JP2002003307A - Industrial sterilizer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sterilizer for industrial use capable of extending antibacterial spectra of isothiazolone-based industrial sterilizers, stable for a long time of storage, good in compatibility for emulsions and giving no emulsion shock. SOLUTION: In this industrial sterilizer, a nitroalcohol compound (a) and an isothiazolone-based compound (b) are used as effective ingredients, an alkali metal nitrate (c) is added as a stabilizer, and further, an alkali metal chloride (d) and a water soluble glycol-based solvent are added. The industrial sterilizer has solved all the aforesaid problems.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial germicide containing a nitro alcohol compound and an isothiazolone compound as active ingredients, and more particularly to a stabilized industrial germicide containing a nitro alcohol compound and an isothiazolone compound. The present invention relates to a method for stabilizing an industrial bactericide containing an agent and a nitro alcohol compound and an isothiazolone compound.

[0002]

2. Description of the Related Art Conventionally, water used in the papermaking process of the pulp and paper industry, various types of water such as circulating cooling water in various industrial fields, and aqueous paints, coating solutions for paper, latex emulsions, textile emulsions, and spinning oils Water used in the production of cutting oil, printing paste, leather, etc. is susceptible to propagation of harmful microorganisms. The water in which the microorganisms have propagated causes the generation of offensive odors and the like, thereby deteriorating the working environment and lowering the productivity and product quality in the industry. For this reason, many kinds of preservatives and disinfectants are used in industrial water and the like for controlling and sterilizing the propagation of the microorganisms. Isothiazolone compounds are known as one of the agents for suppressing or controlling the generation of harmful microorganisms in industrial water and the like, and have excellent effects as industrial germicides and antibacterial agents. However, this isothiazolone-based compound has a problem that the antibacterial spectrum is narrow at a practical concentration and cannot be applied to various microorganisms. Further, the free form of the isothiazolone-based compound is very sensitive to water, moisture, temperature, and the like, and is easily decomposed. Therefore, it is usually stored in a state of being dissolved in an organic solvent containing no water.

[0003] In order to broaden the antibacterial spectrum of industrial bactericides, various antibacterial agents, fungicides and antialgal agents have been studied in combination, and for example, antibacterial agents such as 2-bromo-2-nitro-1,3-propanediol. It has also been proposed to use it in combination (Japanese Patent Publication No. 58-4682), but the stability of the active ingredient is still insufficient, and when incorporated in an emulsion, the emulsion phase is destroyed, so-called emulsion shock tends to occur. is there. As an organic solvent suitable for dissolving the isothiazolone-based compound, a glycol-based organic solvent or the like is usually used. However, preparations made into a solution with the glycol-based organic solvent are specified as dangerous substances by the Fire Service Act, and special care must be taken in their handling and storage. There was a problem that it was difficult to use safely and easily. Thus, as a preparation containing an isothiazolone compound that can be used safely, a preparation diluted with water and having a reduced concentration of an organic solvent has been proposed. However, when a formulation dissolved in a glycol-based organic solvent is diluted with water so as to have an appropriate concentration as an industrial fungicide, problems such as decomposition of the isothiazolone-based compound in a short period of time and formation of a precipitate occur.

To solve these problems, for example, Japanese Patent Application Laid-Open Nos. 5-21813, 5-170608 and 5-286815 disclose bromic acid or iodine in an aqueous solution of an isothiazolone compound. A composition containing an alkali metal salt of an acid as a stabilizer is disclosed, and the effect that the isothiazolone-based compound in the composition does not decompose and exists stably for a long period of time is described. . However, even in a preparation containing an alkali metal salt of bromate or iodate, for example, water stabilized with potassium bromate and an isothiazolone compound, when the concentration of the potassium bromate is reduced, the thermal stability of the isothiazolone compound is reduced. There is a problem in that the isothiazolone-based compound is easily decomposed. In addition, in a preparation containing a high concentration of an alkali metal salt of bromate or iodic acid, when the temperature of the preparation is lowered to about several degrees Celsius or less, the alkali metal salt is precipitated, and the performance of the preparation is deteriorated. This is because the solid content of the alkali metal salt or the like once deposited is difficult to re-dissolve, so that the concentration of the alkali metal salt of bromate or iodate is substantially reduced, and the isothiazolone-based compound is destabilized.

[0005]

SUMMARY OF THE INVENTION Under the above circumstances, an object of the present invention is to provide a broad antibacterial spectrum, a stable active ingredient for a long period of time without using an organic solvent, and a shock to an emulsion. There is no need to provide industrial germicides.

[0006]

The present inventors have conducted various studies to solve the above-mentioned problems. As a result, the present inventors have used nitro alcohol compounds and isothiazolone compounds as active ingredients, and nitric acid as a stabilizer for these active ingredients. By blending an alkali metal salt and, if necessary, further an alkali metal chloride, it has a broad antibacterial spectrum, maintains high storage stability for a long time even when an organic solvent is not used, and can be blended into an emulsion. We have succeeded in obtaining an excellent industrial germicide that does not cause emulsion shock. That is, the present invention provides an industrial bactericide comprising (1) a nitro alcohol compound (a), an isothiazolone-based compound (b) and an alkali metal nitrate (c), (2)
The industrial disinfectant according to the above (1) further containing an alkali metal chloride (d), (3) the above (1) or (2) further containing a water-soluble glycol solvent (e). An industrial fungicide of formula (4) (a) having the general formula (1)

Embedded image (Wherein, X ¹ is an alkyl group having 1 to 4 carbon atoms having a hydroxyl group or a halogen atom, Y ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, and Y ² is A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms having a hydroxyl group or an alkenyl group having 2 to 4 carbon atoms which may have a hydroxyl group.) The industrial bactericide according to (1), wherein (5) (a) is 2-bromo-2-nitropropane-1,3-diol or 2,2-dibromo-2-nitroethanol. Fungicide,
(6) (b) is a general formula (2)

[0007]

Embedded image (Wherein X ² and X ³ are the same or different and are each a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms,
Y ³ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent. And (7) (b) is 2-methyl-4-isothiazolin-3-one or 5-chloro-2-methyl-4-isothiazoline-. The industrial germicide according to the above (1), which is 3-one, (8) (c) is sodium nitrate or potassium nitrate, the industrial germicide according to the above (1), (9) (d) is sodium chloride or (10) The industrial bactericide according to the above (2), which is potassium chloride.
(E) is ethylene glycol, propylene glycol,
The industrial bactericide according to the above (3), which is diethylene glycol, dipropylene glycol or diethylene glycol monomethyl ether, wherein (11) (a) is 0.01
(1) comprising -40% by weight, 0.01-20% by weight of (b) and 0.01-30% by weight of (c).
The industrial disinfectant according to any one of (12) to (11), wherein
The industrial disinfectant according to the above (11) comprising 5% by weight, (13) the industrial disinfectant according to the above (11) or (12) further comprising (e) 0.1 to 90% by weight. (1) to (1), which are a latex preservative, a synthetic resin emulsion preservative, or a paint preservative.
(3) Stabilization of (a) and (b), wherein the industrial disinfectant according to any one of (3) and (15), a nitro alcohol compound (a) and an isothiazolone compound (b) are mixed with an alkali metal nitrate (c). (16) The method of (15), wherein (a) is further mixed with an alkali metal chloride (d).
And (b) the stabilization method.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The nitro alcohol compound (a) used in the present invention is, for example, a compound represented by the following general formula (1):

Embedded image(Where X¹Has a hydroxyl group and has 1 to 4 carbon atoms.
Alkyl group or halogen atom, Y¹Is a hydrogen atom, carbon
Alkyl group having 1 to 4 carbon atoms or alkenyl having 2 to 4 carbon atoms
Group, Y²Represents a hydrogen atom, a halogen atom, a hydroxyl group
C 1-4 alkyl or hydroxyl group
Represents an alkenyl group having 2 to 4 carbon atoms which may have
You. )). (1) Formula smell
And X¹And Y²Having a hydroxyl group represented by
Examples of the alkyl group having 1 to 4 carbon atoms include, for example, methyl
Group, ethyl group, propyl group, isopropyl group, butyl
Group, an alkyl group having 1-4 carbon atoms such as an isobutyl group.
A group having at least one hydroxyl group substituted at a desired position;
I can do it. X¹And Y ²And a halogen atom represented by
For example, fluorine, chlorine, bromine, iodine, etc.
can give. Y¹Alkenyl having 2-4 carbon atoms represented by
For example, vinyl groups, allyl groups, isoprene
Examples include a lophenyl group and a 2-methyl-1-propenyl group.
Can be Y²Even if it has a hydroxyl group represented by
Examples of the good alkenyl group having 2 to 4 carbon atoms include the aforementioned carbon atoms.
At least one at any position of the alkenyl group represented by the formula (2-4);
And a group in which a hydroxyl group is substituted.

Specific examples of the nitro alcohol compound represented by the formula (1) include, for example, 2-bromo-2-nitropropane-1,3-diol (BNPD), 2-bromo-2-nitrobutane-1, 3-diol, 3-bromo-3-nitropentane-2,4-diol, 2,2-dibromo-2-nitro-1-ethanol (DBNE), 2
-Nitro-1,3-propanediol, tris (hydroxymethyl) nitromethane, 3,3-dibromo-3-nitro-2-propanol, 2-chloro-2-nitroethanol, 2-chloro-2-nitro-1, 3-propanediol, 3-chloro-3-nitro-2-propanol,
And so on.

The isothiazolone compound used in the present invention includes, for example, a compound represented by the following general formula (2)

Embedded image (Wherein X ² and X ³ are the same or different and are each a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms,
Y ³ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent. )).

In the formula (2), examples of the halogen represented by X ² and X ³ include fluorine, chlorine, bromine and iodine, among which chlorine is preferred. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group,
And a methyl group. In the alkyl group,
For example, a group having 1 carbon atom such as a methyl group, an ethyl group, and a propyl group.
The alkyl group of -4 is preferred. Among the substituents described above, X ² is preferably hydrogen or chlorine, and more preferably chlorine. X ³ is preferably hydrogen or chlorine, and more preferably hydrogen. Examples of the substituent of the hydrocarbon group having 1 to 8 carbon atoms which may have a substituent represented by Y ³ include a hydroxyl group, a halogen (eg, chlorine, fluorine, bromine, iodine, etc.), a cyano group, an amino group , A carboxyl group, an alkoxy group having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group, etc.), 6 to 10 carbon atoms.
(E.g., a phenoxy group), an alkylthio group having 1 to 4 carbon atoms (e.g., methylthio group, ethylthio group, etc.) and an arylthio group having 6 to 10 carbon atoms (e.g., phenylthio group, etc.). Among the substituents, a halogen atom, an alkoxy group having 1 to 4 carbon atoms and the like are preferable. In these substituents, the hydrogen of the hydrocarbon group may be substituted in the range of 1 to 5, preferably 1 to 3, and the substituents may be the same or different.

The hydrocarbon group of the optionally substituted hydrocarbon group represented by Y ³ includes, for example, a group having 1 to 1 carbon atoms.
Examples thereof include an alkyl group having 0, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 6 to 14 carbon atoms. Among the hydrocarbon groups, an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms are preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. The carbon number 1
As the alkyl group of -10, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, Examples include an isooctyl group, a sec-octyl group, a tert-octyl group, a nonyl group, and a decyl group. Among these alkyl groups, an alkyl group having 1 to 3 carbon atoms such as a methyl group and an ethyl group, and an alkyl group having 7 to 9 carbon atoms such as an octyl group and a tert-octyl group are more preferable. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, and a 2-methyl-1-propenyl group. Among the alkenyl groups, a vinyl group and an allyl group are preferred. Examples of the alkynyl group having 2 to 6 carbon atoms include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, and a pentynyl group. Among the alkynyl groups, an ethynyl group and a propynyl group are preferable.

The cycloalkyl group having 3 to 10 carbon atoms includes, for example, cyclopropyl group, cyclobutyl group,
Examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Among the above cycloalkyl groups, a cyclopentyl group and a cyclohexyl group are preferred. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, an anthryl group,
A phenanthryl group and the like. Among the aryl groups, a phenyl group is preferred. As described above, Y ³
There may be various hydrocarbon groups which may be substituted, and among these hydrocarbon groups, a methyl group and an octyl group are more preferred, and a methyl group is more preferred. Specific examples of the isothiazolone-based compound represented by the above formula (1) include, for example, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4
-Isothiazolin-3-one, 2-n-octyl-4-
Isothiazolin-3-one, 4,5-dichloro-2-n
-Octyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4 -Isothiazoline-3
-One, 5-chloro-2-t-octyl-4-isothiazolin-3-one and the like. Among the above compounds, 5-chloro-2-methyl-4-isothiazoline-3
-One, 2-methyl-4-isothiazolin-3-one,
2-n-octyl-4-isothiazolin-3-one,
4,5-Dichloro-2-n-octyl-4-isothiazolin-3-one is preferred, and 5-chloro-2-methyl-
4-isothiazolin-3-one and 2-methyl-4-
Isothiazolin-3-one is particularly preferred.

The isothiazolone compounds represented by the formula (2) are used alone or in combination of two or more. Therefore,
The two or more compounds may be used in a mixed state.
These isothiazolone compounds are all known compounds, for example, US Pat. No. 3,761,488, US Pat. No. 3,849,430, US Pat.
No. 870797, U.S. Pat. No. 4,067,878, U.S. Pat. No. 4,15,0026, U.S. Pat. No. 4,241,214, U.S. Pat. No. 3,517,022, U.S. Pat. No. 3,065,123, U.S. Pat. No. 3,761,489. Description and US Patent No. 3849
It can be produced by the method described in the specification of JP-A-430-430 or a method analogous thereto. Next, the alkali metal nitrate (c) contained as a stabilizer in the nitro alcohol compound (a) and the isothiazolone compound (b) according to the present invention will be described. Examples of the alkali metal of the alkali metal nitrate include lithium, sodium, potassium, rubidium and the like. Among them, sodium and potassium are preferable. Examples of the alkali metal of the alkali metal chloride (d) used in the present invention include lithium, sodium, potassium, rubidium and the like. Among them, sodium and potassium are preferable, and sodium is particularly preferable.
When these alkali metal nitrates or alkali metal chlorides are dissolved in water and used, an appropriate solvent may be appropriately added. Examples of the solvent include water-soluble glycol solvents, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and the like. Among these, ethylene glycol,
Propylene glycol, diethylene glycol and dipropylene glycol are preferred.

The water-soluble glycol solvent (e) used in the present invention includes, for example, those having 2 carbon atoms such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol and 1,5-pentanediol. -6 alkylene glycol solvents and glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and triprolene glycol monomethyl ether. Can also be given. Among the alkylene glycols having 2 to 6 carbon atoms, dipropylene glycol is preferable, and among glycol ether compounds, diethylene glycol monomethyl ether is preferable. The mixing ratio of each component excluding water in the industrial germicide of the present invention is (a) 0.01 to 40% by weight, preferably 0.1 to 25% by weight, and (b) 0.01 to 20% by weight. %, Preferably 0.1 to 10% by weight, and (c) is 0.01% by weight.
-30% by weight, preferably 0.1-15% by weight;
0.1 to 5% by weight, preferably 0.5 to 3% by weight when using (d), and 0.1 to 90% when using (e).
%, Preferably 5 to 70% by weight. The pH of the industrial germicide of the present invention may be adjusted when preparing a formulation containing water. The pH when adjusting is preferably about 3
~ 6.

Examples of the pH adjusting agent include an inorganic acid, an organic compound having a carboxyl group, sulfonic acid,
Acids such as phenolic compounds are mainly used. Specific examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, nitrous acid, carbonic acid, hydrofluoric acid, hydrogen sulfide and the like. Specific examples of the organic compound having a carboxyl group include, for example, acetic acid, trifluoroacetic acid, phthalic acid, citric acid, formic acid, oxalic acid, tartaric acid,
In addition to benzoic acid, ethylenediaminetetraacetic acid (EDTA), potassium hydrogen phthalate and the like, amino acids such as glutamic acid and glycine can be mentioned. Specific examples of the sulfonic acid include, for example, p-toluenesulfonic acid and methanesulfonic acid, and specific examples of the phenolic compound include, for example, phenol. In addition, in finely adjusting the pH, for example, an inorganic base, a nitrogen-containing organic compound, or a base of an amino acid compound is used together with the acid. Specific examples of the inorganic base include, for example, sodium hydroxide, potassium hydroxide, ammonia, calcium hydroxide, magnesium oxide, sodium carbonate, sodium hydrogen carbonate and the like. Specific examples of the nitrogen-containing organic compound include, for example, aniline, piperazine, piperidine, triethylamine, pyridine and the like. Specific examples of the amino acid compound include histidine and glutamine.

The method for preparing the industrial bactericide (formulation) of the present invention is not particularly limited, and the compounds may be blended in any order, but the following method is considered. Nitro alcohol compound, isothiazolone compound in water,
An alkali metal nitrate and, if necessary, an alkali metal chloride are added, and mixed using a mixer or the like until the mixture is completely uniform. The alkali metal nitrate and the alkali metal chloride to be added may be once dissolved in water or a mixture of water and an organic solvent as described above, and then mixed with water. The composition containing an isothiazolone-based compound according to the present invention may contain the water-soluble glycol-based solvent described above.

When a water-soluble glycol solvent is used, the method of preparing the liquid preparation is the same as in the case where the solvent is not used. A predetermined amount of a nitro alcohol compound, an isothiazolone compound and other components are blended, and then a stirrer is used. Stir and mix until completely uniform to obtain product. The industrial disinfectant according to the present invention may further contain another disinfectant. Examples of the fungicide include 2,2-dibromo-3-nitrilopropionamide, 3-iodo-2-propynylbutyl carbamate, methyl 2-benzimidazole carbamate, 3,3,4,4-tetrachloromethane Tetrahydrothiophen-1,1-dioxide, 4,5-dichloro-1,2-dithiole-3-one, tetrachloroisophthalonitrile, methylenebisthiocyanate, 1,2-
Benzoisothiazoline-3-one zinc pyrithione and the like. The addition amount of these fungicides is preferably about 0.1 to 20 parts by weight based on 100 parts by weight of the isothiazolone compound. Further, known additives such as a surfactant and an antioxidant may be added to the industrial disinfectant according to the present invention, depending on the purpose, use, and the like.

Examples of the surfactant include known surfactants such as soaps, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and polymeric surfactants. Among them, a nonionic surfactant and an anionic surfactant are preferable. Examples of the nonionic surfactant include polyoxyalkylene aryl phenyl ether, polyoxyethylene nonyl phenyl ether, and a block copolymer of ethylene oxide and propylene oxide. Examples of the anionic surfactant include a metal salt of alkyl benzene sulfonic acid, a metal salt of alkyl naphthalene sulfonic acid, a metal salt of polycarboxylic acid, a metal salt of dialkyl sulfosuccinate, a ammonium salt of polyoxyethylene distyrenated phenyl ether sulfate, Metal salts of lignin sulfonic acid, metal salts of lignin sulfonic acid and the like can be mentioned. Examples of the metal salt include a sodium salt, a potassium salt, and a magnesium salt.

Examples of the antioxidant include phenolic antioxidants such as 2,6-di-t-butyl-4-methylphenol and 2,2′-methylenebis [4-methyl-6-t-butylphenol]; Diphenylamine, N,
And amine antioxidants such as N'-di-s-butyl-p-phenylenediamine. The amount of the surfactant and antioxidant to be added is, for example, preferably 0.1 to 5 parts by weight for 100 parts by weight of the liquid in the case of the liquid. When adding the other bactericides, surfactants, and additives such as antioxidants to the industrial germicides according to the present invention, alkali metal nitrates, alkali metal chlorides, water-soluble glycol solvents, water, etc. Is preferably changed according to the type of these additives. Industrial disinfectant of the present invention is used in various fields of industry conventionally used, among them white water in the papermaking process,
Suitable for latex, synthetic polymer emulsion, pigment, paint, processing solution for printing plate, adhesive, cooling water, ink, cutting oil, cosmetics, non-woven fabric, spinning oil, leather, etc., synthetic polymer emulsion More suitable for spinning oil, cutting oil, ink and the like.

When using the industrial disinfectant according to the present invention, known methods such as a dropping method, an intermittent addition method, a coating method, a spraying method and a dipping method can be used. The above method may be properly used depending on the object and purpose. In this case, the industrial fungicide is added so that the total final concentration of the active ingredient is 1 to 5000 relative to the target water-containing composition.
ppm, preferably 5 to 1000 p
More preferably, it is added to about pm. For example, in the case of latex, the final concentration of the active ingredient (nitro alcohol compound and isothiazolone compound) is 5 to 5.
It is preferable to add so as to be 500 ppm.

[0022]

The present invention will now be described more specifically with reference to examples, comparative examples and test examples. Example 1 2-Methyl-4-isothiazolin-3-one (MIT)
0.75 g, 5-chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT) 2.25 g, 2-bromo-2-nitropropane-1,3-diol (BNP
D) 15 g, 4.3 g of sodium nitrate (NaNO ₃ ) and 1.3 g of sodium chloride (NaCl) in 75.4 of water.
g (solution A). Further, 1 g of water was added to obtain a preparation (100 g).

Example 2 The solution A obtained in Example 1 was further added with potassium nitrate (K
NO ₃ ) (1.0 g) was added and dissolved to obtain a preparation (100 g). Example 3 0.75 g of MIT, 2.25 g of Cl-MIT, 2,2-
1.0 g of dibromo-2-nitroethanol (DBNE)
4.3 g of sodium nitrate and 1.3 g of common salt were dissolved in a mixture of 40 g of diethylene glycol and 49.4 g of water (solution B). Further, 1 g of water was added to obtain a preparation (100 g). Example 4 The solution B obtained in Example 3 was further added with potassium nitrate 1.
0 g was added and dissolved to obtain a preparation (100 g).

Comparative Example 1 MIT 0.75 g, Cl-MIT 2.25 g, BNPD
15 g and 0.3 g of 5-bromo-5-nitro-1,3-dioxane (Bronidox K; manufactured by Rohm and Haas Co.) were mixed with 18 g of dipropylene glycol and water 6
The mixture was dissolved in 3.7 g of the mixture to obtain a preparation (100 g). Comparative Example 2 MIT 0.27 g, Cl-MIT 2.73 g, BNPD
15 g and 0.3 g of potassium bromate were added to and mixed with a mixture of 22 g of ethylene glycol and 59.7 g of water to obtain a preparation (100 g).

Comparative Example 3 MIT 0.21 g, Cl-MIT 2.79 g, BNPD
15 g, magnesium nitrate [Mg (NO ₃ ) ₂ ] 3.2
g and 1.9 g of magnesium chloride (MgCl ₂ ) were dissolved in 76.9 g of water to obtain a preparation (100 g). Comparative Example 4 0.27 g of MIT, 2.73 g of Cl-MIT and B
15 g of NPD was added to and dissolved in a mixture of 22 g of ethylene glycol and 60 g of water to obtain a preparation (100 g). Comparative Example 5 MIT 0.27 g, Cl-MIT 2.73 g, BNPD
15 g and 0.3 g of 5-bromo-5-nitro-1,3-dioxane (Bronidox K; manufactured by Rohm and Haas Company) were added to 81.7 g of water, dissolved, and the formulation (1
00g). Comparative Example 6 MIT 0.27 g, Cl-MIT 2.73 g, DBNE
1 g and potassium bromate (0.3 g) were mixed with ethylene glycol (22 g), diethylene glycol (21 g) and water.
The mixture was dissolved in 7 g of the mixture to obtain a preparation (100 g).
The compositions of the preparations of Example 1-4 and Comparative Example 1-6 are summarized in [Table 1].

[0026]

[Table 1]

Test Example 1 Residual ratio of active ingredient and change in appearance after storage for 4 weeks The preparations of Examples 1 to 4 and Comparative Examples 1 to 6 were respectively sealed in glass bottles and stored in a thermostat at 60 ° C for 4 weeks. And the active ingredient, 2-
Methyl-4-isothiazolin-3-one (MIT), 5
-Chloro-2-methyl-4-isothiazolin-3-one (Cl-MIT), 2-bromo-2-nitropropane-
1,3-diol (BNPD), 2,2-dibromo-2
-The residual ratio (%) of nitroethanol (DBNE) was measured, and the change in appearance was visually observed. The judgment was made according to the following criteria, and the results are shown in [Table 2]. No appearance of turbidity or sediment: ○ No precipitation but turbidity: △ Turbidity or sediment: ×

[0028]

[Table 2] As is clear from Table 2, the preparations of Example 4 containing alkali nitrate and those of Example 1-3 further containing sodium chloride were stable regardless of the presence of glycols and remained MIT. Rate exceeds 70%,
95% of l-MIT, BNPD and DBNE remaining
In contrast, the preparation of Comparative Example 1-6 in which alkali nitrate and sodium chloride were not blended had a MIT residual rate of 60% or less, and C
The residual rates of 1-MIT, BNPD and DBNE were all 90% or less. From these results, in the industrial disinfectant containing both the nitro alcohol compound (a) and the isothiazolone compound (b) as active ingredients, the addition of alkali nitrate and further sodium chloride is remarkable in stabilizing the active ingredients. It has been proved to have a great effect.

Test Example 2 Compatibility test for SBR latex SBR latex (SA-22) and each of the preparations obtained in Examples 1-4 and Comparative Examples 1-6 were placed on a slide glass in a volume ratio of 1: 1. The mixture was mixed at a ratio, and the presence or absence of aggregation of the latex was determined by visual observation according to the following criteria.
The results are shown in [Table 3]. Non-aggregated: ○ Somewhat agglomerated: △ Agglomerated: ×

[0030]

[Table 3] As is clear from Table 3, the formulation of Example 1-4 did not give so-called emulsion shock to the latex, whereas the formulation of Comparative Example 1-6 did not give any effect to the latex. Gave.

[0031]

The industrial bactericide of the present invention is stable for a long time even in the case of a water preparation containing no organic solvent such as water-soluble glycols, and has good compatibility with emulsions such as latex. Does not give so-called emulsion shock.

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[Procedure amendment]

[Submission date] June 28, 2000 (2006.2.
8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

When a water-soluble glycol solvent is used, the method of preparing the liquid preparation is the same as in the case where the solvent is not used. A predetermined amount of a nitro alcohol compound, an isothiazolone compound and other components are blended, and then a stirrer is used. Stir and mix until completely uniform to obtain product. The industrial disinfectant according to the present invention may further contain another disinfectant. Examples of the fungicide include 2,2-dibromo-3-nitrilopropionamide, 3-iodo-2-propynylbutyl carbamate, methyl 2-benzimidazole carbamate, 3,3,4,4-tetrachloromethane Tetrahydrothiophen-1,1-dioxide, 4,5-dichloro-1,2-dithiole-3-one, tetrachloroisophthalonitrile, methylenebisthiocyanate, 1,2-
Benzoisothiazolin-3-one , zinc pyrithione and the like. The addition amount of these fungicides is preferably about 0.1 to 20 parts by weight based on 100 parts by weight of the isothiazolone compound. Furthermore, the industrial bactericide according to the present invention includes:
Known additives such as a surfactant and an antioxidant may be added according to the purpose, use and the like.

[Procedure amendment 2]

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[Table 1]

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[Table 2] As is clear from Table 2, the preparation of Example 1-4 containing alkali nitrate and sodium chloride was stable regardless of the presence or absence of glycols, and the residual ratio of MIT was 70% in all cases. Over, Cl-MIT, BNPD and D
While the residual ratio of BNE was 95% or more, the preparation of Comparative Example 1-6 in which the alkali nitrate and sodium chloride were not blended had a residual ratio of MIT of 60% or less, Cl-MIT, BNPD and D
The residual ratio of BNE was 90% or less in all cases. From these results, in the industrial disinfectant containing both the nitro alcohol compound (a) and the isothiazolone compound (b) as active ingredients, the addition of alkali nitrate and further sodium chloride is remarkable in stabilizing the active ingredients. It has been proved to have a great effect.

Continued on the front page F term (reference) 4H011 AA02 BA04 BA06 BB04 BB10 BC03 BC18 DD01 DD07 DE15 DE17

Claims (16)

[Claims] 1. A nitro alcohol compound (a), an isothiazolone compound (b) and an alkali metal nitrate (c)
An industrial fungicide comprising: 2. The industrial germicide according to claim 1, further comprising an alkali metal chloride (d). 3. The industrial fungicide according to claim 1, further comprising a water-soluble glycol solvent (e). (A) is a compound represented by the general formula (1): (Wherein, X ¹ is an alkyl group having 1 to 4 carbon atoms having a hydroxyl group or a halogen atom, Y ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, and Y ² is A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms having a hydroxyl group, or an alkenyl group having 2 to 4 carbon atoms which may have a hydroxyl group.) The industrial bactericide according to the above. 5. The industrial fungicide according to claim 1, wherein (a) is 2-bromo-2-nitropropane-1,3-diol or 2,2-dibromo-2-nitroethanol. (B) is a compound represented by the general formula (2): (Wherein X ² and X ³ are the same or different and are each a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms,
Y ³ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent. The industrial fungicide according to claim 1, which is a compound represented by the formula: 7. The industrial fungicide according to claim 1, wherein (b) is 2-methyl-4-isothiazolin-3-one or 5-chloro-2-methyl-4-isothiazolin-3-one. 8. The industrial fungicide according to claim 1, wherein (c) is sodium nitrate or potassium nitrate. 9. The industrial fungicide according to claim 2, wherein (d) is sodium chloride or potassium chloride. 10. The industrial fungicide according to claim 3, wherein (e) is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol or diethylene glycol monomethyl ether. (11) 0.01 to 40% by weight of (a), (b)
From 0.01 to 20% by weight and (c) from 0.01 to 30% by weight.
The industrial bactericide according to claim 1, which is contained by weight%. 12. The industrial fungicide according to claim 11, further comprising (d) in an amount of 0.1 to 5% by weight. 13. The industrial fungicide according to claim 11, further comprising (e) in an amount of 0.1 to 90% by weight. 14. The industrial fungicide according to claim 1, which is a preservative for a latex, a synthetic resin emulsion, or a preservative for paints. 15. A method for stabilizing (a) and (b) wherein an alkali metal nitrate (c) is blended with a nitro alcohol compound (a) and an isothiazolone compound (b). 16. The method for stabilizing (a) and (b) according to claim 15, further comprising blending an alkali metal chloride (d).