JP2003212705A - Water-based microorganism-killing method under reductive atmosphere - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a microorganism-killing method in water system under reductive atmosphere, particularly in a reductive bleaching step of pulp including recovery of waste paper and steps after reductive bleaching of pulp in a papermaking process, and in a starch slurry preparation step. <P>SOLUTION: This water-based microorganism-killing method under reductive atmosphere comprises simultaneously adding (A) a quaternary ammonium salt compound represented by general formula (1) (wherein one to three groups among R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>are methyl groups and/or ethyl groups and the other(s) is selected from a 6-22C alkyl group which may have hydroxy group and/or benzene ring, an 8-22C alkenyl group and an 8-22C aryl group) and (B) one or more kinds of a specific halogenated nitroamide compound, a nitroalcohol compound, a halogenated acetate compound, a halogenated (hydroxy)oxime compound, a thiocyanate compound, an aldehyde compound and an isothiazoline compound to a water system under reductive atmosphere. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-reducing atmosphere for reducing water in a reducing atmosphere, in particular, a reducing bleaching process water for pulp including recovery of used paper in a papermaking process, and a method for microbiocidal treatment of a pulp slurry containing the treated water.

[0002]

2. Description of the Related Art In recent years, paper recycling has progressed in the paper manufacturing industry, and the use of used paper has expanded from newsprint to medium-quality and high-quality paper, and it has been desired to increase the whiteness of recycled paper.

In order to increase the whiteness of paper, pulp is usually bleached. Until now, pulp bleaching has been dominated by chlorine-based bleaching, such as chlorine, sodium hypochlorite (hypo), and chlorine dioxide. , A two-stage bleaching method combining bleaching with a reducing agent such as sodium sulfite, sodium hydrosulfite, thiourea dioxide, and sodium thiosulfate has come to be used.
Oxidizing microbicides have been mainly used for the microbiocidal treatment in the bleaching process, but in a reducing atmosphere, their microbicidal activity is greatly reduced, and a sufficient microbicidal effect is obtained. Not seen, slime is seen. If slime adheres to the wall surface or equipment in the process, corrosion under the surface where the slime adheres occurs, or part of the adhered slime peels off and re-adheres to the paper product, causing paper breakage, resulting in temporary suspension of operation. Since it causes a great loss such as a defect (defective portion) in paper and a deterioration in quality such as generation of stains, there is an increasing demand for suppression of slime generation in a water system under a reducing atmosphere, that is, microbiocidal treatment.

In the production of starch such as corn starch, sodium sulfite is added to adjust the whiteness of powdered starch. Generally, a microbicide is used for the purpose of preserving paste liquids and starch slurries that use starch, but when starch containing a reducing substance such as sodium sulfite is used, the starch slurry has a reducing atmosphere, and thus microbicides are used. The action is greatly reduced, and the starch slurry is easily decomposed.

Various bactericides have been proposed as a sterilizing method in the presence of a reducing substance (in a reducing atmosphere). For example, an industrial sterilization method in which maleic anhydride is added as an active ingredient (JP-A-10-72304), N,
Sterilization method in which 4-dihydroxy-α-oxobenzeneethaneimidoyl chloride and maleic anhydride or a water-soluble derivative thereof are added in combination (JP-A-3-170).
No. 404), 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and an isothiazolin-3-one compound, and a sterilization method in which a brominated acetic acid ester is added in combination (JP-A-7-258002). No.), a sterilization method in which a dihalogenated glyoxime derivative is added (JP-A-8-20505), methylenebisthiocyanate and 2,2-dibromo-2-nitroethanol and 5-chloro-2-methyl-4-isothiazoline- 3-one and 4,5-dichloro-1,2-dithiol-
A sterilization method in which 3-one is added in combination (Japanese Patent Application Laid-Open No. HEI 10-29138).
-36202), 2,2-dibromo-3-nitrilopropionamide and bromoacetate compound and 2-
A sterilization method in which bromo-2-nitro-1,3-diacetoxypropane or 2,2-dibromo-2-nitroethanol is added in combination (JP-A-10-67608), α-chlorobenzaldoxime and 2, 2-dibromo-3-nitrilopropionamide, 1,4-bis (bromoacetoxy) -2-butene, 1,2-bis (bromoacetoxy) ethane, 1,2-bis (bromoacetoxy) propane, 1,2, Sterilization method of adding methylenebisthiocyanate in combination with any one of 3-tris (bromoacetoxy) propane, 2-bromo-2-nitro-1,3-diacetoxypropane and 2,2-dibromo-2-nitroethanol (JP-A-10-10
No. 9907), a sterilization method in which benzisothiazoline and didecyldimethylammonium chloride, alkyldimethylbenzylammonium chloride and didecylmethylpolyoxyethylammonium propionate are added in combination (JP-A No. 11-71211).
Etc. have been proposed. However, a satisfactory effect has not yet been obtained, and a more effective microbiocidal method is strongly desired.

[0006]

Under these circumstances, an object of the present invention is to provide a water system under a reducing atmosphere, particularly process water after reduction bleaching treatment of pulp including recovery of waste paper in a papermaking process, and It is an object of the present invention to provide a microbicidal method for a pulp slurry containing the process water, a starch slurry containing a reducing agent for adjusting whiteness, a paste solution thereof, and a blended composition containing the same.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that in a water system under a reducing atmosphere, (A) a specific quaternary ammonium salt compound,
(B) It was found that a compound having a specific microbicidal action is simultaneously acted to exert an excellent microbicidal effect in a reducing atmosphere, and the present invention has been completed based on this finding.

That is, the invention according to claim 1 relates to (A) the general formula (1) in an aqueous system under a reducing atmosphere.

[0009]

[Chemical 2]

(In the formula, ^{1 to 3 of} R ¹ , R ² , R ³ and R ⁴ are a methyl group and / or an ethyl group, and the others are 8 to 8 carbon atoms.
22 is selected from a hydroxyl group and / or an alkyl group which may have a benzene ring, an alkenyl group having 8 to 22 carbon atoms and an aryl group having 8 to 22 carbon atoms. X
^n- is a monovalent carboxylic acid anion that may contain a hydroxy group having 2 to 22 carbon atoms, and n is an integer of 1 or 2. In the case of a divalent to trivalent carboxylate anion, a part thereof may be a sodium salt or a potassium salt. ) A quaternary ammonium salt compound represented by
(B) 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitro-1-ethanol,
1,2-bis- (bromoacetoxy) -ethane, 1,4
-Bis- (bromoacetoxy) -2-butene, 1-bromo-3-chloro-5,5-dimethylhydantoin, 1-
Chloro-3-bromo-5,5-dimethylhydantoin,
Dichloroglyoxime, α-chlorobenzaldoxime, 2- (p-hydroxyphenyl) glyoxyhydroxymoyl chloride, methylenebisthiocyanate, 5
-Chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,
5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-
3-one, 1,2-benzisothiazolin-3-one and at least one selected from the group consisting of these isothiazoline compounds and a metal salt, glutaraldehyde, and o-phthalaldehyde are added at the same time. It is a water-based microbiocidal method in an atmosphere.

The invention according to claim 2 provides an aqueous microbiocidal method under the reducing atmosphere according to claim 1,
In the quaternary ammonium salt compound of the component (A), in the general formula (1), ^two of R ¹ , R ² , R ³ and R ⁴ are a methyl group and / or an ethyl group, and the other two have a carbon number of 8 ~ 18
Is selected from linear alkyl groups of.

The invention according to claim 3 provides an aqueous microbiocidal method under the reducing atmosphere according to claim 1,
The quaternary ammonium salt compound of the component (A) is didecyldimethylammonium laurate, didodecyldimethylammonium laurate, didecyldimethylammonium gluconate, didodecyldimethylammonium gluconate, didecyldimethylammonium sodium glutarate, glutaric acid. Sodium didodecyldimethylammonium, Bis (didecyldimethylammonium) glutarate, Bis (didecyldimethylammonium) glutarate, Didecyldimethylammonium sodium adipate, Didodecyldimethylammonium sodium adipate, Bis (didecyldimethylammonium adipate) ), And at least one selected from bis (didodecyldimethylammonium adipate).

The invention according to claim 4 relates to claims 1 to 3.
In the water-based microbicidal method under a reducing atmosphere according to any one of (1) to (B), 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-2-nitro-1-ethanol, 2- (p-hydroxyphenyl) glyoxylohydroxymoyl chloride, 4,5
-Dichloro-2-n-octyl-4-isothiazoline-
One or more selected from 3-one, glutaraldehyde and o-phthalaldehyde.

According to a fifth aspect of the present invention, in the aqueous microbiocidal method under a reducing atmosphere according to any one of the first to fourth aspects, a sulfoxylate ion, a sulfite ion, and a thiol ion are added to the aqueous system under a reducing atmosphere. One or two or more kinds of sulfate ions are present in an amount of 5 to 100 mg / l.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The water system under a reducing atmosphere in the present invention is
In the pulp and paper manufacturing industry, the process water of the reducing bleaching stage in the bleaching process of pulp including the recovery of waste paper and the pulp slurry containing the process water after the reducing bleaching process, and the process water and the pulp slurry of the subsequent process including these, Reducing agent-containing process water remaining after the process water after the oxidative bleaching treatment is treated with a reducing agent, a pulp slurry containing the process water, a starch slurry prepared by using a reducing agent-containing starch, and a starch slurry thereof. It also includes process water in which a paste liquid is present, a compounding composition such as a pulp slurry and a size liquid, a coating liquid, and an aqueous system in which hydrogen sulfide is mixed into a reducing atmosphere in other industrial fields.

In an aqueous system under these reducing atmospheres, hydrosulfite salts, thiosulfates, thioglycolates, thiourea dioxide, etc. are used as reducing agents, and as sulfoxylate ions, sulfite ions, thiosulfate ions, etc. Existing.

In the aqueous system of the present invention in a reducing atmosphere, one or more reducing substances such as sulfoxylate ion, sulfite ion and thiosulfate ion are contained in an amount of 5 to 200 mg /
L is an aqueous system present, preferably 5 to 100 mg / L
And more preferably 5 to 50 mg / L.

The quaternary ammonium salt compound of the component (A) of the present invention is a quaternary ammonium salt compound represented by the following general formula (1).

[0020]

[Chemical 3]

In the general formula (1), ^{1 to 3 of} R ¹ , R ² , R ³ and R ⁴ are methyl groups and / or ethyl groups, and the others are hydroxy groups having 8 to 22 carbon atoms and /
Alternatively, it is selected from an alkyl group which may have a benzene ring, an alkenyl group having 8 to 22 carbon atoms and an aryl group having 8 to 22 carbon atoms.

A hydroxy group having 8 to 22 carbon atoms and /
Or as the alkyl group which may have a benzene ring, 2-ethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, coconut alkyl group, tetradecyl group, hexadecyl group, 12-hydroxyl stearyl group, stearyl Group, isostearyl group, behenyl group, branched alkyl group having 10 to 18 carbon atoms obtained by oxo method-hydrogenation of olefin, and the like. 8 to 22 carbon atoms
Examples of the alkenyl group include a diisobutylene group, an alkenyl group of an internal olefin having 10 to 18 carbon atoms obtained by the oxo method, an oleyl group, a linoleyl group, and the like, and an aryl group having 8 to 22 carbon atoms is an ethylphenyl group. and so on.

Of these, preferably ^two of R ¹ , R ² , R ³ and R ⁴ are methyl groups and / or ethyl groups,
The other two are alkyl groups having 8 to 18 carbon atoms, for example, octyl group, decyl group, dodecyl group, tetradecyl group, stearyl group and isostearyl group. Still more preferably, ^two of R ¹ , R ² , R ³ and R ⁴ are methyl groups, and the other two are decyl group, dodecyl group and tetradecyl group.

If R ¹ , R ² , R ³ and R ⁴ are composed of a methyl group or an ethyl group, the effect of the present invention cannot be obtained. In addition, ^{1 to 3 of} R ¹ , R ² , R ³ and R ⁴ are methyl groups and / or
Alternatively, the effect of the present invention cannot be obtained even if it is composed of an ethyl group and the other is composed of an alkyl group having less than 8 carbon atoms. Further, even if R ¹ , R ² , R ³ and R ⁴ are constituted by an alkyl group having less than 8 carbon atoms, the effect of the present invention cannot be obtained. When ^{1 to 3 of} R ¹ , R ² , R ³ and R ⁴ are composed of a methyl group and / or an ethyl group and the others have more than 22 carbon atoms, the water solubility of the quaternary ammonium salt compound decreases. The effect of the present invention cannot be obtained.

X ^n- in the general formula (1) is a monovalent carboxylic acid anion which may contain a hydroxyl group having 2 to 22 carbon atoms. As the monovalent carboxylic acid, acetic acid, acrylic acid, methacrylic acid, butyric acid, valeric acid,
Gluconic acid, hexanoic acid, lauric acid, stearic acid,
There are isostearic acid, oleic acid, salicylic acid, cinnamic acid, etc., and as divalent carboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Sebacic acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, aspartic acid, malic acid, tartaric acid and the like, and trivalent carboxylic acids include citric acid and the like. Of these, lauric acid, gluconic acid, glutaric acid, and adipic acid are preferable. Formic acid having 1 carbon atom does not provide the microbicidal effect of the present invention, and carboxylic acid having more than 22 carbon atoms does not provide the microbicidal effect of the present invention because the water solubility of the quaternary ammonium salt compound decreases. Sometimes. Further, in the case of the divalent to trivalent carboxylic acid, a part thereof may be in the form of sodium salt or potassium salt.

Specific examples of the quaternary ammonium salt compound as the component (A) include octyl trimethyl ammonium succinate, decyl triethyl ammonium gluconate, dodecyl trimethyl ammonium gluconate, and gluconic acid 1
2-hydroxystearyltrimethylammonium, didecylmethylammonium gluconate, didecyldiethylammonium gluconate, didodecyldimethylammonium gluconate, didodecyldiethylammonium gluconate, distearyldimethylammonium gluconate, octyltriethylammonium laurate, lauric acid Decyltrimethylammonium, stearyltriethylammonium laurate, didodecyldimethylammonium laurate, didodecyldiethylammonium laurate, distearyldimethylammonium laurate, octyltrimethylammonium sodium glutarate, decyltrimethylammonium sodium glutarate, trimethylstearylammonium glutarate Potassium, guru Sodium didecyldimethylammonium acid salt, Didecyldiethylammonium sodium glutarate, Didecyldimethylammonium potassium glutarate, Didodecyldimethylammonium sodium glutarate, Didodecyldiethylammonium sodium glutarate, Bis (dioctyldimethylammonium) glutarate, Glutar Acid bis (didecyldimethylammonium), bis (didecyldiethylammonium) glutarate, bis (didodecyldimethylammonium) glutarate, bis (didecyldiethylammonium) glutarate, octyltrimethylammonium adipate, decyltriethyl adipate Sodium ammonium, trimethylstearyl ammonium sodium adipate, Dimethy adipate Dioctyl ammonium potassium, didecyl dimethyl ammonium sodium adipate, didecyl diethyl ammonium sodium adipate, didodecyl dimethyl ammonium sodium adipate, didodecyl diethyl ammonium sodium adipate, bis (dioctyl dimethyl ammonium) adipate, bis (dipic acid adipate Decyldimethylammonium), bis (didecyldiethylammonium) adipate, bis (didodecyldimethylammonium) adipate, bis (didodecyldiethylammonium) adipate, and the like. Of these, preferably didecyldimethylammonium laurate, didodecyldimethylammonium laurate, didecyldimethylammonium gluconate, didodecyldimethylammonium gluconate, didecyldimethylammonium sodium glutarate, didodecyldimethylammonium glutarate sodium, glutaric. Acid bis (didecyldimethylammonium), glutaric acid bis (didodecyldimethylammonium), didecyldimethylammonium adipate, didodecyldimethylammonium adipate, bis (didecyldimethylammonium adipate), bis (dipicadiate) adipate Dodecyldimethylammonium), more preferably didecyldimethylammonium laurate, didodecyl laurate. Methylammonium, glutaric acid bis (didecyl dimethyl ammonium), glutaric acid bis (di-dodecyl dimethyl ammonium), adipic acid bis (didecyldimethylammonium) adipate bis (didodecyldimethylammonium). These (A) quaternary ammonium salt compounds may be used alone or in combination of two or more.

The component (B) of the present invention is a compound having a microbicidal effect, such as 2,2-dibromo-3-nitrilopropionamide and 2-bromo-2-nitropropane-.
1,3-diol, 2,2-dibromo-2-nitro-1
-Ethanol, 1,2-bis- (bromoacetoxy)-
Ethane, 1,4-bis- (bromoacetoxy) -2-butene, 1-bromo-3-chloro-5,5-dimethylhydantoin, dichloroglyoxime, α-chlorobenzaldoxime, 2- (P-hydroxy Phenyl) glyoxylohydroxymoyl chloride, methylenebisthiocyanate, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazoline-3
-One, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one and these isothiazolones A complex of a system compound and a metal salt, glutaraldehyde, or o-phthalaldehyde, and of these, preferably 2,2
-Dibromo-3-nitrilopropionamide, 2,2-
Dibromo-2-nitro-1-ethanol, 2- (p-hydroxyphenyl) glyoxylohydroxymoyl chloride, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, glutaraldehyde, o-phthalate Aldehydes, more preferably 2,2-dibromo-3-
Nitrilopropionamide, 2,2-dibromo-2-nitro-1-ethanol, 2- (p-hydroxyphenyl) glyoxyhydroxymoyl chloride. These may be used alone or in combination of two or more.

The compounds as the component (B) have a high microbiocidal effect in an aqueous system under a non-reducing atmosphere, but the microbicidal effect is reduced under a reducing atmosphere. A) When used in combination with a quaternary ammonium salt compound, it exhibits a higher microbicidal action even in a reducing atmosphere.

The water-based microbiocidal method in the reducing atmosphere of the present invention is not particularly limited, and the component (A) and the component (B) are individually added to the target water system in the reducing atmosphere, Alternatively, any of the methods of adding the components (A) and (B) in a mixed state may be used.

In the method of adding the components (A) and (B) in a mixed state, the components (A) and (B) are added to water, a mixed solvent of water and a water-soluble organic solvent, a water-soluble organic solvent, or a water-soluble solvent. It is used by appropriately selecting from a mixed solvent of a water-soluble organic solvent and a water-insoluble organic solvent or a water-insoluble organic solvent and dissolving it.

Examples of the water-soluble organic solvent include ketones such as acetone, alcohols such as methanol, ethanol, propanol and isopropanol, ethylene glycol,
Propylene glycol, glycols such as diethylene glycol, methyl cellosolve, glycol ethers such as diethylene glycol monomethyl ether, pyrrolidones such as N-methylpyrrolidone and 2-methylpyrrolidone, lactones such as γ-butyrolactone and β-butyrolactone, diethyl carbonate, Examples thereof include dioxane and dimethylformamide.

Examples of the non-water-soluble organic solvent include glycols such as polypropylene glycol and carbonates such as propylene carbonate.

If necessary, surface activity and the like may be added, but the present invention does not limit the addition of these. As the surfactant, a nonionic surfactant,
Cationic surfactants are preferred.

The use ratio of the component (A) and the component (B) in the microbiocidal method of the present invention is 9: 1 to 1: 9 by weight.
Preferably 7: 3 to 3: 7, more preferably 7: 3 to.
The range is 5: 5.

Further, the addition amounts of the component (A) and the component (B) greatly differ depending on the process conditions of the water system such as water quality and temperature, the type of living microorganisms, the number of microorganisms, the degree of slime generation, and the frequency of addition. Therefore, it is not uniformly determined, but with respect to the target treated water system, (A) component,
The component (B) is usually 0.1 to 500 mg / L, preferably 1 to 200 mg / L, more preferably 5 to 10 each.
It is added at 0 mg / L. If the added amount of the components (A) and (B) is less than 0.1 mg / L, the effect of the present invention may not be obtained, and if it is more than 500 mg / L,
Although the effect is sufficient, the effect is not great relative to the added amount, which may be economically disadvantageous.

The method of adding the components (A) and (B) to the aqueous system is not particularly limited, and the components are added continuously or intermittently using, for example, a normal chemical injection pump. Further, the locations where the components (A) and (B) are added are appropriately selected in consideration of the location where the failure occurs or the process,
It is determined, and although not particularly limited, it is usually added directly to the place or process where the trouble occurs or is added upstream thereof.

The microbicidal method of the present invention is less affected by the pH of the target aqueous system and can be applied from the acidic range of pH 4 to the alkaline range of pH 10 or less.

Within the range that does not interfere with the effects of the present invention,
Other microbicides, surfactants may be used in combination, or may be used together with other process additives such as defoaming agents and scale control agents, but the present invention does not limit the addition of these chemicals. is not.

[0039]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Component (A) (Quaternary Ammonium Compound)] A-1: Used as a 0.5 wt% aqueous solution of distearyldimethylammonium acetate [reagent, manufactured by Tokyo Kasei KK]. (Hereinafter, "weight% concentration aqueous solution" is referred to as "%") A-2: 50% gluconic acid aqueous solution [reagent, manufactured by Kanto Chemical Co., Ltd.] 157 parts (0.40 mol in terms of pure content) and water 30
Didecyldimethylammonium methyl carbonate [reagent, Kanto Chemical Co., Ltd., keeping 0 part at 80 to 90 ° C]
Of methanol solution) (0.40 mol in terms of pure content) was gradually added over 2 hours to distill off carbon dioxide and methanol generated to obtain an aqueous solution of didecyldimethylammonium gluconate. Ion-exchanged water was used as a 0.5 wt% aqueous solution. A-3: Didodecyldimethylammonium gluconate [reagent, manufactured by Tokyo Kasei Co., Ltd.] was used as a 0.5% aqueous solution. A-4: Methyl trioctyl ammonium octanoate [reagent, manufactured by Tokyo Kasei Co., Ltd.] was added with 0.5% acetone (20
%)-Water (80%) aqueous solution. (Hereinafter, "acetone (20%)-water (80%) aqueous solution" is referred to as "acetone-aqueous solution".) A-5: Didecyldimethylammonium laurate [reagent, manufactured by Tokyo Kasei Co., Ltd.] Used as 5% acetone-water solution. A-6: Didodecyldimethylammonium laurate [Reagent, Tokyo Kasei Co., Ltd.] was used as a 0.5% acetone-water solution. A-7: Bis (stearyltrimethylammonium) succinate [Reagent, Tokyo Kasei Co., Ltd.] was used as a 0.5% aqueous solution. A-8: Bis (didecyldimethylammonium) glutarate [reagent, manufactured by Kanto Chemical Co., Inc.] was used as a 0.5% aqueous solution. A-9: Bis (didodecyldimethylammonium) glutarate [reagent, manufactured by Kanto Chemical Co., Inc.] was used as a 0.5% aqueous solution. A-10: Didecyldimethylammonium sodium adipate [Reagent, Tokyo Chemical Industry Co., Ltd.] was used as a 0.5% aqueous solution. A-11: Didodecyldimethylammonium potassium adipate [reagent, manufactured by Kanto Chemical Co., Inc.] was used as a 0.5% aqueous solution. A-12: Bis (didecyldimethylammonium adipate) [“Osmolin DA-50” (trade name), manufactured by Sanyo Chemical Industry Co., Ltd.] was used as a 0.5% aqueous solution. A-13: Bis (didodecyldimethylammonium) adipate [reagent, manufactured by Kanto Chemical Co., Inc.] was used as a 0.5% aqueous solution. A-14: (Used in Comparative Example) Hexyltrimethylammonium acetate [reagent, manufactured by Kanto Chemical Co., Inc.] was used as a 0.5% aqueous solution. A-15: (Used in Comparative Example) Benzalkonium chloride [reagent, manufactured by Kanto Chemical Co., Inc.] was used as a 0.5% aqueous solution.

[Component (B)] B-1: 2,2-dibromo-3-nitrilopropionamide [“DBNPA” (trade name), Chemiclear Co., Ltd.
Was manufactured as a 0.5% N-methylpyrrolidone solution. B-2: A mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one [“Zonen F” (trade name), manufactured by Chemicle Co., Ltd.] Was used as a 0.5% aqueous solution. B-3: Orthophthalaldehyde [“OPA” (trade name), manufactured by Showa Kako Co., Ltd.] was used as a 0.5% aqueous solution. B-4: Glutaraldehyde ["Acucar 550"
(Trade name, manufactured by Union Carbide) was used as a 0.5% aqueous solution. B-5: 4,5-Dichloro-2-n-octyl-isothiazolin-3-one [“Clarix 4000” (trade name), manufactured by Rohm & Haas] was used as a 0.5% aqueous solution. B-6: 2-Bromo-2-nitropropane-1,3-diol [“BNPD” (trade name), manufactured by Nagase Kasei Co., Ltd.]
Was used as a 0.5% aqueous solution. B-7: 2,2-dibromo-2-nitro-1-ethanol [“Dibunyrrole” (trade name), manufactured by KI Kasei] was used as a 0.5% N-methylpyrrolidone solution. B-8: 1,2-bis- (bromoacetoxy) -ethane [“BBAE” (trade name), manufactured by Chemiclear Co., Ltd.] was adjusted to 0.
Used as a 5% N-methylpyrrolidone solution. B-9: 1,4-bis- (bromoacetoxy) -2-butene [“BBAB” (trade name), manufactured by Chemicle Co., Ltd.]
Was used as a 0.5% N-methylpyrrolidone solution. B-10: 1-Bromo-3-chloro-5,5-dimethylhydantoin [“Bromide” (trade name), manufactured by Great Lakes Chemical Co.] was used as a 0.5% aqueous solution. B-11: Dichloroglyoxime [“DCO” (trade name), manufactured by Junsei Kagaku Co., Ltd.] was used as a 0.5% N-methylpyrrolidone solution. B-12: α-chlorobenzaldoxime [“CBO”
(Trade name, manufactured by Bayer) was used as a 0.5% N-methylpyrrolidone solution. B-13: 2- (p-hydroxyphenyl) glyoxyhydroxymoyl chloride [“HP-100” (trade name), manufactured by Keiai Kasei Co., Ltd.] was used as a 0.5% N-methylpyrrolidone solution. B-14: Methylenebisthiocyanate [“MBT”]
(Trade name, manufactured by Chemicle Co., Ltd.) was used as a 0.5% N-methylpyrrolidone solution. B-15: 2-n-octyl-4-isothiazoline-3
-ON [“Scene 8” (trade name), manufactured by Rohm & Haas] was used as a 0.5% N-methylpyrrolidone solution. B-16: 1,2-benzisothiazolin-3-one (“Proxel Press Paste (D)” (trade name), manufactured by Zeneca Corporation) was used as a 0.5% aqueous solution.

[Microorganism used for microbiocidal test] Microorganism 1: Pseudomonas aeruginosa of gram-negative bacterium Pseudomonas aeruginosa :
IFO-12689) Microorganism 2: Bacillus subtilis ( Bac)
ilus subtils: IAM-1633) microorganism 3: Staphylococcus aureus is a gram-positive bacteria (Staphlococcus aureu
s : IAM-12082) Microorganism 4: Gram-negative bacteria producing polysaccharides and high slime-forming ability Xanthomonas campestris ( Xant
hmonas campestris : IFO-135
51) Microorganism 5: Mold of Trichoderma viride ( Tricho
derma virde: IFO-5720) microorganisms 6: yeast Saccharomyces cerevisiae (Sach
aromyces cerevisiae : IAM-4
274) [Microbicide test 1] Plate medium for bacteria (glucose 1.0
g, peptone 5.0 g, yeast extract 2.5
g, 18 g of agar were dissolved in 1 L of distilled water, and the pH was adjusted to 6.8.
Pseudomonas aerug ( Pseudomonas aerug)
Inosa : IFO-12689) (microorganism 1) was cultured at 25 ° C for 1 to 2 days so that the logarithmic growth phase was reached. After adding 1 platinum loop of a strain in the logarithmic growth phase to 100 mL of sterilized water, sodium sulfite was added as a reducing substance to S.
O ₃ ²⁻ concentration: 5 mg / L, 50 mg / L, 100 mg
It was added so that it became / L, and it was adjusted to pH6. Next, (A) quaternary ammonium salt compound: A-1 to A-1
3: 0.1 ml and (B) microbicide: B-1 to B-1
After 5: 0.1 ml was added and shaken at 30 ° C. for 30 minutes, the number of bacteria (cells / mL) was measured by the colony counting method. The results are shown in Tables 1 to 3.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

In the conventional microbicide, the reducing substance is SO ₃
^{2-When the} concentration was 50 mg / L, the microbicidal effect was remarkably reduced. On the other hand, in the microbicidal method of the present invention, even if the reducing substance was present at 100 mg / L, a high microbicidal effect was obtained as compared with the conventional microbicides.

[Microbicide test 2] Pseudomonas ae of Gram-negative bacterium Pseudomonas ae
ruginosa : IFO-12689) (microorganism 1)
Was cultured in the same plate medium as used in Microbicide Test 1 at 25 ° C. for 1 to 2 days so that the logarithmic growth phase was reached. 100 mL of sterilized water was placed in a 300 ml Erlenmeyer flask, and 1 platinum loop of a strain in a logarithmic growth phase was placed therein, and sodium hydrosulfite (reducing substance) was added so that SO ₃ ²⁻ concentration was 50 mg / L. Then, the pH was adjusted to 8. Similarly, 100 mL of sterilized water was put into another 300 mL Erlenmeyer flask, thiourea dioxide (reducing substance) was added so that the concentration of sulfoxylic acid was 50 mg / L, and the pH was adjusted to 8. Then (A) 4
Primary ammonium salt compound: 0.1 ml of A-1 and (B)
Microbicide: 0.1 ml of B-1 was added, 30 ° C, 30
After shaking for a minute, the number of bacteria (cells /
(mL) was measured. Similarly, (A) quaternary ammonium salt compound: A-1 to A-2, A-4, A-5, A-
8, A-10, A-12, (B) Microbicide: B-1 in place of B-3, B-4, B-5, B-7, B-1
A microbicide test was carried out by substituting 3 for the test. The results are shown in Table 4.

[0048]

[Table 4]

According to the microbicidal method of the present invention, it was confirmed that even in the presence of sodium hydrosulfite and thiourea dioxide, a remarkable microbicidal effect was obtained as compared with conventional microbicides.

[Microbicide Test 3] Microorganism 2 was cultured in a plate medium at 25 ° C. for 1 to 2 days in the logarithmic growth phase in the same manner as in the method used in Microbicide Test 1.
100 mL of sterilized water was placed in a 200 mL Erlenmeyer flask, then 1 platinum loop of each strain of microorganisms 2 to 4 in the logarithmic growth phase was taken and placed in sterilized water in the Erlenmeyer flask to give a bacterial test suspension. Sodium sulfite is added to this microbial suspension as S
O ₃ ^2- concentration of 50 mg / L was added to adjust pH to 4, respectively.
Adjusted to 7, 10, (A) quaternary ammonium salt compound:
A-5: 0.1 ml and (B) Microbicide: B-1, B-
0.1 ml of one of 3, B-4, B-5, B-7, and B-13 was added, shaken at 30 ° C. for 30 minutes, and then the number of bacteria (cells / mL) was determined by the colony counting method. The measurement was performed. Similarly, the microorganism 3 and the microorganism 4 are cultured to prepare a bacterial test suspension, and the fungus microorganism 5: Trichoderma virde : IFO-
5720) and yeast microorganism 6: Saccharomyces
Cerevisiae (Sacharomyces cerevi
siae : IAM-4274).
After culturing in A plate medium (manufactured by Tanabe Seiyaku Co., Ltd.) at 25 ° C for 3 days, scrape the surface with a platinum loop, put in 100 mL of sterilized water in a 200 mL Erlenmeyer flask, and shake to suspend the bacteria (and yeast). I made a liquid. (A) Quaternary ammonium salt compounds: A-9, A-1 in the same manner as the microorganism 2 using the obtained bacterial (and mold, yeast) test suspensions of the microorganisms 3 to 6
1, A-12, A-13 and (B) Microbicide: B
A combination of -1, B-3, B-5, B-7 and B-13 was subjected to a microbicidal effect test. The results are shown in Tables 5-9.

[0051]

[Table 5]

[0052]

[Table 6]

[0053]

[Table 7]

[0054]

[Table 8]

[0055]

[Table 9]

It can be seen that the microbicidal method of the present invention exhibits a high microbicidal effect in a wide range of pH = 4 to 10 in a reducing atmosphere.

[0057]

INDUSTRIAL APPLICABILITY In a water system under a reducing atmosphere, a bleaching process including a reducing bleaching stage of pulp including recovery of waste paper in a papermaking process which has not been able to obtain a sufficient microbicidal effect, and pulp after the bleaching process, It is possible to prevent adverse effects such as suspension of operation due to microbial damage in the pulp slurry and further starch slurry preparation step, and greatly contribute to operation stabilization, productivity improvement, and product quality improvement.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C02F 1/50 520 C02F 1/50 520P 532 532C 532D 532E 532H D21H 17/07 D21H 17/07 21/04 21 / 04

Claims (5)

[Claims] 1. In a water system under a reducing atmosphere, (A) general formula (1) (in the formula, ^{1 to 3 of} R ¹ , R ² , R ³ and R ⁴ are methyl groups and / or ethyl groups) Yes, others have 6 to 2 carbon atoms
2 hydroxyl groups and / or an alkyl group optionally having a benzene ring, an alkenyl group having 8 to 22 carbon atoms and an aryl group having 8 to 22 carbon atoms. X
^n- is a monovalent carboxylic acid anion that may contain a hydroxy group having 2 to 22 carbon atoms, and n is an integer of 1 or 2. In the case of a divalent to trivalent carboxylate anion, a part thereof may be a sodium salt or a potassium salt. ) And a quaternary ammonium salt compound, (B) 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitro-1-ethanol,
1,2-bis- (bromoacetoxy) -ethane, 1,4
-Bis- (bromoacetoxy) -2-butene, 1-bromo-3-chloro-5,5-dimethylhydantoin, 1-
Chloro-3-bromo-5,5-dimethylhydantoin,
Dichloroglyoxime, α-chlorobenzaldoxime, 2- (p-hydroxyphenyl) glyoxyhydroxymoyl chloride, methylenebisthiocyanate, 5
-Chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,
5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-
3-one, 1,2-benzisothiazolin-3-one and at least one selected from the group consisting of these isothiazoline compounds and metal salts, glutaraldehyde, and o-phthalaldehyde are added at the same time. Water-based microbicidal method under atmosphere. 2. The quaternary ammonium salt compound as the component (A), wherein in the general formula (1), ^two of R ¹ , R ² , R ³ and R ⁴ are a methyl group and / or an ethyl group, and The aqueous microbiocidal method according to claim 1, wherein two are selected from linear alkyl groups having 8 to 18 carbon atoms. 3. The quaternary ammonium salt compound of component (A) is didecyldimethylammonium laurate, didodecyldimethylammonium laurate, didecyldimethylammonium gluconate, didodecyldimethylammonium gluconate, didecyldimethyl glutarate. Sodium ammonium, didecyldimethylammonium glutarate, bis (didecyldimethylammonium) glutarate, bis (didodecyldimethylammonium) glutarate, didecyldimethylammonium adipate, didodecyldimethylammonium adipate, bis adipate 2. One or more selected from (didecyldimethylammonium) and bis (didodecyldimethylammonium) adipate.
The water-based microbiocidal method described. 4. The component (B) is 2,2-dibromo-3-
Nitrilopropionamide, 2,2-dibromo-2-nitro-1-ethanol, 2- (p-hydroxyphenyl) glyoxylohydroxymoyl chloride, 4,5
-Dichloro-2-n-octyl-4-isothiazoline-
The water-based microbicidal method according to any one of claims 1 to 3, which is one or more selected from 3-one, glutaraldehyde, and o-phthalaldehyde. 5. The aqueous system in a reducing atmosphere contains 5 to 100 mg / l of one or more of sulfoxylate ion, sulfite ion and thiosulfate ion.
5. The water-based microbiocidal method according to any one of 4 to 4.