JPH0859414A - Antiseptic-mildew-proofing agent for industry and industrial method of antiseptic-mildew-proofing - Google Patents

Abstract

PURPOSE: To obtain an antiseptic-mildew-proofing agent for industry capable of exhibiting excellent antiseptic-mildew-proofing activity with a small quantity, especially effective against an objective material even in the presence of a reducing material by compounding a hydrogen peroxide producing substance with 3-isothiazolone derivative or its metal salt complex. CONSTITUTION: This antiseptic-mildew-proofing agent is obtained by compounding a hydrogen peroxide-generating substance with at least one kind selected from 3-isothiazolone derivatives or their metal salt complexes expressed by the formula (R1 and R2 are each H or a halogen; R3 is H or a 1-10C alkyl) in the ratio of 1:20 to 40:1 (weight ratio). Hydrogen peroxide is suitable as the hydrogen peroxide-supplying substance. Further, 5-chloro-2-methyl-4- isothiazoline-2-one is suitable as the 3-isothiazolone derivative of the formula and a magnesium chloride complex is suitable as the metal salt complex. An objective liquid to be treated with the industrial septic-mildew-proofing agent includes an aqueous liquid of polyacrylamide, a vinyl acetate emulsion, a latex emulsion, a water base paint, a metal processing oil, a water soluble adhesion, a starch sizing agent, etc.

Description

Detailed Description of the Invention

[0001]

[Industrial field of application] The present invention relates to industrial water-containing products and water-containing materials, especially polyacrylamide aqueous solution, vinyl acetate emulsion, latex emulsion, water-based paint, metal working oil, water-based adhesive, starch paste, paper coating. TECHNICAL FIELD The present invention relates to an industrial antiseptic and fungicide and a method for industrial antiseptic and fungicide, which are useful for controlling and controlling spoilage and deterioration due to microorganisms such as liquids, fiber oils and lignin liquids.

[0002]

2. Description of the Related Art Various latex emulsions, polyacrylamide aqueous solutions, which have been industrial products and materials, have been used.
Industrial water-containing products and water-containing materials such as water-based paints, metalworking liquids, water-based adhesives, starch pastes, paper coating liquids, fiber oils, lignin liquids are harmful to bacteria, molds and yeasts. Microbes breed and cause damage such as decay, deterioration, and contamination of products and materials, which causes a decrease in production efficiency and a decrease in quality value. So far, we have suppressed the generation of harmful microorganisms,
Or, many antiseptic and fungicides are used for the purpose of controlling. However, it has been difficult to obtain a satisfactory effect with only one kind of antiseptic / antifungal agent. So Shokoku Sho 6
No. 0-54281 or Japanese Patent Publication No. 6-47524
As disclosed in Japanese Patent Laid-Open Publication No. 2003-242, the combined use of a complex compound with an isothiazolone derivative or a specific inorganic salt thereof and a halogenated nitroalcohol compound is disclosed, and a considerable improvement has been made.

[0003]

However, as a result of a long-term study conducted by the present inventors, it cannot be said that the antiseptic / antifungal effect is still sufficient even in such a conventional combination system.
Furthermore, it was found that if a reducing substance is present in the added product or material, its effect is significantly reduced.

Such a reducing substance is a residual substance or a decomposed substance of a polymerization initiator of redox polymerization, which is widely used as a synthetic means of an aqueous phase dispersion liquid, an emulsion liquid, a solution, etc. of a polymer, pulp or Industrial water in the papermaking process, or
It may be a reducing substance contained in the lignin solution. The reducing substance to which the present invention is applied is not particularly limited. Examples of representative reducing substances include sulfites such as potassium sulfite, calcium nitrite, zinc sulfite, and ammonium sulfite; hydrogen sulfites such as sodium hydrogen sulfite, potassium hydrogen sulfite, calcium hydrogen sulfite, and ammonium hydrogen sulfite; sodium pyrosulfite. , Pyrosulfites such as calcium pyrosulfite and ammonium pyrosulfite; dithionite salts such as sodium dithionite, potassium dithionite, calcium dithionite and ammonium dithionite; sodium trithionite, Trithionates such as potassium trithionate; Tetrathionates such as sodium tetrathionate and potassium tetrathionate; Thiosulfates such as sodium thiosulfate and potassium thiosulfate; Sodium nitrite, potassium nitrite, calcium nitrite Such as nitrite; dimethyl Min, organic amines such as triethylamine; hydroxylamine hydrochloride, hydroxylamine sulfate, sulfur dioxide, sodium sulfide, ascorbate, formaldehyde sulfoxylate salts, formic acid,
Examples include citric acid and nitrotrispropionamide.

The present inventor has solved these problems of the conventionally used chemicals and has an excellent antiseptic and fungicidal effect even in a small amount, and in particular, an antiseptic and fungicide which is effective even for a target system in the presence of a reducing substance. The present invention seeks to provide an agent and an antiseptic / antifungal method.

[0006]

As a result of various studies on these problems, the present inventors have found that a hydrogen peroxide-supplying compound and a 3-isothiazolone derivative (hereinafter abbreviated as MIT) or a metal salt complex thereof are used. If used together,
With a much smaller amount than when used alone, the bactericidal and bacteriostatic power is synergistically enhanced, and it exhibits an excellent antiseptic effect.
In particular, they have found that they exhibit an effective antiseptic / antifungal effect even for a target system in the presence of a reducing substance, and completed the present invention.

The present invention thus provides a hydrogen peroxide feed and a general formula

[Chemical 5] (In the formula, R ₁ and R ₂ each represent a hydrogen atom or a halogen atom, and R ₃ represents a hydrogen atom or a carbon number of 1-10.
Means an alkyl group. And a one or more kinds of 3-isothiazolone derivative or metal salt complex thereof represented by the formula (1), at a weight ratio of 1:20 to 40: 1, and an industrial antiseptic and fungicide. The present invention relates to an industrial antiseptic / antifungal method using an industrial antiseptic / antifungal agent.

In the above and subsequent description of the present specification, suitable examples and explanations of the various definitions included within the scope of the present invention are explained in detail below. Suitable "1 carbon number
“10 alkyl groups” refers to straight or branched chain alkyl having 1 to 10 carbon atoms, eg, methyl,
Ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, nonyl, decyl,
Among them, preferred is an alkyl group having 1 to 8 carbon atoms, and most preferred is a methyl group.

A suitable "halogen atom" is chlorine,
Examples include bromine and iodine. Specific examples of MIT and its metal salt complex are given below. 2-Methyl-4-isothiazolin-3-one and its magnesium chloride complex, 5-chloro-2-methyl-4-isothiazolin-3-one and its magnesium chloride complex, 4,5-dichloro-2-methyl-4- Isothiazolin-3-one and its zinc chloride complex, 2-n-butyl-4-isothiazolin-3-one and its zinc chloride complex, 2-n-octyl-4
-Isothiazolin-3-one and its zinc chloride complex, 4,5-dichloro-2-n-octyl-4-
Isothiazolin-3-one and its iron chloride complex 5-chloro-2-n-decyl-4-isothiazolin-3
-On and its calcium chloride complex,

Specific examples of the hydrogen peroxide-supplying compound which is another active ingredient in the present invention include hydrogen peroxide, hydrogen peroxide of sodium metasilicate and sodium metaborate, sodium or potassium salt of peroxodicarbonate,
Examples thereof include compounds that easily generate hydrogen peroxide in water or acidic water, such as calcium, sodium or barium peroxide, potassium peroxodisulfate, ammonium, potassium or sodium peroxodisulfate. Among them, the hydrogen peroxide solution is particularly preferable in terms of economy and handling.

As the treatment liquid in the present invention, polyacrylamide aqueous solution, vinyl acetate emulsion, latex emulsion, water-based paint, metal working oil, water-based adhesive, starch paste, coating liquid for paper, fiber oil, lignin liquid, etc. for industrial use Includes water-containing products and materials.

In a preferred embodiment of the present invention, the antiseptic and antifungal treatment is carried out by adding the active ingredient of the present invention (MIT or its metal salt compound and hydrogen peroxide supplying compound) as a complex preparation to the antiseptic and antifungal system. Alternatively, by adding and mixing a hydrogen peroxide supplying compound to the target system and then adding MIT or a metal salt compound thereof, a very effective antiseptic and antifungal method is provided. The ratio (weight ratio) at which the synergistic bactericidal antiseptic effect is exhibited in the combination of the hydrogen peroxide supplying compound and MIT or its metal salt complex in the present invention is preferably 1:20 to 40: 1. It is more preferable that the ratio is 1:10 to 10: 1.

In applying the present invention, the addition amount varies depending on the object to be used, the required period of antiseptic and fungi, etc.
When used for the purpose of antiseptic and mildew protection of industrial products or industrial materials for usually 1 to 3 months, the added amount is 0.1 to 1000 mg / l, preferably 1 to 500 mg in total concentration of active ingredients.
/ L so that it will be about 1 /.

When the active ingredient of the present invention is formulated into a composite preparation and applied to such a system to be used, additives (glycols for antifreezing, storage stability of the preparation) which do not impair the effects of the present invention are used. For improvement, for example, 2,
2-dibromo-2-nitro-1-ethanol, 2-bromo-2-nitro-1,3-propanediol and other organic bromonitro compounds) may be contained. The present invention will be described below with reference to examples.

[0015]

【Example】

Examples 1 to 9 and Controls 1 to 9 Sodium pyrosulfite (Na ₂
S ₂ O ₅ ) was added in a predetermined amount, and then bacteria (Pseudomonas pu) separated from the acrylic emulsion were added.
(Tida) was pre-cultured in a broth medium in advance, and fungus (Cladospo) separated from an acrylic emulsion
ium sp. Inoculate a fixed amount of the spore dispersion liquid of 1) and use it as test water. Each drug was added to this test water so as to have the addition method and the addition concentration shown in Tables 1 and 2, and the number of bacteria and the number of molds in the test water were measured daily. The results are shown in Tables 1-2.

[0016]

[Table 1] The drug A in the table represents a 12% hydrogen peroxide solution. Drug B
Is a product name of Rohm & Haas Co. Caison WT (5-chloro-2-methyl-3-isothiazolone magnesium chloride 16.5%, 2-methyl-3-isothiazolone magnesium chloride 7.0%, magnesium nitrate approximately 13%. Aqueous solution). The drug C is a trade name of Ichikawa Gosei Kagaku Co., Ltd. Sonnen F (5-chloro-2-methyl-
4-isothiazolin-3-one 10%, 2-methyl-
An aqueous solution containing 1% of 4-isothiazolin-3-one and 89% of ethylene glycol). The drug D represents Skane M8 (2-n-octyl-4-isothiazolone 40% solution, propylene glycol 60% solution) manufactured by Rohm & Haas Company.

[0017]

[Table 2]

Examples 10 to 13 Active ingredient A is diluted to a predetermined concentration with water, and active ingredient B or active ingredient D is added thereto to prepare a liquid preparation. If necessary, a glycol organic solvent and a bromonitro compound are added. Table 3 describes formulation examples of the composition of the present invention. In the table,% is a weight percentage.

The active ingredient A used was a commercially available 35% hydrogen peroxide solution, and the active ingredient (B) was Caison WT (5-chloro-2-methyl-3-isothiazolone magnesium chloride 16. 5%, 2-methyl-3
An isothiazolone magnesium chloride 7.0%, an aqueous solution containing about 13% magnesium nitrate). The active ingredient (D) is a product name of Rohm & Haas Company, Skane M8.
(2-n-octyl-4-isothiazolone 40%, propylene glycol 60% solution).

[0020]

[Table 3] * 1 Bromonitro compound; 2-nitro-2-bromo-
1,3-Propanediol * 2 (Tetronic 702); Polyoxyethylene and polyoxypropylene adducts of ethylenediamine

Evaluation of the preparation according to Example 10 in a hydrous product Sodium pyrosulfite (Na ₂ S ₂ O ₅ ) as reducing substance
As a preservative in a vinyl acetate emulsion containing 100 mg / l of Caesone WT (5-chloro-2-methyl-3-isothiazolone, 16.5% magnesium chloride, 2-methyl-3-methyl-3-isothiazolone as a preservative. An aqueous solution containing 7.0% magnesium isothiazolone and about 13% magnesium nitrate was added at 200 mg / l and shipped, and one month later, the customer turned to yellow and complained that the product had a rotting odor. did. An investigation of the complained product revealed that the product was contaminated by alteration by bacterial fungi. Therefore, thereafter, Formulation I (Example 10) described in the formulation example of the formulation of the present invention was administered at 500 mg / l.
When added (containing 100 mg / l as caisson WT) and shipped, the damage due to putrefaction disappeared and the quality was stable. After 3 months, the number of bacteria and mold in the stored sample of the shipped product was measured, and none was detected.

The bacterium (Pseud) was added to a polyacrylamide aqueous solution having a nonvolatile content of 15% (sodium pyrosulfite was used as a redox polymerization initiator in an amount of 270 ppm).
Omonas putida) and the mold (Cl)
adosporium sp. A certain amount of the spore dispersion liquid of 1) was inoculated to obtain a test water. The drug A was added to the test water so that the ratio was as shown in Table 4, the drug B was added 5 minutes later, and the number of bacteria and the number of molds in the test water after 7 days were measured.

[Table 4]

Claims (7)

[Claims] 1. Hydrogen peroxide feed and general formula: (In the formula, R ₁ and R ₂ each represent a hydrogen atom or a halogen atom, and R ₃ represents a hydrogen atom or a carbon number of 1-10.
Means an alkyl group. (3) A 3-isothiazolone derivative or one or more kinds of metal salt complexes thereof are contained in a weight ratio of 1:20 to 40: 1, and an industrial antiseptic and fungicide. 2. The industrial antiseptic and fungicide according to claim 1, wherein the hydrogen peroxide supply is hydrogen peroxide. 3. The 3-isothiazolone derivative is 5-chloro-2-methyl-4-isothiazolin-3-one,
The industrial antiseptic and fungicide according to claim 1, wherein the metal salt complex is a magnesium chloride complex. 4. The 3-isothiazolone derivative is 2-n-octyl-4-isothiazolin-3-one.
The industrial antiseptic and fungicide described. 5. Hydrogen peroxide feed and general formula (In the formula, R ₁ and R ₂ each represent a hydrogen atom or a halogen atom, and R ₃ represents a hydrogen atom or a carbon number of 1-10.
Means an alkyl group. 1) or a mixture of one or more of the 3-isothiazolone derivative represented by the formula 1) or a metal salt complex thereof is added to the liquid to be treated at a ratio of 1:20 to 40: 1 by weight or a hydrogen peroxide feed is added. After that, the general formula: (In the formula, R ₁ and R ₂ each represent a hydrogen atom or a halogen atom, and R ₃ represents a hydrogen atom or a carbon number of 1-10.
Means an alkyl group. ) The 3-isothiazolone derivative represented by 1) or one or more metal salt complex thereof is added and used in a ratio of 1:20 to 40: 1 in the liquid to be treated in combination for industrial use. Antiseptic and antifungal method. 6. A hydrogen peroxide feed and a general formula: (In the formula, R ₁ and R ₂ each represent a hydrogen atom or a halogen atom, and R ₃ represents a hydrogen atom or a carbon number of 1-10.
Means an alkyl group. ) The 3-isothiazolone derivative represented by 1) or one or more kinds of metal salt complexes thereof are contained in a weight ratio of 1:20 to 40: 1 to treat an industrial antiseptic and fungicide. The industrial antiseptic and fungicide method according to claim 5, wherein 0.1 to 1000 mg / l is used for the target liquid. 7. A liquid to be treated is a reducing substance such as polyacrylamide aqueous solution, vinyl acetate emulsion, latex emulsion, water-based paint, metal working oil, water-based adhesive, starch paste, paper coating liquid, fiber oil, lignin liquid, etc. The industrial antiseptic and fungicide method according to claim 5 or 6, which is an industrial water-containing product or water-containing material.