling species is subjected to treatments such as cutting, drying, and pulverization as necessary, and then using a suitable extraction solvent at room temperature or under heating at normal pressure or under pressure ( Extraction is performed under pressure in an autoclave or a pressure pan, and then, if necessary, filtered, and then concentrated so that the extraction solvent is distilled off. Plants belonging to the Hakoshi species may be used alone or in combination of two or more.

As the extraction solvent, for example, the same solvent as the extraction solvent used for the above-mentioned river extraction solvent is used. Preferably, alcohols and ketones are used.
The amount of the extraction solvent used may be within a range that does not impair the extraction efficiency and the extraction operation. The extraction temperature is, for example, 0 to 150 ° C, preferably 10 to 120 ° C.

The extract from the extract thus obtained is 100 parts by weight in total of 3-iodo-2-propynylbutylcarbamate and an organic salt of a quaternary ammonium compound represented by the following general formula (2). For example, 2.5 to 500 parts by weight, preferably 5 to 250 parts by weight are contained.
The microorganism control agent of the present invention comprises 3-iodo-2-propynylbutylcarbamate , an organic salt of a quaternary ammonium compound, and, if necessary, a river extract and / or a pepper extract, depending on the purpose and application. It can be formulated by a known method. The dosage form is not particularly limited, and various known dosage forms such as a liquid (including a water suspension and an oil), a paste, a powder, a granule, and a microcapsule can be employed. Among these, Preferably, a liquid agent is mentioned.

  In order to prepare as a liquid agent, for example, the above-described components and a solvent may be blended and mixed. In the case of formulating as a liquid agent, for example, an active ingredient comprising a haloacetylene compound, an organic salt of a quaternary ammonium compound, a river extract and / or a box extract extracted optionally in 100% by weight of the solution The total amount is 0.1 to 95% by weight, and the solvent may be mixed and dissolved or dispersed in such a ratio that the remaining amount is left.

  The solvent used for preparing the liquid agent may be any solvent that does not affect the effect of the active ingredient. For example, water, for example, methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol Alcohol solvents such as branched alcohols such as 2-methyl-1-propanol, 2-methyl-2-propanol, 3-methyl-3-methoxybutanol, such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene Glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether Glycol solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and tripropylene glycol monomethyl ether, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and propylene carbonate, for example ethers such as dioxane, tetrahydrofuran and ethyl ether Solvents such as ethyl acetate, butyl acetate, isobutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate, dimethyl succinate and the like, for example, dimethylformamide, Examples include polar solvents such as dimethylacetamide, dimethyl sulfoxide, acetonitrile, and N-methylpyrrolidone.

Of these solvents, water, alcohol solvents, glycol solvents, and polar solvents are preferable. These solvents may be used alone or in combination of two or more.
Each component described above can be mixed with a solvent, mixed, and then adsorbed onto, for example, an inorganic carrier to be granulated or powdered, and further microencapsulated.
The microbial control agent of the present invention may be added with known additives such as other microbial control agents, surfactants, antioxidants, light stabilizers and the like depending on the purpose and application.

  Examples of other microorganism control agents include isothiazoline compounds, nitroalcohol compounds, dithiol compounds, thiophene compounds, phthalimide compounds, haloalkylthio compounds, pyrithione compounds, phenylurea compounds, triazine compounds, guanidines. Compounds, triazole compounds, benzimidazole compounds, quaternary ammonium salt compounds, bis quaternary ammonium salt compounds, and the like.

  Examples of the isothiazoline-based compound include 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-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- Examples include isothiazoline-3-one, 1,2-benzisothiazoline-3-one, and Nn-butyl-1,2-benzisothiazoline-3-one.

Examples of the nitroalcohol compound include 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitro-1-ethanol, and the like.
Examples of the dithiol-based compound include 4,5-dichloro-1,2-dithiol-3-one.
Examples of the thiophene compound include 3,3,4-trichlorotetrahydrothiophene-1,1-dioxide, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, and the like.

  Examples of the phthalimide compound include N-1,1,2,2-tetrachloroethylthio-tetrahydrophthalimide (Captafol), N-trichloromethylthio-tetrahydrophthalimide (Captan), N-dichlorofluoromethylthiophthalimide (Fluorolpet), N- And trichloromethylthiophthalimide (Folpet).

Examples of the haloalkylthio compounds include N-dimethylaminosulfonyl-N-tolyl-dichlorofluoromethanesulfamide (Tolylfluoride), N-dimethylaminosulfonyl-N-phenyl-dichlorofluoromethanesulfamide (Dichlofluoride) and the like. Can be mentioned.
Examples of the pyrithione compound include sodium pyrithione and zinc pyrithione.

Examples of the phenylurea compound include 3- (3,4-dichlorophenyl) -1,1-dimethylurea.
Examples of the triazine compound include 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine.
Examples of the guanidine compound include 1,6-di- (4′-chlorophenyldiguanide) -hexane, polyhexamethylene biguanidine hydrochloride, and the like.

  Examples of triazole compounds include α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (common name: tebuconazole). ), 1-[[2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole (common name: propico) Nazole), 1-[[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole (common name: azaconazole), α- (4 -Chlorophenyl) -α- (1-cyclopropylethyl) -1H-1,2,4-triazole-1-ethanol (common name: cyproconazole) and the like.

Examples of the benzimidazole compound include methyl 2-benzimidazole carbamate, ethyl 2-benzimidazole carbamate, 2- (4-thiazolyl) benzimidazole, and the like.
Examples of the quaternary ammonium salt compound include known compounds excluding the organic salt of the quaternary ammonium compound represented by the general formula (2), and specific examples thereof include, for example, N, N-didecyl- N-methyl-N- (2-hydroxyethyl) ammonium alkylcarboxylate, N-decyl-N, N-dimethyl-N- (2- (2-hydroxyethoxy) ethyl) alkylcarboxylate, N-decyl-N -Methyl-N- (2-hydroxyethyl) -N- (2- (2-hydroxyethoxy) ethyl) .alkylcarboxylate and the like.

  Examples of bisquaternary ammonium salt compounds include N, N′-hexamethylenebis (4-carbamoyl-1-decylpyridinium acetate), 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium). Acetate), N, N′-hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide), 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide), and the like.

  Other examples of the algae and / or fungicides include, for example, organic iodine compounds such as diiodomethyl-p-toluylsulfone and p-chlorophenyl-3-iodopropargyl formal, such as tetramethylthiuram disulfide. Thiocarbamate compounds such as 2,4,5,6-tetrachloroisophthalonitrile and other nitrile compounds such as 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine Pidylline compounds such as benzothiazole compounds such as 2- (4-thiocyanomethylthio) benzothiazole, such as 3-benzo [b] thien-2-yl-5,6-dihydro-1,4,2- Examples thereof include oxathiazine compounds such as oxathiazine-4-oxide.

Examples of the surfactant include known surfactants such as soaps, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants. Preferably, nonionic surfactants and anionic surfactants are used.
Examples of the antioxidant include phenol-based antioxidants such as 2,6-di-t-butyl-4-methylphenol and 2,2′-methylenebis [4-methyl-6-t-butylphenol], for example, Examples thereof include amine-based antioxidants such as alkyldiphenylamine and N, N′-di-s-butyl-p-phenylenediamine.

For example, in the case of a liquid agent, the surfactant and the antioxidant are added in an amount of 0.1 to 5 parts by weight with respect 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 with respect to 100 parts by weight of the liquid agent.

  The thus obtained microorganism control agent of the present invention exhibits a sufficient control effect even at low concentrations against a wide variety of microorganisms. In addition, since organic acids are used as counter ions for quaternary ammonium compounds, the halogen content can be reduced, the environmental load can be reduced, and metal corrosiveness and skin irritation can be achieved. Can be significantly reduced. Therefore, it can be effectively used in various fields as a microorganism control agent that is environmentally friendly and excellent in safety.

Further, the extract of the extract of the present invention can be further improved in the microbial control effect by being contained in the microbial control agent.
The microorganism control agent of the present invention can be applied to various wood materials, wood products, industrial materials, and industrial products. Specific applications include, for example, wood and wood products, pulp, fibers, paints, and adhesives. Leather, paper processed products, electronic parts, wall coverings and the like.

  The microorganism control agent of the present invention may be added to the control target in an effective amount that exhibits the control effect of the microorganisms depending on the control target, and the concentration thereof is not particularly limited. For example, 1 to 8000 mg (active ingredient) / Kg (product), preferably 5 to 5000 mg (active ingredient) / kg (product).

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the symbol of a component used for a following example and a comparative example, a brand name, a manufacturer, etc. are shown below.
IPBC: 3-iodo-2-propynylbutylcarbamate (trade name “MP-100”, Bayer, IPBC content 97.0% by weight)
RBDA: N-lauryl-N-benzyl-N, N-dimethylammonium propionate (trade name “03033TX”, Takemoto Yushi Co., Ltd., RBDA content 85 wt%, solvent: propylene glycol 5 wt% and water 10 wt% %)
Example 1
"MP-100" 3.1 parts by weight (IPBC 3.0 parts by weight), "03033TX" 1.2 parts by weight (RBDA 1.0 part by weight), diethylene glycol monomethyl ether 95.7 parts by weight, By uniformly mixing with a stirrer, a liquid was obtained.

Example 2
"MP-100" 2.1 parts by weight (IPBC 2.0 parts by weight), "03033TX" 2.4 parts by weight (RBDA 2.0 parts by weight), diethylene glycol monomethyl ether 95.5 parts by weight, By uniformly mixing with a stirrer, a liquid was obtained.
Example 3
"MP-100" 1.0 part by weight (IPBC 1.0 part by weight), "03033TX" 3.5 parts by weight (RBDA 3.0 parts by weight), diethylene glycol monomethyl ether 95.5 parts by weight, By uniformly mixing with a stirrer, a liquid was obtained.

Example 4
“MP-100” 1.0 part by weight (IPBC 1.0 part by weight), “03033TX” 3.5 part by weight (RBDA 3.0 part by weight), and a river extract (Production Example 1: Kawa stem with acetone) After extraction, the solvent was distilled off) 0.5 parts by weight, “ISOFOL 14T” (branched alcohol, Sasol German GmbH) 49.0 parts by weight, “ISOFOL 16” (branched alcohol, Sasol German GmbH) 21 0.0 parts by weight and 25.0 parts by weight of propylene glycol were blended and mixed uniformly with a stirrer to obtain a liquid agent.

Example 5
“MP-100” 1.0 part by weight (IPBC 1.0 part by weight), “03033TX” 3.5 part by weight (RBDA 3.0 part by weight), and extract of extract of kokoshi (Production Example 3: extract of kokoshi with acetone) Thereafter, the solvent was distilled off) 0.5 part by weight, "ISOFOL 14T" (branched alcohol, Sasol German GmbH) 49.0 parts by weight, "ISOFOL 16" (branched alcohol, Sasol German GmbH) 21.0 The liquid agent was obtained by mix | blending a weight part and 25.0 weight part of propylene glycol, and mixing uniformly with a stirrer.

Comparative Example 1
"MP-100" 4.1 parts by weight (IPBC 4.0 parts by weight) and diethylene glycol monomethyl ether 95.9 parts by weight were blended and mixed uniformly with a stirrer to obtain a liquid agent.
Comparative Example 2
"03033TX" 4.7 parts by weight (RBDA 4.0 parts by weight) and diethylene glycol monomethyl ether 95.3 parts by weight were blended and mixed uniformly with a stirrer to obtain a liquid agent.

Evaluation of microbial control effect The liquid agents obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were added to a sterilized plastic petri dish having a diameter of 90 mm so that the concentration in the agar medium would be a predetermined concentration. did. Subsequently, a glucose broth agar medium (for bacteria) or potato dextrose agar medium (for molds and yeast) previously dissolved in an autoclave was poured and sufficiently mixed, and then allowed to cool and solidify. Using the medium thus obtained, the microorganism control effects of the liquid preparations obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated by the following Test Examples 1 to 3.

Test Example 1 (Measurement of MIC for bacteria)
The bacterial broth for inoculation was inoculated using a microplanter (manufactured by Sakuma Seisakusho) on a glucose broth agar medium to which the above solution was added, and cultured at 33 ° C. for 18 hours. Subsequently, the growth of the bacterium after the culture was observed to determine the minimum inhibitory concentration MIC (μg / mL).
Test Example 2 (Measurement of MIC for mold and yeast)
Using a microplanter (manufactured by Sakuma Seisakusho), the mold spore suspension and the yeast for inoculation were inoculated into the potato dextrose agar medium to which the above solution was added, and cultured at 28 ° C. for 3 days. Subsequently, the growth of the bacterium after the culture was observed to determine the minimum inhibitory concentration MIC (μg / mL).

Test Example 3 (Measurement of MIC for Pseudomonas aeruginosa and Kawaratake)
A fungus bed sample having a diameter of 6 mm is punched out from a well-grown Oozutake mushroom and Kawaratake mushroom bed with a cork borer, and this sample is placed on a potato dextrose agar medium to which the above-mentioned solution is added, at 26 ° C., with a humidity of 90 The cells were cultured for 7 days under the condition of% RH. Subsequently, the growth of the bacterium after the culture was observed to determine the minimum inhibitory concentration MIC (μg / mL).

  Table 1 shows the names of bacteria, molds and yeasts used in the MIC measurement. Table 2 shows the results of Test Examples 1 to 3.

Production method 1
The stem (upper part) of the river was pulverized with a pulverizer, and 100 g of the pulverized powder was extracted with 500 mL of acetone. In the extraction, the operation of applying ultrasonic vibration at 30 ° C. for 15 minutes was repeated twice. The obtained extract was allowed to stand at 40 ° C. for 1 week, then Toyo Filter Paper No. The resulting filtrate was concentrated and dried under reduced pressure to obtain an acetone extract.

Production Example 2
An ethanol extract was obtained in the same manner as in Production Example 1 except that ethanol was used instead of acetone as the extraction solvent.
Method for producing box extract extract Production Example 3
Hakoshi (manufactured by Matsuura Hanpo Co., Ltd.) was pulverized with a pulverizer, and 100 g of the pulverized powder was extracted with 500 mL of acetone. Extraction was repeated twice by applying ultrasonic vibration at 30 ° C. for 15 minutes. The obtained extract was allowed to stand at 40 ° C. for 1 week, then Toyo Filter Paper No. The resulting filtrate was concentrated and dried under reduced pressure to obtain an acetone extract.

Production Example 4
An ethanol extract was obtained in the same manner as in Production Example 3, except that ethanol was used instead of acetone as the extraction solvent.

Claims (6)

A microorganism control agent comprising 3-iodo-2-propynylbutylcarbamate and an organic salt of a quaternary ammonium compound represented by the following general formula (2) .
One general formula (2):

(In the formula, R ³ represents an alkyl group having 12 to 16 carbon atoms. Y ₁ represents an organic anion.) In the general formula (2), the organic anions represented by Y ₁ is free, is characterized in that an organic carboxylic acid ion of 1 to 4 carbon atoms, microbial control agent of claim 1. The organic salt of the quaternary ammonium compound represented by the general formula (2) is N-lauryl-N-benzyl-N, N-dimethylammonium propionate, according to claim 1 or 2 . Microbial control agent. The weight ratio of 3-iodo-2-propynylbutyl carbamate and the organic salt of the quaternary ammonium compound represented by the general formula (2) is in the range of 1:19 to 19: 1. The microorganism control agent according to any one of claims 1 to 3 . The microorganism control agent according to any one of claims 1 to 4 , further comprising a kava extract. Furthermore, the microorganism control agent in any one of Claims 1-4 characterized by containing a box extract extract.