JPH0733614A - Industrial bactericidal-bacteriostatic agent - Google Patents

Abstract

PURPOSE:To provide the agent comprising an isothiazolone compound, a nitro or cyanobromo compound., and methylene bisthiocyanate in a specific ratio, and exhibiting a remarkable antimicrobial effect and its persistence against various wide microorganisms. CONSTITUTION:An industrial bactericidal.bacteriostatic agent comprises a 3-isothazolone compound of formula I (X<1>, Y<1> are H, halogen; R<1> is 1-8C alkyl) or its metal salt complex, a nitrobromo or cyanobromo compound of formula II [X<2> is nitro, cyano; Y<2>, Y<3> are Br, carbamoyl, group of formula III (R<2>-R<4> are H, methyl), (substituted)alkyl; Y<2> and Y<3> form group of formula IV (A is H, halogen, nitro, alkyl; m is 1-3], and methylene bisthiocyanate. Especially, the agent preferably comprises 1 pt.wt. of the 3-isothiazolone compound, 0.1-9 pts.wt. of the nitrobromo or cyanobromo compound, and 0.03-1.5wt.% (per pt.wt. of the nitro or cyanobromo compound) of the methylene bisthiocyanate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial bactericidal / bacteriostatic agent. More specifically, papermaking process water in the paper and pulp industry, cooling water and washing water for various industries, metalworking oils,
The present invention relates to a fiber oil, a paint, an antifouling paint, a coating liquid for paper, a latex, a sizing agent, and the like, and more particularly to an industrial sterilization / bacteriostatic agent which is useful for preserving and sterilizing starch slurry.

[0002]

2. Description of the Related Art Conventionally, in the papermaking process in the paper and pulp industry and in the cooling water system in various industries, slimes caused by bacteria and fungi are generated, and there are obstacles such as deterioration of product quality and production efficiency. Are known. Also, many industrial products such as metalworking oils, fiber oils, paints, various latexes, sizing agents, and starch slurries are apt to be rotted or contaminated by bacteria and fungi, which spoils the product and reduces its value.

Of these industrial products, starch is known for various uses as a slurry or paste. For example, in paper mills, they are used in large amounts for surface size, color binder and internal addition. Rhizophores such as potato starch and tapioca starch and wheat starch have soil bacteria attached to them, and many Bacillus bacteria with heat-resistant spores are present.

These spores survive at 100 ° C.,
It propagates in a starch slurry in which starch, which is a nutrient source for microorganisms, is abundant along with falling bacteria. When the spoilage progresses due to the growth of microorganisms, spoilage odors, clogging of strainers, and deterioration of quality due to viscosity decrease and pH decrease occur.
Many fungicides have been used to prevent damage by these microorganisms. In the old days, organic mercury compounds, chlorinated phenol compounds and formalin were used,
These drugs are highly toxic to humans and seafood, and their use has been regulated because they cause environmental pollution. Recently, methylenebisthiocyanate, which has relatively low toxicity,
1,2-benzisothiazolin-3-one, organic nitrogen-sulfur system represented by 5-chloro-2-methyl-4-isothiazolin-3-one, 2,2-dibromo-2-nitroethanol, 2,2- Dibromo-3-nitrilopropionamide, 1,2-bis (bromoacetoxy) ethane,
1,4-bis (bromoacetoxy) -2-butene, an organic bromine type represented by bistribromomethylsulfone and an organic sulfur type represented by 4,5-dichloro-1,2-dithiole-3-one The compound is widely used as an industrial fungicide (see "Encyclopedia of Antibacterial and Antifungal Agents" published by the Japan Society for Antibacterial and Antifungal Agents in 1986).

A combination of 2.2-dibromo-2-nitroethanol and methylenebisthiocyanate, 2,
Combination of 2-dibromo-3-nitrilopropionamide and methylenebisthiocyanate 2.2-dibromo-
A combination of 2-nitroethanol and a 3-isothiazolone compound, a combination of 2,2-dibromo-3-nitrilopropionamide and a 3-isothiazolone compound, and 3-
Industrial fungicides have been proposed which exhibit a synergistic effect by combining an isothiazolone compound and methylenebisthiocyanate (JP-A-2-53703, JP-A-57-114502).
JP-A-60-54281, JP-A-61-83105 and JP-A-1
-163106).

[0006]

Since the above-mentioned various low-toxicity bactericides alone are effective only for a narrow range of microorganisms in the sterilization target system, sufficient bactericidal efficacy is obtained in the target system in which various microorganisms are mixed. In addition to the drawback of not being obtained, there was a problem that resistant bacteria appeared even when used for a long time even against effective microorganisms.

In addition, a bactericidal agent comprising a combination of bactericidal agents for the purpose of exerting a synergistic effect has a remarkable bactericidal activity against bacteria and fungi, but the effect is not sustainable, and it is effective against yeast. Has a drawback that its bactericidal power is not sufficient, and its effect is insufficient especially in a target system that requires continuous bactericidal effect for a long period of time by adding a bactericidal agent, such as starch slurry. Therefore, it was not possible to sufficiently prevent the damage caused by microorganisms such as the generation of rotten odor, the strainer clogging, and the product quality deterioration.

The object of the present invention is to provide an industrial bactericidal / bacteriostatic agent having an effective bactericidal activity against a wide variety of microorganisms such as bacteria, molds and yeasts, and maintaining the effect. .

[0009]

From this point of view, the inventor of the present invention has studied the combination and content ratio of various industrial bactericides, and as a result, isothiazolone compounds, nitrobromo compounds or cyanobromo compounds and methylenebisthiocyanate. It has been found that, by combining and in a specific ratio, a remarkable bactericidal effect against a wide variety of microorganisms, which cannot be predicted from the combination of two components, and the sustainability of the bactericidal effect are exhibited.

Thus, according to the present invention, 1) the general formula (1):

[0011]

[Chemical 5] (Wherein X ¹ and Y ¹ are hydrogen atoms or halogen atoms, R ¹ is C
An alkyl group having ₁ -C _8. ) At least one of 3-isothiazolone compounds represented by the formula) or their metal salt complexes 2) General formula (2):

[0012]

[Chemical 6] [In the formula, X ² represents a nitro group or a cyano group, and Y ² , Y ³
Are the same or different and are bromine atom, carbamoyl group or formula

[0013]

[Chemical 7] (In the formula, R ² , R ³ and R ⁴ are each a hydrogen atom or a methyl group)
A group represented by, or Y ² and Y ³ are taken together to form a formula

[0014]

[Chemical 8] (In the formula, A is a hydrogen atom, a halogen atom, a nitro group or C
_{1 to} C ₄ alkyl group, m represents an integer of 1 to 3), or a C _{1 to} C ₄ alkyl group substituted with a hydroxyl group, a bromine atom or a cyano group]. There is provided an industrial bactericidal / bacteriostatic agent comprising at least one of nitrobromo compounds or cyanobromo compounds and 3) methylenebisthiocyanate as an active ingredient.

Although the details of the reason why such a remarkable effect is exerted are not clear, it is considered to be a synergistic effect of a combination of specific compounds in specific ratios. In the present invention, as the 3-isothiazolone compound represented by the general formula (1), 5-chloro-2-methyl-isothiazolin-3-one, 2-methyl-isothiazolin-3-one,
4,5-Dichloro-2-n-octyl-isothiazolin-3-one, 2-n-octyl-isothiazolin-3-one
Onium and metal salt complexes of these with magnesium chloride or calcium chloride. Among these compounds, 5-chloro-2-methyl-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-
It is preferable to use isothiazolin-3-one or a complex thereof with magnesium chloride or calcium chloride from the viewpoint of the bactericidal effect.

As the nitrobromo compound or cyanobromo compound represented by the general formula (2), 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-2-nitroethanol, 2-bromo- 2-nitro-
1,3-diacetoxypropane, 2-bromo-2-nitro-1,3-diformyloxypropane, tribromonitromethane, 1,1-dibromo-1-nitro-2-propanol, 1,1-dibromo-1 -Nitro-2-acetoxyethane, 1,1-dibromo-1-nitro-2-acetoxypropane, 2-nitro-2-bromo-1,3-propanediol, 1,2-dibromo-2,4-dicyanobutane , Β-bromo-β-nitrostyrene, β-bromo-4-chloro-β-nitrostyrene, β-bromo-β-
p-dinitrostyrene and β-bromo-4-methyl-β
-Nitrostyrene. Among these compounds, 2,2-dibromo-3-nitrilopropionamide,
It is preferable to use 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitro-1,3-diacetoxypropane, and β-bromo-β-nitrostyrene from the viewpoint of the bactericidal effect.

In the present invention, the weight ratio of the 3-isothiazolone compound, the nitrobromo or cyanobromo compound and the methylenebisthiocinnate is such that the 3-isothiazolone compound is 1 and the nitrobromo or cyanobromo compound is 0.1 to 9 parts, preferably 0.2-5 parts, 3
It is preferable that the total amount of the isothiazolone compound and the nitrobromo-type or cyanobromo-type compound is 1 and the methylenebisthiocinnate is 0.03 to 1.5 parts, preferably 0.1 to 1 part because a more remarkable synergistic effect is exhibited.

The active ingredient of the present invention is usually preferably used in the form of a liquid formulation. However, the present invention is not limited to this, and may be used in the form of powder or the like depending on the object of use. When the system to be sterilized is process water in the papermaking process, various water systems such as industrial cooling water, starch slurry or synthetic resin emulsion, etc., in consideration of dissolution and dispersibility of the active ingredient, a hydrophilic organic solvent and a dispersant are used. It is preferable to use a liquid formulation containing

Examples of the hydrophilic organic solvent include amides such as dimethylformamide, glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Glycol ethers such as tripropylene glycol monomethyl ether, alcohols having up to 8 carbon atoms or methyl acetate, ethyl acetate, 3-methoxybutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, propylene carbonate, dimethyl glutarate, etc. Esters of water and water.

Among these hydrophilic solvents, ethylene glycol, propylene glycol,
Glycols such as diethylene glycol and dipropylene glycol, methyl cellosolve, phenyl cellosolve,
Glycol ethers such as diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether,
Alcohols or ester type ones having up to 8 carbon atoms such as methyl acetate, ethyl acetate, 3-methoxybutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, propylene carbonate and dimethyl glutarate. Is preferred.

As the dispersant, a cationic surfactant,
Anionic surfactants, nonionic surfactants or amphoteric surfactants are suitable, and nonionic surfactants are preferred from the viewpoint of stability as a preparation. The mixing ratio of these preparations is such that the total amount of the bactericide active ingredient is 1 to 50 parts by weight, the dispersant is at least 0.01 parts by weight to the total 1 part by weight of the active ingredient, and the balance is the hydrophilic organic solvent. Is preferred.

When the system to be sterilized is an oil system such as cutting oil or oil paint, it is preferable to use a liquid agent using a hydrocarbon solvent such as kerosene, heavy oil or spindle oil, and various surfactants are used. You may be asked. Furthermore, for the system to be sterilized in which the active ingredient of the present invention can be directly dissolved or dispersed, a direct or solid diluent (for example, kaolin, clay,
It may be used as a powder agent diluted with bentonite, CMC, etc., or various surfactants may be used. In addition, depending on the combination, a preparation containing only the active ingredient may be used without a solvent or a surfactant.

The amount of the composition of the present invention to be added varies depending on the combined active ingredients and the object to be sterilized, but a concentration of about 0.5 to 200 mg / l is usually sufficient as the concentration of the active ingredient and is added to the starch slurry. When it does, about 1 to 100 mg / l is sufficient. In the method of the present invention, when the above-mentioned active ingredients are added simultaneously, it is convenient to use them as the same preparation as described above, but the same effect is exhibited even if they are added separately. Also in this case, the above-mentioned formulation form is preferable. This invention is illustrated by the following formulation examples and test examples.

[0024]

【Example】

 Formulation Example 1 5-chloro-2-methyl-isothiazolin-3-one 4 parts by weight 2,2-dibromo-3-nitrilopropionamide 8 parts by weight Methylenebisthiocyanate 3 parts by weight Diethylene glycol monomethyl ether 85 parts by weight Formulation Example 2 5- Chloro-2-methyl-isothiazolin-3-one 4 parts by weight 2,2-dibromo-2-nitroethanol 8 parts by weight Methylenebisthiocyanate 3 parts by weight Diethylene glycol monomethyl ether 85 parts by weight Formulation Example 3 5-chloro-2-methyl- Isothiazolin-3-one 4.5 parts by weight 2-Methyl-isothiazolin-3-one 0.5 parts by weight 2,2-dibromo-3-nitrilopropionamide 8 parts by weight Methylenebisthiocyanate 2 parts by weight Diethylene glycol monomethyl ether 85 parts by weight Made Example 4 5-chloro-2-methyl-isothiazolin-3-one 4.5 parts by weight 2-methyl-isothiazolin-3-one 0.5 parts by weight 2,2-dibromo-2-nitroethanol 8 parts by weight methylenebisthiocyanate 2 parts by weight Diethylene glycol monomethyl ether 85 parts by weight Formulation Example 5 4,5-dichloro-2-n-octyl-isothiazolin-3-one 4 parts by weight 2,2-dibromo-3-nitrilopropionamide 8 parts by weight Methylenebisthiocyanate 3 Part by weight Diethylene glycol monomethyl ether 85 parts by weight Formulation Example 6 4,5-dichloro-2-n-octyl-isothiazolin-3-one 4 parts by weight 2,2-dibromo-2-nitroethanol 8 parts by weight Methylenebisthiocyanate 3 parts by weight Diethylene glycol monomethyl ether 5 parts by weight Comparative Preparation Example 1 5-chloro-2-methyl-isothiazolin-3-one 4 parts by weight 2,2-dibromo-3-nitrilopropionamide 11 parts by weight Diethylene glycol monomethyl ether 85 parts by weight Comparative Preparation Example 2 5-chloro 2-Methyl-isothiazolin-3-one 4 parts by weight 2,2-dibromo-2-nitroethanol 11 parts by weight Diethylene glycol monomethyl ether 85 parts by weight Comparative Preparation Example 3 5-chloro-2-methyl-isothiazolin-3-one 7 0.5 parts by weight Methylenebisthiocyanate 7.5 parts by weight Diethylene glycol monomethyl ether 85 parts by weight Comparative Preparation Example 4 2,2-dibromo-3-nitrilopropionamide 7.5 parts by weight Methylenebisthiocyanate 7.5 parts by weight Diethylene glycol monomethyl ether 85 parts by weight Comparative Preparation Example 5 2,2-dibromo-2-nitroethanol 7.5 parts by weight Methylenebisthiocyanate 7.5 parts by weight Diethylene glycol monomethyl ether 85 parts by weight Comparative Preparation Example 6 4,5-dichloro-2-n- Octyl-isothiazolin-3-one 4 parts by weight 2,2-dibromo-2-nitroethanol 11 parts by weight diethylene glycol monomethyl ether 85 parts by weight Comparative Preparation Example 7 4,5-dichloro-2-n-octyl-isothiazolin-3-one 4 parts by weight 2,2-dibromo-3-nitrilopropionamide 11 parts by weight diethylene glycol monomethyl ether 85 parts by weight Comparative Preparation Example 8 4,5-dichloro-2-n-octyl-isothiazolin-3-one 4 parts by weight Methylenebisthiocyanate 11 parts by weight diethylene glycol Cole monomethyl ether 85 parts by weight

Test Example 1 [Continuous efficacy confirmation test for starch slurry] (Test method) Slurry liquid (pH: 5.4, solid content concentration: 35 w / w) prepared from raw tapioca starch slurry using industrial water
%) To which 1% of spoilage deposits collected from a starch slurry storage tank of a certain paper mill was added (sample species: Bacillus sp., Pseudomonas sp., Alcaligenes s)
p., viable cell count: 1.6 × 10 ⁶ cells / ml). 10g of test sample
Is dispensed into L-shaped test tubes, and each drug contains 15 mg as an active ingredient.
The mixture was added so that the concentration became 1 / l, and shaken at 25 ° C. After 3 days, the viable cell count of each sample was measured. The results are shown in FIGS.

Test Example 2 [Continuous efficacy confirmation test for starch slurry] (Test method) Urea phosphorylated starch slurry used for coating color (pH: 6.5, solid content concentration: 40 w / w)
%, Species: Pseudomonas sp., Alcaligenes sp., Micro
Cocus sp., viable cell count: 1.8 × 10 ⁸ cells / ml), each drug was added as an active ingredient to a concentration of 15 mg / l, shaken at 30 ° C. for 7 days, and then the viable cell count was measured. The measurement results are shown in Table 1.

[0027]

[Table 1]

Test Example 3 [Continuous efficacy confirmation test for adhesive] (Test method) Vinyl acetate adhesive (pH: 4.9, bacterial species: P
seudomonas sp., Alcaligenes sp., Geotrichum sp.,
Candida sp., Viable cell count: bacteria 3.6 × 10 ⁶ cells / ml, mold 1.1
Each drug was added as an active ingredient to a concentration of 30 mg / l to × 10 ⁴ cells / ml and yeast 4.5 × 10 ⁵ cells / ml), and the mixture was allowed to stand at 30 ° C. and the viable cell count was measured one month later. . The measurement results are shown in Table 2.

[0029]

[Table 2]

[0030]

[Table 3]

[Brief description of drawings]

FIG. 1 shows the antibacterial / bacteriostatic agent (DBNPA: Cl of the present invention.
-A graph showing the bactericidal action depending on the component ratio of (MIT: MBTC).

FIG. 2 shows the antibacterial / bacteriostatic agent (DBNPA: Cl of the present invention.
-A graph showing the bactericidal action depending on the component ratio of (MIT: MBTC).

FIG. 3 shows the antibacterial / bacteriostatic agent (DBNPA: Cl of the present invention.
-A graph showing the bactericidal action depending on the component ratio of (MIT: MBTC).

FIG. 4 shows the antibacterial / bacteriostatic agent (DBNE: Cl- of the present invention.
The graph which shows the bactericidal action by the component ratio of (MIT: MBTC).

FIG. 5 shows the antibacterial / bacteriostatic agent of the present invention (DBNE: Cl-
The graph which shows the bactericidal action by the component ratio of (MIT: MBTC).

FIG. 6 shows the antibacterial / bacteriostatic agent of the present invention (DBNE: Cl-
The graph which shows the bactericidal action by the component ratio of (MIT: MBTC). DBNPA: 2,2-dibromo-3-nitrilopropionamide Cl-MIT: 5-chloro-2-methyl-isothiazolin-3-one MBTC: methylenebisthiocyanate DBNE: 2,2-dibromo-3-nitro-1-ethanol

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 6, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[0027]

[Table 1]

Claims (7)

[Claims] 1. A general formula (1): (Wherein X ¹ and Y ¹ are hydrogen atoms or halogen atoms, R ¹ is C
An alkyl group having ₁ -C _8. At least one of 3-isothiazolone compounds represented by the formula (1) or a metal salt complex thereof, 2) General formula (2): [In the formula, X ² represents a nitro group or a cyano group, and Y ² , Y ³
Are the same or different and are bromine atom, carbamoyl group or formula (In the formula, R ² , R ³ and R ⁴ are each a hydrogen atom or a methyl group)
A group represented by, or Y ² and Y ³ are taken together and represented by the formula: (In the formula, A is a hydrogen atom, a halogen atom, a nitro group or C
_{1 to} C ₄ alkyl group, m represents an integer of 1 to 3), or a C _{1 to} C ₄ alkyl group substituted with a hydroxyl group, a bromine atom or a cyano group]. An industrial germicidal / bacteriostatic agent comprising at least one of nitrobromo compounds or cyanobromo compounds and 3) methylenebisthiocyanate as an active ingredient. 2. A nitrobromo compound or a cyanobromo compound is added in an amount of 0.1 to 1 part by weight of a 3-isothiazolone compound.
It is 9 parts by weight, and the methylenebisthiocinnate is 0.03 to 1.5 parts by weight based on 1 part by weight of the total amount of the 3-isothiazolone compound and the nitrobromo compound or cyanobromo compound. Sterilizing / bacteriostatic agent for 3. The 3-isothiazolone compound is 5-chloro-2-methyl-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-isothiazolin-3-one, or magnesium chloride or calcium chloride. The industrial sterilizing / bacteriostatic agent according to claim 1 or 2, which is a complex of 4. The nitrobromo compound or cyanobromo compound is 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-2-nitroethanol or 2-.
The industrial sterilizing / bacteriostatic agent according to any one of claims 1 to 3, which is bromo-2-nitro-1,3-diacetoxypropane. 5. A system for industrial sterilization comprising a 3-isothiazolone compound represented by the general formula (1), a nitrobromo or cyanobromo compound represented by the general formula (2) and methylenebisthiocyanate. The method for industrial sterilization / bacteriostatic treatment is characterized in that the sterilization / bacteriostatic method is added simultaneously or separately so that the total concentration becomes 0.5 to 200 mg / l. 6. The 3-isothiazolone compound is 5-chloro-2-methyl-isothiazolin-3-one or 4,5-
The industrial sterilization / bacteriostatic method according to claim 5, which is dichloro-2-n-octyl-isothiazolin-3-one. 7. The nitrobromo- or cyanobromo-based compound is 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-2-nitroethanol or 2-
The industrial sterilization / bacteriostatic method according to claim 5 or 6, which is bromo-2-nitro-1,3-diacetoxypropane.