JPH09249506A - Industrial germicide and industrial disinfection - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an industrial germicide effective against bacteria, etc., causing decay of process water, etc., in paper/pulp industries, having germicidal effects at a low concentration even in an alkali region, by using a specific compound. SOLUTION: This industrial germicide comprises a glycol derivative (e.g. a 2-6C aliphatic glycol) of formaldehyde (A) and an organic nitrogen sulfur-based germicide (e.g. methylenebisthiocyanate) (B) as active ingredients. The ratio of the components A/B is 99/1 to 1/1. The components are dissolved in an organic solvent (ethylene glycol, etc.) an the concentration of the active ingredients in use is preferably 10-1,000mg/l.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrial sterilizer and an industrial sterilization method which contain a glycol derivative adduct of formaldehyde and an organic nitrogen-sulfur sterilizer as active ingredients. More specifically, the present invention relates to an industrial sterilizer and an industrial sterilization method which are useful for a system to be sterilized in an alkaline to neutral to acidic range, particularly in an alkaline range.

[0002]

2. Description of the Related Art Conventionally, process water in the paper and pulp industry and cooling water systems in various industries generate slime due to bacteria and fungi, which causes deterioration of product quality and production efficiency. It is known that there are obstacles such as deterioration. Also, many industrial products such as metalworking oils (cutting oils), fiber oils, paper coating fluids (coating color, calcium carbonate slurry), paints, latex, resin emulsions, rosin emulsions Corrosion and contamination by fungi and fungi stain the product and reduce its value.

Therefore, the conventional low toxicity bactericidal agent 5-
Chloro-2-methyl-4-isothiazolin-3-one,
2-Methyl-4-isothiazolin-3-one, 4,5-
Isothiazolones represented by dichloro-2-n-octyl-isothiazolin-3-one, 2-n-octyl-isothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, 2-bromo Industrial bactericides such as 2-nitropropanol, 1,4-bisbromoacetoxy-2-butene, and organic bromine compounds represented by bisbromoacetoxyethane have been used.

On the other hand, among the above-mentioned sterilization target systems, process water in the paper and pulp industry, metalworking oil agents (cutting oil agents), fiber oil agents, paper coating liquids (coating color, calcium carbonate slurry), paints, latexes, resins Industrial products such as emulsions, rosin emulsions, and sizing agents tend to increase in the number of cases where their properties become alkaline with a pH of 7 or higher due to changes or improvements in raw materials.

For example, in the paper and pulp industry, a neutral sizing agent is used to prevent deterioration of paper quality, and in a neutral papermaking system using calcium carbonate as a filler, the pH of the papermaking process water is 7
The above becomes alkaline. In addition, a latex modified by carboxylation is manufactured to improve stability, but the pH of this latex is alkaline, and the coating color using this latex and the coating color liquid containing calcium carbonate as the pigment are used. Sex is pH 7
The above becomes alkaline. An alkali swelling latex is used for gravure printing, and the liquidity of this alkali swelling latex is also alkaline with a pH of 7 or more.

In the case of an emulsion type cutting oil, mineral oil and a surfactant are mixed and used in the state of an emulsion after being diluted with water at the cutting site. It contains an alkali, etc., so that it has a pH of 7 or higher. However, many of the conventionally known industrial bactericides are stable in the acidic region and decomposed in the alkaline region, and a long-term bactericidal effect could not be expected.

For the purpose of exerting a synergistic effect, an adduct of formaldehyde and an aliphatic glycol, which is one of the active ingredients of the present invention, is combined with a known bactericide thiadiazin-2-thione compound. It is known that two components are used in combination, and that three components are used in combination with 5-chloro-2-methyl-4-isothiazolin-3-one and dimethylolurea (JP-A-51-98333, JP-A-51-98333). 54-1291
(See No. 25).

It is known that methylenebisthiocyanate is used as a combination of two components with an isothiazolone compound or a complex salt thereof (see Japanese Patent Laid-Open No. 5-163107). These compositions have a bactericidal effect due to synergistic action, but in the alkaline region, a sufficient long-term bactericidal effect cannot be expected, or a bactericidal agent containing a complex salt or a stable salt of an isothiazolone compound is highly effective such as latex. When added to a molecular emulsion, the emulsion phase is destroyed and phase separation and coagulation occur.
There is a problem that so-called emulsion shock occurs.

Therefore, in order to prevent damages caused by various microorganisms in the alkaline region, a bactericidal agent which exerts an excellent bactericidal effect in a low concentration in the alkaline region as in the acidic to neutral region, and which maintains the effect. Is requested.

[0010]

SUMMARY OF THE INVENTION The inventors of the present invention have
From this point of view, as a result of various studies, by combining an adduct of formaldehyde with an aliphatic glycol and a specific organic nitrogen-sulfur fungicide, a remarkable bactericidal effect on a wide range of microorganisms and its bactericidal effect can be obtained especially in an alkaline region. We have found a surprising fact that the effect is lasting.

Thus, according to the present invention, there is provided an industrial bactericide characterized by containing a formaldehyde glycol derivative adduct (component A) and an organic nitrogen-sulfur bactericide (component B) as active ingredients. . Further, according to the present invention, there is provided an industrial sterilization method characterized in that the A component and the B component are added to the system to be sterilized simultaneously or separately so that the total amount becomes 10 to 2000 mg / L. It

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The system to be sterilized according to the present invention is, for example, a liquid having an alkaline property, particularly a pH of 8 or more. Calcium), 2) Metalworking oils (compounding organic and inorganic alkali rust preventives), latexes (carboxylated and modified or alkali swelling), coating colors (use of the above latex or calcium carbonate as pigment) Stuff),
Examples include industrial products such as fiber oils (using the above latex), calcium carbonate slurry, starch paste solution, and the like.

[0013] In glycol derivative adducts of formaldehyde which is the component A of this invention, the term "glycol" derivative means a C _2-6 aliphatic glycol or its monoalkyl ether, in particular C _2-6 aliphatic As the group glycol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,4- Pentane diol, 1,5-pentane diol, 2,5-hexane diol, 1,6-hexane diol, diethylene glycol, dipropylene glycol and the like can be mentioned, and the alkyl ether thereof can be monomethyl ether, monoethyl ether, monopropyl. Ether, monobutyl ether Of these, ethylene glycol, propylene glycol, 1,4-butanediol,
Diethylene glycol or diethylene glycol monoethyl ether is preferable, and ethylene glycol or diethylene glycol is particularly preferable.

In the present invention, the glycol derivative adduct of formaldehyde, which is the component A, is an adduct of 1 to 2 mol of formaldehyde and 1 mol of C _2-6 aliphatic glycol, or 1 mol of formaldehyde and C _2-6 aliphatic. An adduct with 1 mol of glycol monoalkyl ether is mentioned, and an adduct with 2 mol of formaldehyde and 1 mol of C _2-6 aliphatic glycol is particularly preferable. The adduct which is the component A can be obtained by heating the corresponding glycol with paraformaldehyde in the presence of an alkaline agent such as potassium carbonate.

The organic nitrogen-sulfur fungicide which is the B component in the present invention comprises methylenebisthiocyanate and an isothiazolone derivative. Examples of the isothiazolone derivative include 1,2-benzisothiazoline-
3-one, 4,5-dichloro-2-n-octylisothiazolin-3-one, 2-n-octylisothiazolin-3-one and the like can be mentioned, and particularly 1,2-benzisothiazolin-3-one is preferable.

All of these compounds are known compounds, and commercially available products may be used. The industrial bactericide of the present invention preferably contains the component A and the component B in a weight ratio of 99: 1 to 1: 1 because a remarkable synergistic effect is exhibited. The synergistic effect of the present invention means an effect that the bactericidal concentration is reduced to 1/2 to 1/3 and an effect that the bactericidal effect lasts for 3 to 4 weeks as compared with the case of using each alone.

The industrial bactericidal agent of the present invention is usually in the form of a liquid agent in which the active ingredients (adducts (A component) and B component produced in advance) are dissolved in an organic solvent and a surfactant is added if necessary. It is preferably used in the form of a formulation. As the organic solvent, particularly a hydrophilic organic solvent is used, for example, glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, methyl cellosolve, phenyl cellosolve, diethylene glycol monomethyl ether, dipropylene glycol. Glycol ethers such as monomethyl ether and tripropylene glycol monomethyl ether, alcohols having up to 8 carbon atoms, methyl acetate, ethyl acetate, 3
Examples include esters such as methoxybutyl acetate, 2-ethoxymethyl acetate, 2-ethoxyethyl acetate, propylene carbonate and dimethyl glutarate. These organic solvents may be used as a mixture with water.

As the surfactant, a cationic surfactant, an anionic surfactant, a nonionic surfactant or an amphoteric surfactant is suitable, and a nonionic surfactant is preferable from the viewpoint of stability as a preparation. preferable. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene polyoxypropylene copolymers, and alkyl betaines.

Further, the preparation can be made only from the components A and B. In this case, it is preferable that the content of the component B is 10% by weight or less, preferably 5% by weight or less, from the viewpoint of formulation stability of the liquid preparation. Further, 2-bromo-2-nitropropane-1,3-diol and 2,2-dibromo-2-nitro, which are known bactericides in the formulation of the present invention, to the extent that they do not inhibit the synergistic effect of the present invention. An organic bromine compound such as -1-ethanol or 2,2-dibromo-3-nitrilopropionamide may be added.

The industrial sterilization method of the present invention is as described above. In the industrial sterilization method of the present invention, the amount of the active ingredient added varies depending on the system to be industrially sterilized, but the total amount of the active ingredients is usually 10 to 2000 mg / L, preferably 50 to 1000 mg / L. Exhibits an effective bactericidal effect. In the present invention, if the addition amount is less than the minimum concentration, it is not preferable because a sufficient bactericidal effect cannot be obtained, and even if it is added more than the maximum concentration, a further bactericidal effect cannot be obtained, which is economically undesirable. Also in the industrial sterilization method of the present invention, the above-mentioned known bactericide may be used in combination.

[0021]

The present invention is illustrated by the following formulation examples and test examples.

[0022]

[Formulation Example] In the presence of potassium carbonate, the following glycols and paraformaldehyde are heated to 70 to 80 ° C (manufacture of adduct of component A), and the resulting adduct is mixed with the drug of each component B and each of the following solvents. Was prepared.

Formulation Example 1 Formulation Example 2 FEG 99 parts by weight FEG 30 parts by weight MBTC 1 part by weight MBTC 1 part by weight MDG 69 parts by weight

Formulation Example 3 Formulation Example 4 FEG 5 parts by weight FDEG 60 parts by weight MBTC 5 parts by weight MBTC 2 parts by weight MDG 90 parts by weight MDG 38 parts by weight

Formulation Example 5 Formulation Example 6 FPG 60 parts by weight FMDG 60 parts by weight MBTC 2 parts by weight MBTC 2 parts by weight DEG 8 parts by weight MDG 10 parts by weight MDG 30 parts by weight DEG 28 parts by weight

Formulation Example 7 Formulation Example 8 FBD 60 parts by weight FEG 10 parts by weight MBTC 2 parts by weight BIT 1 part by weight MDG 13 parts by weight MDG 89 parts by weight DEG 25 parts by weight

Formulation Example 9 Formulation Example 10 FDEG 30 parts by weight FBD 50 parts by weight BIT 3 parts by weight BIT 5 parts by weight MDG 67 parts by weight MDG 30 parts by weight DEG 15 parts by weight

Formulation Example 11 Formulation Example 12 FMDG 50 parts by weight FEG 5 parts by weight BIT 5 parts by weight BIT 5 parts by weight MDG 45 parts by weight MDG 50 parts by weight EG 40 parts by weight

Formulation Example 13 Formulation Example 14 FEG 99 parts by weight FEG 50 parts by weight BIT 1 part by weight BIT 5 parts by weight MBTC 5 parts by weight MDG 40 parts by weight

The above abbreviations mean the following compounds. FEG: Addition product of 2 mol of formaldehyde and 1 mol of ethylene glycol FDEG: Addition product of 2 mol of formaldehyde and 1 mol of diethylene glycol FPG: Addition product of 2 mol of formaldehyde and 1 mol of propylene glycol FMDG: 1 mol of formaldehyde and diethylene glycol monomethyl ether Addition product with 1 mol FBD: Addition product with 2 mol of formaldehyde and 1 mol of 1,4-butanediol DEG: Diethylene glycol MDG: Diethylene glycol monomethyl ether MBTC: Methylenebisthiocyanate BIT: 1,2-Benzisothiazolin-3-one

[0031]

[Test example]

Test Example 1 [Test for confirming bactericidal effect on putrefaction coating color] Putrefaction coating color (pH
9.5) (1% of rotten coating color was added to the obtained coating color to prepare a sample), various chemicals were added so as to have various concentrations (mg / L), and the mixture was allowed to stand in a constant temperature bath at 30 ° C. Then, the viable cell count was measured daily. The results are shown in Tables 1 to 3. The viable cell count was examined for the following bacterial species in the coating color. Pseudomonas sp .,
Alcaligenes s p., Flavobacterium sp ., Klebsiella
sp.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

EFFECTS OF THE INVENTION By using an adduct of formaldehyde with an aliphatic glycol and a specific organic nitrogen-sulfur fungicide,
In particular, in the alkaline range of pH 8.0 or more, a remarkable and persistent bactericidal effect is exhibited against a wide range of microorganisms.

Claims (11)

[Claims] 1. An industrial bactericide containing, as active ingredients, a glycol derivative adduct of formaldehyde (component A) and an organic nitrogen-sulfur bactericide (component B). 2. The glycol derivative that forms an adduct with formaldehyde as the component A is a C _2-6 aliphatic glycol or its monoalkyl ether (provided that the number of carbon atoms in the ether residue is 1 to 4). Item 1. The industrial fungicide according to Item 1. 3. The glycol derivative is ethylene glycol, diethylene glycol, propylene glycol,
The industrial bactericide according to claim 1 or 2, which is 1,4-butanediol or diethylene glycol monomethyl ether. 4. The industrial bactericide according to any one of claims 1 to 3, wherein the component A is an ethylene glycol or diethylene glycol adduct of formaldehyde. 5. The industrial bactericide according to claim 1, wherein the organic nitrogen-sulfur bactericide of the component B is a methylenebisthiocyanate or isothiazolone derivative. 6. The isothiazolone derivative is 1,2-benzisothiazolin-3-one, 4,5-dichloro-2-
The industrial fungicide according to any one of claims 1 to 5, which is a compound selected from n-octylisothiazolin-3-one and 2-n-octylisothiazolin-3-one. 7. The industrial bactericide according to claim 1, wherein the isothiazolone derivative is 1,2-benzothiazolin-3-one. 8. The industrial bactericide according to claim 1, wherein the component A and the component B are contained in a weight ratio of 99: 1 to 1: 1. 9. An industrial sterilization method, which comprises simultaneously and separately adding components A and B in a total amount of 10 to 2000 mg / L to the system to be sterilized. 10. The industrial sterilization method according to claim 9, wherein the combined use ratio of the component A and the component B is 99: 1 to 1: 1 by weight. 11. The industrial sterilization method according to claim 9, wherein the system to be sterilized contains water and the pH thereof is alkaline.