JP2017095371A - Industrial preservative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial preservative which can be used in wide industrial applications and has, in each of the applications, good antibacterial, antifungal, antiseptic, and algae-proofing activity.SOLUTION: Provided is an industrial preservative, comprising an isothiazoline-based compound and N-phenylmaleimide.SELECTED DRAWING: None

Description

  The present invention relates to an industrial preservative, and more particularly to an industrial preservative used as a control agent for bacteria, molds, yeasts, and algae.

Conventionally, harmful microorganisms such as bacteria, molds, yeasts, and algae are easily propagated in various industrial products, which causes a decrease in productivity and quality and generation of malodor. Among them, water used for the production of paper pulp, various waters such as circulating cooling water in the industrial field, water-based paints, emulsions, printing pastes, water used for the production of leather, etc. It causes corrosion and mold on the object to be cleaned or processing equipment.
Therefore, it is widely known to add various industrial sterilizing compositions that exert control effects on bacteria, molds, yeasts, and algae to industrial products and industrial water, thereby suppressing or controlling the generation of harmful microorganisms. As one of such drugs, isothiazoline compounds are known. However, the isothiazoline-based compounds have a problem that the antibacterial spectrum is narrow at practical concentrations and cannot cope with various microorganisms.
Therefore, in order to broaden the antibacterial spectrum of isothiazoline-based compounds, combined use with various antibacterial, antifungal and antialgal agents has been studied. For example, halogenated aliphatic nitroalcohol (Patent Document 1), halocyanoacetamide compounds (patents) Reference 2), a combination of a cresol compound (Patent Document 3) and a zinc oxide / zinc pyrithione composite compound (Patent Document 4) have been proposed.

Japanese Patent Laid-Open No. 08-133913 JP 2000-063210 A JP 2002-338812 A JP 2013-189404 A

However, with the recent diversification of industrial products, there is a demand for the development of an industrial preservative having superior efficacy and excellent durability, but for example, described in Patent Documents 1 to 4 The combination that was made could not fully meet the demand.
Then, this invention makes it a subject to develop the industrial preservative which has the outstanding control effect with respect to bacteria, mold, yeast, and algae.

  As a result of intensive studies to solve the above problems, the present inventors have significantly improved the control effect on bacteria, mold, yeast, and algae when an isothiazoline-based compound and N-phenylmaleimide are used in combination. The present inventors have found that it can be an industrial preservative having an effect superior to the additive effect, and have solved the above-mentioned problems.

［式中、Ｒ_１は水素原子または炭素数１〜２０の炭化水素基を示し、Ｒ_２およびＲ_３は同一または異なって、それぞれ水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基を示す。］
一般式（２）：

［式中、Ａ_１環は、ハロゲン原子または炭素数１〜６のアルキル基で置換されていてもよいベンゼン環を示し、Ｙは水素原子または炭素数１〜２０の炭化水素基を示す。］
２．一般式（２）で表されるイソチアゾリン系化合物が、１，２−ベンゾイソチアゾリン−３−オンまたはＮ−ｎ−ブチル−１，２−ベンゾイソチアゾリン−３−オンである、１．に記載の工業用保存剤。
３．イソチアゾリン系化合物とＮ−フェニルマレイミドとを、重量比で９９：１〜１：９９の割合で含有することを特徴とする、１．または２．に記載の工業用保存剤。
４．イソチアゾリン系化合物とＮ−フェニルマレイミドとを、重量比で９８：２〜１：９９の割合で含有することを特徴とする、１．または２．に記載の工業用保存剤。
５．一般式（１）で表されるイソチアゾリン系化合物が、２−メチル−４−イソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オン、４−クロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オン、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、５−クロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オンおよび４，５−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オンよりなる群から選択される１種または２種以上である、１．、３．、４．いずれかに記載の工業用保存剤。
６．１．〜５．いずれかに記載の工業用保存剤を含有する、工業製品。
７．１．〜５．いずれかに記載の工業用保存剤を、工業用材料に適用する工業用材料の保存方法。 The gist of the present invention is specifically as follows.
1. An industrial preservative comprising an isothiazoline compound represented by the general formula (1) or the general formula (2) and N-phenylmaleimide.
General formula (1):

[Wherein, R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. Show. ]
General formula (2):

[Wherein, A ₁ ring represents a benzene ring optionally substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms, and Y represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ]
2. The isothiazoline-based compound represented by the general formula (2) is 1,2-benzisothiazolin-3-one or Nn-butyl-1,2-benzisothiazolin-3-one; An industrial preservative as described in 1.
3. 1. It contains isothiazoline-based compound and N-phenylmaleimide in a weight ratio of 99: 1 to 1:99. Or 2. An industrial preservative as described in 1.
4). 1. The isothiazoline-based compound and N-phenylmaleimide are contained in a weight ratio of 98: 2 to 1:99. Or 2. An industrial preservative as described in 1.
5. The isothiazoline compound represented by the general formula (1) is 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- 1. one or more selected from the group consisting of n-octyl-4-isothiazolin-3-one; 3. 4. The industrial preservative in any one.
6.1. ~ 5. An industrial product containing the industrial preservative according to any one of the above.
7.1. ~ 5. A method for preserving industrial materials, wherein any of the industrial preservatives is applied to industrial materials.

  The industrial preservative of the present invention expresses excellent antibacterial, antifungal, antiseptic and algal control effects and is excellent in controlling effect, and can be applied to various industrial products, for example, indoors and outdoors. Paint, rubber, fiber, resin, plastic, adhesive, jointing agent, sealing agent, building material, caulking agent, soil treatment agent, wood treatment agent, white water, pigment, printing plate treatment liquid, cooling water, ink in papermaking process, An excellent antimicrobial activity can be exerted by adding a very small amount of an additive for antimicrobial expression to cutting oil, cosmetics, non-woven fabric, spinning oil, leather and the like.

Hereinafter, the industrial preservative of the present invention and the method for preserving industrial materials will be described in detail.
The preservative in the present invention is a composition having a controlling activity against bacteria, fungi such as fungi such as molds, yeasts and wood-rotting fungi, and algae, which are problematic in industrial applications such as industrial products and industrial materials. Means.

The industrial preservative of the present invention contains an isothiazoline compound and N-phenylmaleimide as active ingredients.
The isothiazoline compound of the present invention is represented by the following general formula (1).

[Wherein, R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. Show. ]

In the general formula (1), examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ₁ include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl 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, 2,2-dimethylpropyl, n-hexyl, isohexyl, 2-ethylbutyl, n-heptyl, isoheptyl, n-octyl, isooctyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1,1- Examples thereof include alkyl groups having 1 to 10 carbon atoms such as dimethylhexyl, 1-ethyl-1-methylpentyl, 1,1-diethylbutyl, 2-ethylhexyl, nonyl and decyl, and preferably alkyl groups having 1 to 8 carbon atoms. .

  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.

R ₁ is preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n- An alkyl group having 1 to 4 carbon atoms such as butyl, isobutyl, sec-butyl, tert-butyl, and the like, and n-octyl, isooctyl, sec-octyl (1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, etc.), tert -Alkyl groups having 8 carbon atoms such as octyl (1,1-dimethylhexyl, 1-ethyl-1-methylpentyl, 1,1-diethylbutyl, etc.), 2-ethylhexyl, etc. are more preferable, methyl, ethyl, n-butyl N-octyl is particularly preferred.

R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon group.
In the general 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 preferable.

Examples of the hydrocarbon group represented by R ₂ or R ₃ include the same hydrocarbon groups represented by R ₁ described above, and include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Alkyl groups having 1 to 4 carbon atoms such as sec-butyl and tert-butyl are particularly preferable.

R ₂ and R ₃ are the same or different and are each preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom or a chlorine atom.

As the isothiazoline-based compound represented by the general formula (1), a compound in which R ₁ is an alkyl group having 1 to 20 carbon atoms, R ₂ and R ₃ are the same or different and each is a hydrogen atom or a halogen atom is preferable.
Preferable specific examples of the isothiazoline-based compound include 2-methyl-4-isothiazolin-3-one (hereinafter sometimes referred to as “H-MIT”), 2-ethyl-4-isothiazoline-3-one, 2 -N-octyl-4-isothiazolin-3-one (hereinafter also referred to as “OIT”), 5-chloro-2-methyl-4-isothiazolin-3-one (hereinafter referred to as “Cl-MIT”) And 5-chloro-2-ethyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4 -Isothiazoline-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (hereinafter sometimes referred to as "DCOIT"), 4,5-dichloro-2-cyclo Xyl-4-isothiazolin-3-one, and a mixture of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one (hereinafter referred to as “MITs”). And the like.) And the like. 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, 4,5-dichloro-2-n-octyl-4-isothiazoline-3- Preferred is a mixture of ON and 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro -2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazoline-3 A mixture of one and 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one is particularly preferred. The above isothiazoline-based compounds may be used alone or in combination of two or more.

  The isothiazoline compound of the present invention is represented by the following general formula (2).

[Wherein, A ₁ ring represents a benzene ring optionally substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms, and Y represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ]

In general formula (2), the substituents in the benzene ring which may be substituted with a halogen atom represented by ring A ₁ or an alkyl group having 1 to 6 carbon atoms may be the same or different. -4, preferably 1 or 2 may be substituted. As the benzene ring which may be substituted represented by A ₁ ring, unsubstituted benzene ring.

In the general formula (2), examples of the hydrocarbon group represented by Y include the same hydrocarbon groups represented by R ₁ described above. Among them, an alkyl group having 1 to 8 carbon atoms is preferable, and the carbon number is 1 An alkyl group of ˜4 is more preferred, and an n-butyl group is particularly preferred.
Y is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and most preferably a hydrogen atom or an n-butyl group.

As the isothiazoline-based compound represented by the general formula (2), a compound in which A ₁ ring is an unsubstituted benzene ring and Y is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferable.
Preferable specific examples of the isothiazoline compound represented by the general formula (2) include 1,2-benzisothiazolin-3-one (hereinafter sometimes referred to as “BIT”), Nn-butyl-1 , 2-benzoisothiazolin-3-one and the like. The isothiazoline compounds represented by the general formula (2) may be used alone or in combination of two or more.

When R _{1 to} R ₃ in the general formula (1) or Y in the general formula (2) is a hydrocarbon group, the hydrocarbon group may have a substituent. Examples of the substituent include a hydroxyl group; halogen atoms of chlorine, fluorine, bromine and iodine; a cyano group; an amino group; a carboxyl group; an alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, butoxy; C1-C4 alkylthio groups, such as propylthio and butylthio, are mentioned. The substituents may be the same or different, and 1 to 5, preferably 1 to 3 may be substituted, but an unsubstituted hydrocarbon group is preferred.
Further, as the isothiazoline compound of the present invention, any one of the isothiazoline compound represented by the general formula (1) and the isothiazoline compound represented by the general formula (2) is selected and used. Or two or more of them may be used in combination.

  The N-phenylmaleimide of the present invention is a compound having the chemical structure shown below.

The weight ratio of the isothiazoline-based compound represented by the general formula (1) or the general formula (2) of the present invention (the total amount of each compound when two or more are used) and N-phenylmaleimide is 99: It is preferably 1 to 1:99 (weight ratio), more preferably 98: 2 to 1:99 (weight ratio), and particularly preferably 95: 5 to 1:99 (weight ratio). .
Combining a given concentration of isothiazoline-based compound with N-phenylmaleimide has a specific improvement compared to the control activity against single bacteria, molds, yeasts, and algae, that is, when only two agents are used alone. It has been confirmed by experiments described later that a synergistic effect far exceeding the expected effect is obtained. Although the details of the mechanism of action of the combination of the present invention exhibiting synergistic antibacterial activity are unclear, the result of expression of mutual synergistic action at the point of action by combining two antibacterial agents having different action mechanisms It is estimated that such a remarkable effect can be obtained. That is, according to the classification table according to the mechanism of action of fungicides compiled by the countermeasure committee of the World Agricultural Chemical Industry Federation, isothiazoline compounds are classified as nucleic acid synthesis inhibitors, and N-phenylmaleimide is classified as a multi-acting contact activity inhibitor. It is considered that this nucleic acid synthesis inhibitory action and multi-action point contact activity inhibitory action are the effects obtained as a result of the expression of mutual synergies at any action point level. Therefore, this synergistic effect is an effect obtained for the first time by combining an isothiazoline-based compound at a predetermined concentration and N-phenylmaleimide, and this is a particularly remarkable effect that the present inventor has confirmed the effect for the first time through experiments. is there.

  The industrial preservative of the present invention can be made into various dosage forms by dissolving, dispersing, adsorbing, etc., an isothiazoline compound and N-phenylmaleimide on various carriers such as a liquid carrier and a solid carrier. . For example, solutions such as solutions, wettable powders, suspensions, dispersions, emulsions, and oils; solids such as powders, granules, microcapsules, microspheres, flowables, and foaming agents; pastes and creams A semi-solid agent; a spray agent, an aerosol agent; a paint, and the like. These preparations can be produced by conventional methods.

  Examples of the liquid carrier 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) ), Polyvalent alcohols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and triethylene glycol butyl ether Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and propylene carbonate; ethers such as dioxane, tetrahydrofuran and ethyl ether; ethyl acetate, butyl acetate, isobutyl acetate, 3-methyl-3-methoxybutyl acetate, γ- Esters such as butyrolactone, dimethyl adipate, dimethyl glutarate, dimethyl succinate; aromatic solvents such as benzene, toluene, xylene, methylnaphthalene, dimethylnaphthalene, isopropylnaphthalene, diisopropylnaphthalene, ethylbiphenyl, diethylbiphenyl, solvent naphtha Halogenated hydrocarbon solvents such as carbon tetrachloride, chloroform and methylene chloride; dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonite Examples include polar organic solvents such as ril and N-methylpyrrolidone. These liquid carriers may be used alone or in a combination of two or more. Among these liquid carriers, water, ketones such as propylene carbonate, lower alcohols and polyhydric alcohols are preferably used.

Examples of the solid carrier that can be used in the present invention include diatomaceous earth, mica, clay, kaolin, talc, quartz powder, talc such as bentonite, talc powder, and wax stone powder, clays such as finely divided clay, and calcium carbonate. Mineral powders; sulfur powders; urea powders; plant powders such as wood flour and starch; and various carriers frequently used in industrial preservatives. These solid carriers are often used as extenders. These solid carriers can also be used alone or in combination.
The aerosol agent can be produced by diluting an isothiazoline-based compound and N-phenylmaleimide with an appropriate solvent as necessary, and filling the container together with a propellant. Examples of the solvent include the solvents exemplified above. Examples of the propellant include Freon and liquefied natural gas.

  The industrial preservative of the present invention comprises various additives as required depending on the type of preparation, for example, stabilizers such as antioxidants and ultraviolet absorbers; binders; resins having film-forming ability; emulsifiers, Dispersing agents, spreading agents, wetting agents, penetrating agents; thickeners; flow aids; anti-caking agents; flocculants; UV scattering agents; moisture removing agents;

Examples of the antioxidant include 4,4′-thiobis-6-t-butyl-3-methylphenol, butylated hydroxyanisole (2-t-butyl-4-methoxyphenol and 3-t-butyl-4- A mixture of methoxyphenol), p-octylphenol, mono (or di or tri)-(α-methylbenzyl) phenol, 2,6-di-t-butyl-p-cresol (hereinafter “BHT”). ), Phenol-based antioxidants such as pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate; N, N′-di-2-naphthyl-p-phenylenediamine Amine-based antioxidants such as 2,5-di (t-amyl) hydroquinoline hydroquinoline-based antioxidants; dilauryl thiodipro Sulfur-based antioxidants such as onato; and phosphorus-based antioxidants such as triphenyl phosphite may be exemplified.
Examples of the ultraviolet absorber include benzotriazole compounds such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole. Benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone; salicylic acid compounds such as phenyl salicylate and pt-butylphenyl salicylate; 2-cyano-3,3; -2-ethylhexyl diphenyl acrylate, 2-ethoxy-2'-ethyl oxalic acid bisanilide, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensation Such as things.
Examples of the binder include carboxymethylcellulose sodium salt, methylcellulose, ethylcellulose, hydroxymethylcellulose, dextrin, pregelatinized starch, polyvinyl alcohol, polyvinylpyrrolidone, sodium lignin sulfonate, and potassium lignin sulfonate.
Examples of the resin having a film forming ability include polyolefins such as polyethylene and polypropylene, polyvinyl acetate, polyvinyl alcohol, acrylic resins, polyvinyl chloride, styrene resins, fluororesins, chlorinated polyolefins, alkyd resins, polyamides, polyesters, and the like. Thermosetting resins such as phenol resins, urea resins, melamine resins, furan resins, unsaturated polyester resins, and epoxy resins.

As the emulsifier, dispersant, spreading agent, wetting agent, and penetrating agent, conventional surfactants such as anionic surfactants and nonionic surfactants can be used. Examples of the anionic surfactant include metal soaps, sulfate ester salts such as alkyl sodium sulfate, alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, sodium alkylnaphthalene sulfonate [for example, products manufactured by Takemoto Yushi Co., Ltd. Alkylnaphthalene sulfonates such as the name Neukalgen BX-C], dialkyl sodium 2-sulfosuccinate [for example, trade name Neocor SW-C, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], polyalkyl Carboxylic acid type surfactant [for example, Sanyo Chemical Industries, trade name Toxanone GR-30], α-olefin sulfonate, polyoxyethylene distyrenated phenyl ether sulfate ammonium salt [for example, Daiichi Kogyo Seiyaku Product name, Dixzo, manufactured by Le 60A], sodium lignin sulfonate, potassium lignin sulfonate can be exemplified. Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether [for example, trade name Neugen (EA-142) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], polyoxyethylene aryl ether, Fatty acid polyhydric alcohol ester, fatty acid polyhydric alcohol polyoxyethylene, sucrose fatty acid ester, block copolymer of ethylene oxide and propylene oxide [for example, Sanyo Chemical Industries, Ltd., trade name Newpol PE-64], etc. Can be illustrated.
Examples of the thickener include polyvinyl alcohol, polyacrylic acid and salts thereof, and PAP auxiliary (for example, isopropyl phosphoric acid), wax, polyethylene, fatty acid metal salt, paraffin, silicone oil as flow aids. Examples thereof include organic lubricants such as inorganic lubricants such as talc. Examples of the anti-caking agent include white carbon, diatomaceous earth, magnesium stearate, aluminum oxide, titanium dioxide and the like. Examples of the flocculant include liquid paraffin, ethylene glycol, diethylene glycol, triethylene glycol, and an isobutylene polymer [for example, trade name IP Solvent-2835 manufactured by Idemitsu Kosan Co., Ltd.]. Examples of the ultraviolet scattering agent include titanium dioxide. Examples of the moisture removing agent include desiccants such as anhydrous gypsum and silica gel powder. Examples of the colorant include organic or inorganic pigments and dyes.

  Furthermore, the industrial preservative of the present invention may contain known antiseptic and fungicidal agents, insect repellents, pest repellents, insect growth control agents, and efficacy enhancers.

Bacteria, fungi such as fungi such as molds, yeasts and wood decay fungi, and algae that are targeted for control by the industrial preservative of the present invention are not particularly limited.
Examples of bacteria include Gram-negative bacilli such as Escherichia coli, Pseudomonas aeruginosa, and Serratia; Gram-positive bacilli such as Clostridium; Gram-negative cocci such as Branhamella; Gram-positive cocci such as S. aureus.
Examples of the mold include, for example, zygomycetes such as the genus Absidia, Mucor, and Rhizopus, for example, the genus Ketomium, the genus Eurotium, and the genus Neurospora. Ascomycetes such as Saccharomyces, for example, Acremonium, Alternaria, Aspergillus, Aureobasidium, Cladosporium, Fusarium Incomplete fungi such as (Fusarium) genus, Penicillium genus, Phoma genus, Trichoderma genus, Rhodotorula genus, Candida genus, Trichophyton genus, etc. .
Examples of yeasts include protozoan fungi such as Schizosaccharomyces, Protomyces, and Taphrina; elastocysts such as Endomyces; Saccharomyces ( Saccharomyces genus Ascomycetes; Candida genus Ascomycete yeast incomplete type; Filobasidiella genus basidiomycetes; Rhodotorula genus, Trichosporon genus , Sporobolomyces genus basidiomycetous yeast incomplete type; Rhodosporidium genus, Sporidiobolus genus, Xanthophyllomyces genus basidiomycetous yeast, etc. Is mentioned.
Examples of the wood-rotting fungi include, for example, the genus Coniophora, the Trametes genus, the Postia genus, the Polya genus, the Gloeophylium genus, the Lentinus genus, and the Paxillas ( Paxillus, Fomitopsis, Pleurotus, Donkioporia, Serpula, Glenospora, Perenniporia, Antrodia Etc.

  Algae are plants that inhabit water and land, have an assimilating pigment, and have an independent nutritional life. For example, cyanobacteria, gray algae, red algae, yellow flagellates, yellow-green algae, green algae Diatoms, brown flagellates, dinoflagellates, green flagellates, brown algae, green worms, axle algae, and the like. The industrial preservative of the present invention exhibits an algal control effect that is particularly excellent in controlling cyanobacteria and green algae. Examples of cyanobacteria include, for example, the genus Oscillatoria, the genus Phormidium, and the green algae include, for example, the genus Chlamydomonas, the genus Chlorococcum, the genus Chlorella, and the genus desmodesmus ( Examples include the genus Desmodesmus, the genus Klebsormidium, the genus Trebouxiophyceae, and the genus Ulothrix.

  Industrial preservatives of the present invention include various industrial waters such as paper pulp mills, cooling water circulation processes, metal working fluids such as cutting oil, coated paper, paper coating fluids, paints, adhesives, casein, Various industrial products such as starch paste, glue, synthetic rubber latex, emulsion, printing ink, polyvinyl alcohol film, vinyl chloride film, plastic product, cement admixture, sealing agent, joint material, deodorant, fiber, leather product, filter, etc. It can be effectively used for controlling harmful microorganisms. More specifically, antibacterial and antibacterial agents such as slime control agents in paper pulp mills and cooling water circulation processes, antibacterial and fungicidal agents such as paper products and resin products, paints, synthetic rubber latex, resins, inks, and silicone sealing agents. It is useful as a mold agent.

  The industrial preservative of the present invention may be appropriately selected depending on the application target, the type of microorganism to be controlled (bacteria, mold, yeast, algae, etc.) and the control period. When used as a slime control agent, the total amount of antibacterial components is 0.1 mg to 500 mg, preferably 0.5 mg to 100 mg per kg of product. When used as a preservative, antibacterial is 1 kg of product. 1 mg to 5,000 mg, preferably 10 mg to 1,000 mg as a total amount of sexual components, and when used as a fungicide / yeast agent or an algae proof agent, 10 mg to 50, 000 mg, preferably 100 mg to 10,000 mg may be added.

Hereinafter, the present invention will be described in more detail with reference to formulation examples and test examples, but the present invention is not limited to these examples.
Test examples show that the industrial preservative of the present invention has antibacterial activity against bacteria, molds and yeasts.

<Evaluation of antibacterial properties>
(1) Test specimen The composition of the industrial preservative of Examples 1 to 15 of the present invention is shown in Table 1, and the composition of the industrial preservative of Comparative Examples 1 to 6 is shown in Table 2. In preparing the compositions of the following Examples and Comparative Examples, the following compounds were used as the isothiazoline-based compound and N-phenylmaleimide.
N-phenylmaleimide used “Imirex P” manufactured by Nippon Shokubai Co., Ltd.
“H-MIT”: 2-methyl-4-isothiazolin-3-one (“Zonen MT” manufactured by Chemicrea Co., Ltd.)
“MITs”: a mixture of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one (“Caisson LX-SF25” manufactured by Rohm and Haas, “H-MIT” And the mixing ratio of “Cl-MIT” is 1: 3 by weight.)
“OIT”: 2-n-octyl-4-isothiazolin-3-one (Rohm and Haas)
“DCOIT”: 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (“BIO-DCOIT-97” manufactured by Dalian Baiyun Chemical Co., Ltd.)
“BIT”: 1,2-benzoisothiazolin-3-one (manufactured by Dow Chemical Company)

（２）抗菌性（抗細菌）の試験方法
上記試験検体を、グルコースブイヨン培地（ｐＨ６．０）にそれぞれ添加し、その後、ミクロプランター（（株）佐久間製作所製）を用いて、表３〜７に記載の細菌を含有する細菌懸濁液を接種して、３３℃で１８時間培養した。その後、培養後の細菌の生育を観察して、最小発育阻止濃度（ＭＩＣ：μｇ／ｍＬ）をそれぞれ算出した。試験はそれぞれ５回行い、その平均値をＭＩＣ値として使用した。
（３）抗菌性（防カビ、防酵母）の試験方法
上記試験検体を、グルコースブイヨン培地（ｐＨ６．０）にそれぞれ添加し、その後、ミクロプランター（（株）佐久間製作所製）を用いて、表３〜７に記載のカビを含有するカビ懸濁液および酵母懸濁液を接種して、３３℃で１８時間、２８℃で２日間培養した。その後、培養後の各菌の生育を観察して、最小発育阻止濃度（ＭＩＣ：μｇ／ｍＬ）をそれぞれ算出した。試験はそれぞれ５回行い、その平均値をＭＩＣ値として使用した。

(2) Test method of antibacterial property (antibacterial) Each of the above test specimens was added to a glucose broth medium (pH 6.0), and then a micro planter (manufactured by Sakuma Seisakusho Co., Ltd.) was used. A bacterial suspension containing the bacteria described in 1) was inoculated and cultured at 33 ° C. for 18 hours. Thereafter, the growth of the bacteria after culturing was observed, and the minimum inhibitory concentration (MIC: μg / mL) was calculated. Each test was performed 5 times, and the average value was used as the MIC value.
(3) Antibacterial (antifungal, yeast prevention) test method The above test specimens were added to a glucose broth medium (pH 6.0), respectively, and then a micro planter (manufactured by Sakuma Seisakusho Co., Ltd.) was used. Mold suspension and yeast suspension containing the mold described in 3-7 were inoculated and cultured at 33 ° C. for 18 hours and at 28 ° C. for 2 days. Thereafter, the growth of each bacterium after the culture was observed, and the minimum growth inhibitory concentration (MIC: μg / mL) was calculated. Each test was performed 5 times, and the average value was used as the MIC value.

(4) Antibacterial Evaluation Method Antibacterial evaluation is performed on test specimens of Examples 1 to 15 based on MIC values when N-phenylmaleimide and an isothiazoline compound are used alone (Comparative Examples 1 to 6). The theoretical value of MIC was calculated by the following formula, and the actually measured MIC value was compared with them. When the measured value of MIC is smaller than the calculated value of the theoretical value, that is, when the “measured value / theoretical 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 N-phenylmaleimide is used alone (Comparative Example 1) C _B ; MIC value when each isothiazoline-based compound is used alone (Comparative Examples 2 to 6) x: in antibacterial component Of N-Phenylmaleimide in (% by weight)
y: Ratio of the isothiazoline compound in the antibacterial component (% by weight)

  The evaluation results of antibacterial activity are shown in Tables 3 to 7. “100/0”, “75/25”, “50/50”, “25/75” and “0/100” in each table are blending weight ratios of N-phenylmaleimide and each of the isothiazoline compounds. Indicates.

  Table 3 shows that N-phenylmaleimide and isothiazoline-based compounds are 2-methyl-4-isothiazolin-3-one: “H-MIT” at 100: 0, 75:25, 50:50, 25:75 and 0. : The evaluation result about the industrial preservative (Examples 1-3 and Comparative Examples 1 and 2) contained by the weight ratio of 100 is shown.

  As is clear from Table 3, the industrial preservatives of Examples 1 to 3 have a measured / theoretical value of MIC of less than 1 for bacteria, molds, and yeast, and N-phenylmaleimide and 2-methyl- 4-isothiazolin-3-one: A synergistic improvement in antibacterial activity was observed as compared with the case where each of “H-MIT” was used alone (Comparative Examples 1 and 2).

  Table 4 shows a mixture of N-phenylmaleimide and isothiazoline-based compounds of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one: “MITs”. The evaluation result about the industrial preservative (Examples 4-6 and Comparative Examples 1 and 3) contained by weight ratio of: 0, 75:25, 50:50, 25:75, and 0: 100 is shown.

  As is apparent from Table 4, the industrial preservatives of Examples 4 to 6 have a measured / theoretical value of MIC of less than 1 for bacteria, mold and yeast, and N-phenylmaleimide and 2-methyl- Mixture of 4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one: synergistic antibacterial activity compared to the case where “MITs” was used alone (Comparative Examples 1 and 3) Improvement was observed.

  Table 5 shows N-phenylmaleimide and isothiazoline-based compounds as 2-n-octyl-4-isothiazolin-3-one: "OIT" at 100: 0, 75:25, 50:50, 25:75 and 0. : The evaluation result about the industrial preservative (Examples 7-9 and Comparative Examples 1 and 4) contained by the weight ratio of 100 is shown.

  As is clear from Table 5, the industrial preservatives of Examples 7 to 9 have a measured / theoretical value of MIC of less than 1 for bacteria, fungi and yeast, and N-phenylmaleimide and 2-n- Octyl-4-isothiazolin-3-one: A synergistic improvement in antibacterial activity was observed compared to the case where “OIT” was used alone (Comparative Examples 1 and 4).

  Table 6 shows that N-phenylmaleimide and isothiazoline-based compounds are 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one: “DCOIT” at 100: 0, 75:25, 50:50. Evaluation results for industrial preservatives (Examples 10 to 12 and Comparative Examples 1 and 5) contained at a weight ratio of 25:75 and 0: 100 are shown.

  As is clear from Table 6, the industrial preservatives of Examples 10 to 12 have a measured / theoretical value of MIC of less than 1 for bacteria, molds and yeast, and N-phenylmaleimide and 4,5- Dichloro-2-n-octyl-4-isothiazolin-3-one: A synergistic improvement in antibacterial activity was observed as compared to the case where each of “DCOIT” was used alone (Comparative Examples 1 and 5).

  Table 7 shows weight ratios of N-phenylmaleimide and 1,2-benzisothiazolin-3-one: "BIT" as isothiazoline-based compounds at 100: 0, 75:25, 50:50, 25:75 and 0: 100. The evaluation result about the industrial preservative (Examples 13-15 and Comparative Examples 1 and 6) contained in is shown.

  As is apparent from Table 7, the industrial preservatives of Examples 13 to 15 had a measured / theoretical value of MIC of less than 1 for bacteria, molds, and yeast, and N-phenylmaleimide and 1,2- Benzoisothiazolin-3-one: A synergistic improvement in antibacterial activity was observed as compared to the case where “BIT” was used alone (Comparative Examples 1 and 6).

In Tables 3 to 7, the details of bacteria, molds and yeasts used in the minimum inhibitory concentration test are described below.
<Bacteria>
Bacillus subtilis: Bacillus subtilis
Staphylococcus aureus
Escherichia coli
<Mold>
Cladosporium cladosporioides
Aureobasidium pullulans
Alternaria sp .: Alternaria sp.
<Yeast>
Saccharomyces cerevisiae: Saccharomyces cerevisiae

From the results shown in Tables 3 to 7, the industrial preservative containing the isothiazoline compound and N-phenylmaleimide as active ingredients was used to control bacteria, mold and yeast, each of the isothiazoline compound and N-phenylmaleimide. It was confirmed that a specific improvement compared to the activity, that is, a synergistic effect far exceeding the expected effect when only two agents were used alone, was obtained. In particular, since the growth can be prevented at a low concentration with respect to “Alternaria species” which is a problem in industrial use, it can be expected more practically.
From this result, it was confirmed that the industrial preservative of the present invention has an excellent antibacterial effect.

  Next, regarding the industrial preservative containing the isothiazoline compound represented by the general formula (1) and N-phenylmaleimide, the concentration range having antibacterial activity against bacteria, molds and yeasts was examined.

<Examination of concentration range with antibacterial activity>
(1) Test specimen Table 8 shows the compositions of the industrial preservatives of Examples 16 to 24 of the present invention. In addition, the above-mentioned compound was used for the isothiazoline type compound and N-phenylmaleimide represented by the general formula (1).

  Tests were conducted five times in the same manner as in the above-mentioned “antibacterial evaluation method”, and the results of studies on the concentration range having antibacterial activity are shown in Tables 9 to 12. In each table, "100/0", "99/1", "98/2", "95/5", "75/25", "50/50", "25/75", "1/99" "And" 0/100 "indicate the weight ratio of N-phenylmaleimide and the isothiazoline-based compound.

  As is clear from Tables 9 to 12, the industrial preservative containing the isothiazoline compound represented by the general formula (1) and N-phenylmaleimide is specific to bacteria, molds and yeasts. A synergistic improvement in antibacterial activity was observed within the weight ratio range. Specifically, the isothiazoline-based compound represented by the general formula (1) of “H-MIT”, “OIT”, and “DCOIT” and N-phenylmaleimide in a weight ratio of 99: 1 to 1:99. In the range of containing “MITs” and N-phenylmaleimide in a weight ratio of 98: 2 to 1:99, the isothiazoline compound represented by the general formula (1) and N-phenyl It was confirmed that a synergistic effect far exceeding that expected when maleimides were used alone was obtained.

  The industrial preservative of the present invention has a high control activity against bacteria, molds and yeasts, and therefore can be used for a wide range of industrial uses such as control of harmful microorganisms in industrial water and various industrial products, and each of those uses. It is possible to provide an industrial preservative having a synergistic improvement in antibacterial activity.

Claims (7)

An industrial preservative comprising an isothiazoline compound represented by the general formula (1) or the general formula (2) and N-phenylmaleimide.
General formula (1):

[Wherein, R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ₂ and R ₃ are the same or different and each represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. Show. ]
General formula (2):

[Wherein, A ₁ ring represents a benzene ring optionally substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms, and Y represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ]   2. The isothiazoline compound represented by the general formula (2) is 1,2-benzisothiazolin-3-one or Nn-butyl-1,2-benzisothiazolin-3-one according to claim 1. Industrial preservative.   The industrial preservative according to claim 1 or 2, wherein the isothiazoline-based compound and N-phenylmaleimide are contained in a weight ratio of 99: 1 to 1:99.   The industrial preservative according to claim 1 or 2, wherein the isothiazoline-based compound and N-phenylmaleimide are contained in a weight ratio of 98: 2 to 1:99.   The isothiazoline compound represented by the general formula (1) is 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- The industrial preservative according to any one of claims 1, 3, and 4, which is one or more selected from the group consisting of n-octyl-4-isothiazolin-3-one.   An industrial product containing the industrial preservative according to claim 1.   The preservation | save method of the industrial material which applies the industrial preservative in any one of Claims 1-5 to an industrial material.