JPH09227306A - Industrial bactericide and industrial sterilization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the above agent excellent in stability of preparation thereof, having an excellent bactericidal effect in an alkaline pH region, and also maintaining the effect for a long period of time by adding a specific additive to an aqueous solution of glutaraldehyde. SOLUTION: This industrial bactericide contains (A) glutaraldehyde and (B) an adduct of formaldehyde with a 2-6C aliphatic glycol or monoalkyl ether thereof (provided that the ether residue is a 1-4C alkyl). As the component (B), especially an adduct of formaldehyde with ethylene glycol or diethylene glycol is preferable. The blending ratio of the cojnponents (A) to (B) is preferably (1:1)-(1:50) by weight. An industrial bactericide is obtained by blending 1-30 pts.wt. component (A), 5-98 pts.wt. component (B) and the rest of water. This industrial bactericide is useful for the sterilization of a process water and a pulp slurry in a paper or pulp factory, a slime control of a cooling water or a washing water in various industries, or antisepsis, anti-fungus, etc., of industrial products.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an industrial fungicide containing a glycol adduct of glutaraldehyde and formaldehyde and a method for using the same. More specifically,
Papermaking process in paper and pulp mills Water and pulp slurry,
For slime control and sterilization of cooling water and washing water for various industries, metal working oil (cutting oil), fiber oil, paper coating liquid (coating color, calcium carbonate slurry), paint, latex, paste, etc. It is useful as an antiseptic, antifungal and sterilizer for industrial products.

[0002]

2. Description of the Related Art Conventionally, process water in the paper / pulp industry, cooling water systems in various industries, and wash water for circulating use in the steel industry and paper / pulp industry generate slime due to bacteria and fungi, and It is known that there are obstacles such as deterioration of quality and deterioration of production efficiency.

In many industrial products such as metalworking oils (cutting oils), fiber oils, paper coating liquids (coating colors, calcium carbonate slurries), paints, latices, sizing agents, etc., they are decomposed by bacteria and fungi. Contamination occurs, polluting the product and reducing its value. Therefore, 5-chloro-2-methyl-4-isothiazoline-3 has been conventionally used.
-One, 2-methyl-4-isothiazolin-3-one,
4,5-Dichloro-2-n-octyl-isothiazolin-3-one, 2-n-octyl-isothiazolin-3-one
Isothiazolones represented by on and 2-bromo-2-
Nitropropane-1,3-diol, 2,2-dibromo-2-nitro-1-ethanol, 2,2-dibromo-3
-Many industrial fungicides such as organic bromine compounds represented by nitrilopropionamide have been used.

However, among the above-mentioned industrial sterilization target systems, particularly sterilization target systems containing water and having an alkaline pH, for example, paper containing no neutral sizing agent and using no sulfuric acid band.
Neutral papermaking system of pulp mill, metalworking fluid (cutting fluid),
In the case of fiber oils, paper coating liquids (coating color, calcium carbonate slurry), the bactericidal effect of known industrial bactericides decreases with time, and there is a problem in that an effective bactericidal effect cannot be expected for a long period of time. there were.

Glutaraldehyde, which is one of the active ingredients of the present invention, is known as an industrial bactericidal agent which is particularly effective in an alkaline pH range. Synergistic effect with known bactericides, such as isothiazolones, 2,2-dibromo-2-nitroalcohol, and methylenebisthiocyanate (JP-A-63-88105, JP Kaihei 1
-272506, JP-A-2-53703, and JP-B-6-35366).

The addition product of formaldehyde and an aliphatic glycol having 2 to 8 carbon atoms, which is another active ingredient of the present invention, is a known bactericide such as 2-methyl-3-oxo-5-chlorothiazoline. An industrial preservative which is used in combination with (1, 2) and dimethylolurea is known (see JP-A-54-129125).

[0007]

The above glutaraldehyde is unstable in air and soluble in water,
It is usually commercially available in the form of an aqueous solution. However, when an aqueous solution of glutaraldehyde is stored at room temperature or higher for a long period of time, it gradually polymerizes, causing phenomena such as turbidity or precipitation in the aqueous solution, or when a sticky substance precipitates when added to a system to be sterilized. was there.

[0008] Further, glutaraldehyde alone has a short sterilization duration and is preferably used in combination with other persistent bactericides. However, turbidity, precipitation, and / or formation of sticky substances, etc. were observed in the combined preparation of glutaraldehyde and other fungicides, which was particularly remarkable in the combined preparation of glutaraldehyde and isothiazolones (short term Generated).

As a result, the system to be sterilized is often contaminated, and the intended bactericidal effect is often not exhibited even when such an aqueous solution is used, and it is put into practical use if the period from production to actual use is taken into consideration. It was very difficult. In addition, the bactericidal effect of glutaraldehyde is said to be in the free aldehyde group, and the point of action is considered to be on the surface of bacteria (microbial sterilization / sterilization / mold prevention technology, published by the Sanitary Engineering Association). Therefore, in order to exert the bactericidal effect of glutaraldehyde, it is necessary to leave the aldehyde group free without polymerizing.

The present invention has been made under such circumstances, and has an excellent bactericidal effect in a stable formulation and an alkaline pH range, and an industrial bactericidal agent and an industrial bactericidal agent having a long-lasting bactericidal effect. It is intended to provide a sterilization method.

[0011]

SUMMARY OF THE INVENTION The inventors of the present invention have
As a result of earnest research to achieve the above object, formaldehyde and an aliphatic glycol having 2 to 6 carbon atoms or a monoalkyl ether thereof (in which the ether residue is an alkyl group having 1 to 4 carbon atoms) was added to an aqueous solution of glutaraldehyde.
The fact that the storage stability of a composite preparation in which the same amount or more of the adduct of and is mixed is significantly improved, that is, the phenomenon such as turbidity or precipitation in the storage preparation or the precipitation of an adhesive substance when added to the sterilization target system We have found that the phenomenon never occurs. It is considered that glutaraldehyde is protected by the adduct of formaldehyde and glycols one molecule at a time, which inhibits the polymerization of glutaraldehyde. Further, it has been found that this combined preparation exhibits a remarkable synergistic effect and the bactericidal effect lasts for a long time, and that the effect is remarkable in a system to be sterilized having an alkaline pH.

Thus, according to the present invention, glutaraldehyde (component A), formaldehyde and carbon number 2 to 6
Aliphatic glycol or its monoalkyl ether (provided that the ether residue is an alkyl group having 1 to 4 carbon atoms)
There is provided an industrial bactericide characterized by containing an adduct (component B) with and as an active ingredient.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, glutaraldehyde which is the component A is known, and even if a commercial product (manufactured by Union Carbite Co., trade name "Acucar 550": 50% by weight aqueous solution of glutaraldehyde) is used. Good.

Further, the component B of the present invention is a known substance. "Formaldehyde and an aliphatic glycol having 2 to 6 carbon atoms or a monoalkyl ether thereof (provided that the ether residue has an alkyl group having 1 to 4 carbon atoms) "Adduct with glycols selected from
Examples of the "6 aliphatic glycol" include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,4-Pentanediol, 1,5-pentanediol, 2,5-hexanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and the like can be mentioned, and the “monoalkyl ether” can be any of the above. Examples thereof include glycol monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether. Of these, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol and diethylene glycol monomethyl ether are preferable.

In the present invention, the adduct of the component B is an adduct of 1 to 2 mol of formaldehyde and 1 mol of an aliphatic glycol having 2 to 6 carbon atoms or 1 mol of formaldehyde and an aliphatic glycol having 2 to 6 carbon atoms. An adduct with 1 mol of monoalkyl ether is mentioned. These B component adducts are obtained by heating the corresponding glycols with paraformaldehyde in the presence of an alkaline agent such as calcium carbonate.

It is remarkable that the industrial bactericide of the present invention contains the component A and the component B in a weight ratio of 2: 1 to 1:98, and more preferably in a weight ratio of 1: 1 to 1:50. It is preferable because a synergistic effect is exhibited. The synergistic effect of the present invention refers to an effect that the bactericidal concentration against bacteria is reduced to 1/3 to 1/5 and an effect that the bactericidal effect lasts for 3 to 4 weeks as compared with the case of using each alone. The industrial fungicide formulation of the present invention is preferably an aqueous formulation since each active ingredient is soluble in water. The aqueous preparation is prepared by using the weight ratio of the component A and the component B that exerts the above synergistic effect, and 1 to 30 parts by weight of the component A, 5 to 98 parts by weight of the component B and the balance as water. It is preferable in terms of formulation stability during long-term storage.

When the aqueous preparation of the present invention thus obtained is added to a water-containing sterilization target system in an alkaline pH range, it has good long-term storage stability and precipitation of adhesive substances due to glutaraldehyde. Such a phenomenon does not occur, and the system to be sterilized can be sterilized for a long period of time.

Further, it is a known bactericide in the preparation of the present invention to the extent that it does not impair the above effects of the present invention.
-Chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,
5-dichloro-2-n-octyl-isothiazoline-3
-One, 2-n-octyl-isothiazolin-3-one, isothiazolones such as 1,2-benzisothiazolone; 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-2-nitro -1-ethanol,
An organic bromine compound such as 2,2-dibromo-3-nitrilopropionamide; methylenebisthiocyanate or the like may be blended, and a hydrophilic organic solvent such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, or polyethylene. Glycols, glycols such as polypropylene 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 Esters and the case of the may contain various surfactants.

The addition amount of the industrial sterilizing agent of the present invention varies depending on the system to be sterilized for industrial use, but usually the total amount of active ingredients is 10 to 2000 mg / L, preferably 50 to 1000 mg.
Addition of / L exerts an effective bactericidal effect. The industrial bactericidal agent of the present invention is preferably used as a one-part formulation as described above, but each active ingredient may be separately added to an industrial target system in combination.

According to the present invention, an industrial sterilization target system is
Adduct (component B) of glutaraldehyde (component A) with formaldehyde and aliphatic glycol having 2 to 6 carbon atoms or its monoalkyl ether (provided that the ether residue is an alkyl group having 1 to 4 carbon atoms). And the total amount of 10 to 20
There is provided an industrial sterilization method characterized by being added in combination with 00 mg / L, preferably 50 to 1000 mg / L.

In the present invention, if each active ingredient is less than the above-mentioned minimum concentration, a sufficient bactericidal effect cannot be obtained, which is not preferable, and even if it is added in excess of the above-mentioned maximum concentration, no further bactericidal effect can be obtained, which is economical. Not good for In the present invention, the combination ratio of the component A and the component B is 2: 1 to 1:98 by weight ratio, preferably 1: 1 to 1:50 by weight ratio.
It is more preferable to add them together so that the synergistic bactericidal effect is exhibited.

The industrial sterilizer of the present invention and the industrial sterilization target system in the industrial sterilization method include slime control and sterilization of papermaking process water and pulp slurry in paper and pulp mills, cooling water and washing water for various industries. Or metal working oil (cutting oil), fiber oil, paper coating liquid (coating color, calcium carbonate slurry), paint,
Examples include industrial products such as latex and sizing agent.

In particular, it is preferable that the pH of the industrial sterilization target system is alkaline, particularly pH of 8 or more, since a more remarkable synergistic effect is exhibited. As a system to be sterilized, neutral sizing agents are used, neutral papermaking systems for paper and pulp mills that do not use sulfuric acid bands, metalworking fluids (cutting fluids), fiber oils, paper coating fluids (coating color). , Calcium carbonate slurry), latex, starch paste and other industrial products.

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

[0025]

[Examples] Formulation examples of the industrial bactericide of the present invention are described below. Formulation Example 1 Formulation Example 2 Glutaraldehyde 1 part by weight Glutaraldehyde 4 parts by weight FEG 50 parts by weight FPG 80 parts by weight Water 49 parts by weight Water 16 parts by weight Formulation Example 3 Formulation Example 4 Glutaraldehyde 10 parts by weight Glutaraldehyde 10 parts by weight FDEG 50 Parts by weight FBD 10 parts by weight Water 40 parts by weight Water 70 parts by weight DEG 10 parts by weight Formulation example 5 Formulation example 6 Glutaraldehyde 20 parts by weight Glutaraldehyde 25 parts by weight FMDG 60 parts by weight FBD 50 parts by weight Water 20 parts by weight Water 25 parts by weight Formulation Example 7 Formulation Example 8 Glutaraldehyde 10 parts by weight Glutaraldehyde 10 parts by weight FMDG 50 parts by weight FBD 50 parts by weight BIT 5 parts by weight MIT 1 part by weight Water 35 parts by weight Water 39 parts by weight The abbreviations in each formulation example are as follows. A compound is shown. FEG formaldehyde 2 moles and ethylene glycol 1 mole adduct FDEG formaldehyde 2 moles and diethylene glycol 1 mole adduct FPG formaldehyde 2 moles and propylene glycol 1 mole adduct FMDG formaldehyde 1 mole and diethylene glycol monomethyl ether 1 mole Addition product FBD Addition product of 1 mol of formaldehyde and 1 mol of 1,4-butanediol DEG Diethylene glycol BIT 1,2-Benzisothiazolone MIT 5-Chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4 -Isothiazoline-3
-Mixture with ON (weight ratio 9: 1)

Test Example 1: [ Test for confirming bactericidal effect on putrefaction coating color] The putrefaction coating color (pH) obtained from a paper manufacturing company
Various germicides were added to 8.8) 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. Table 1 shows the results.

[0027]

[Table 1]

Test Example 2: [ Test for confirming bactericidal effect against spoiled cutting oil] 70 parts by weight of mineral oil, 4.5 parts by weight of oleic acid, 3 parts by weight of triethanolamine, Ionet MO-660 (surfactant manufactured by Sanyo Kasei Co., Ltd.) ) 7.5 parts by weight and Ionette S-8
0 (Sanyo Kasei Co., Ltd. Surfactant) A composition (cutting oil) consisting of 15 parts by weight was prepared, diluted 20 times with industrial water, and left standing in a constant temperature bath at 30 ° C to rot. Was used as a test sample. Add various concentrations of various fungicides to this sample,
The viable cell count after standing in a constant temperature bath at 30 ° C was measured daily. Table 2 shows the results.

[0029]

[Table 2]

Test Example 3: [Test for confirming formulation stability during long-term storage and presence of precipitates when added to water] A glutaraldehyde aqueous solution and various compositions in which the B component was mixed with the glutaraldehyde aqueous solution were prepared. The pH of each composition was adjusted to 7 with sodium hydroxide.
Then, it was left in a constant temperature bath at 50 ° C. for 1 month, and the appearance of each composition after standing and the presence or absence of precipitates when added to water were examined. Table 3 shows the results.

[0031]

[Table 3]

[0032]

INDUSTRIAL APPLICABILITY Industrial fungicides containing a glutaraldehyde-formaldehyde glycol adduct have excellent formulation stability, exhibit an excellent bactericidal action due to a remarkable synergistic effect in an alkaline pH range, and The effect lasts for a long time.

Claims (7)

[Claims] 1. Addition of glutaraldehyde (component A) with formaldehyde and an aliphatic glycol having 2 to 6 carbon atoms or a monoalkyl ether thereof (provided that the ether residue is an alkyl group having 1 to 4 carbon atoms). An industrial bactericide characterized by containing a substance (component B) as an active ingredient. 2. The industrial fungicide according to claim 1, wherein the component B is an adduct of formaldehyde and ethylene glycol or diethylene glycol. 3. The industrial bactericide according to claim 1 or 2, wherein the A component and the B component are contained in a weight ratio of 1: 1 to 1:50. 4. The industrial bactericide according to any one of claims 1 to 3, wherein the component A is 1 to 30 parts by weight, the component B is 5 to 98 parts by weight, and the balance is water. 5. An industrial sterilization target system includes glutaraldehyde (component A), formaldehyde, and an aliphatic glycol having 2 to 6 carbon atoms or a monoalkyl ether thereof (however,
An industrial sterilization method, characterized in that a total amount of 10 to 2000 mg / L of an ether residue and an adduct (component B) with an alkyl group having 1 to 4 carbon atoms is added together. 6. The industrial sterilization method according to claim 5, wherein the combined ratio of the component A and the component B is 1: 1 to 1:50 as a weight ratio. 7. The industrial sterilization target system contains water, and its p
The industrial sterilization method according to claim 5 or 6, wherein H is alkaline.