JP2834219B2 - Industrial sterilization / bacteriostatic composition stabilization method - Google Patents

Description

The present invention relates to a method for stabilizing an industrial bactericidal / bacteriostatic composition having good storage stability and good storage. More specifically, it is an aqueous preparation containing a 3-isothiazolone derivative metal salt complex and glutardialdehyde as a bactericidal / bacteriostatic active ingredient. The present invention relates to a stable industrial bacteriostatic / bacteriostatic composition whose decrease has been significantly suppressed.

(B) Conventional technology Conventionally, slime is generated by bacteria and fungi in the paper making process in the paper and pulp industry and in the cooling water system in various industries, which lowers the quality of products and lowers production efficiency. Industrial products such as heavy oil sludge, metalworking oils, fiber oils, paints, various latexes, sizing agents, and the like, cause decay and contamination by bacteria and fungi, thereby fouling the products and reducing their value.

Many fungicides have been used to prevent damage by these microorganisms. In the past, organic mercury compounds and chlorinated phenol compounds were used, but these drugs are highly toxic to the human body and fish and shellfish, and their use is regulated because they cause environmental pollution. Low toxicity compounds are used.

And 3-isothiazolone derivatives and glutardialdehyde are each known as such a low-toxicity bacteriostatic / bacteriostatic agent, and furthermore, by using them in combination, a synergistic bactericidal / bacteriostatic effect is exhibited. (Japanese Patent Laid-Open No. 58-189103).

(C) Problems to be Solved by the Invention When the above-mentioned 3-isothiazolone derivatives and glutardialdehyde are actually used in combination, the dispersibility in the system to be added and the stability as an industrial product are low for the convenience of handling. From the viewpoints of flammability, economy and the like, it is desired that these are handled and used as a one-part aqueous solution preparation.

On the other hand, 3-isothiazolone derivatives are generally available as a stable solution in the form of an aqueous solution of the metal salt complex, and glutardialdehyde is also available as a stable solution in the aqueous solution.

Therefore, when these two components are used in combination, it is conceivable to use an aqueous solution prepared by mixing and preparing the respective aqueous solutions (the aqueous solution of the 3-isothiazolone derivative metal salt complex and the aqueous solution of glutardialdehyde).

However, in such an aqueous solution preparation in which the 3-isothiazolone derivative metal salt complex and glutardialdehyde are dissolved in water, the stability of the preparation is remarkably reduced as compared with the aqueous solution of each component alone. However, there was a problem that insoluble crystals were formed or a precipitate was formed in the system to be added. And as a result, even when using such an aqueous solution preparation, the intended synergistic bacteriostatic and bacteriostatic effects as well as the inherent bactericidal and bacteriostatic effects of each component are often not exhibited, and the period from production to actual use is often caused. In consideration of the above, it has been extremely difficult to put it to practical use.

The present invention has been made under such circumstances, and it is an object of the present invention to provide a one-part aqueous solution preparation which has excellent preparation stability and does not inhibit a synergistic bactericidal / bacteriostatic effect of the two components.

(D) Means for Solving the Problems Thus, according to the present invention, an aqueous preparation containing a 3-isothizolone derivative metal salt complex as a bactericidal / bacteriostatic active ingredient and glutardialdehyde has the general formula (I): HO (wherein, n 2 or 3, m is an integer of _{2~5) (C n H 2n O} ) m H and 10 to 50 parts by weight in 100 parts by weight of the composition of the stabilizing component represented by The present invention provides a method for stabilizing an industrial bactericidal / bacteriostatic composition, which is characterized by imparting long-term storage stability to an aqueous preparation by mixing the same.

The present invention is based on the discovery that formulation stability is significantly improved by allowing a specific glycol compound to coexist in an aqueous solution in which a 3-isothiazolone derivative metal salt complex and glutardialdehyde are dissolved. .

The 3-isothiazolone derivative metal salt complex used as a bactericidal / bacteriostatic active ingredient of the present invention is represented by the following general formula (II): (Wherein, Χ represents a number atom or a chlorine atom;
Represents a metal atom, and Y represents an anion atom or a group which forms a compound with a cation M having sufficient solubility to form a complex compound. P represents an integer of 1 or 2, and q represents a number at which the anion Y satisfies the valence of the cation M. Suitable are metal salt complexes represented by the following formulas: for example, complexes of 2-methyl-3-isothiazolone or 2-methyl-5-chloro-3-isothiazolone with magnesium chloride, calcium chloride, magnesium nitrate or copper nitrate. .

These may be a mixture, usually 2-methyl-
A magnesium chloride complex of 3-isothiazolone and a magnesium chloride complex of 2-methyl-5-chloro-3-isothiazolone are contained in a weight ratio of 1: 3, and are easily available in the form of a mixed aqueous solution containing magnesium nitrate. It is preferable to use one that can.

Another bactericidal / bacteriostatic active ingredient of the present invention is glutardialdehyde.
It is preferred to use one available as an aqueous solution containing up to w / w%.

In the present invention, the following general formula _{(I): HO (C n} H 2n O) m H ...... (I) ( where, n is 2 or 3, m is an integer of 2-5.)
Is used as a stabilizer for the active ingredient. These compounds are known as a kind of hydrophilic organic solvent, and can constitute a part of the solvent in the composition of the present invention. However, it is not known at all that such a specific organic solvent is effective for stabilizing the active ingredient. Preferred examples of the compound of the general formula (I) include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and polyethylene glycol 200.
(Average molecular weight 190-210), polypropylene glycol 25
0 (average molecular weight of about 250). Of course, these may be used in combination of two or more.

The 3-isothiazolone derivative metal salt complex (hereinafter, component (a)) and glutardialdehyde (hereinafter, component (b)) are combined with water (hereinafter, component (c)) and a compound of the above formula (I) (hereinafter, compound (I)). The composition of the present invention can be obtained by dissolving and preparing in an aqueous solvent comprising the component (d)). In this case, the amount of the component (d) in the aqueous solvent is an amount sufficient to stabilize the components (a) and (b) in the aqueous solvent. Considering this point, the composition of the present invention
In 100 parts by weight, component (a) is 0.1 to 15 parts by weight, component (b) is 1 to 50 parts by weight, component (c) is 10 to 88.9 parts by weight,
And it is preferable to mix | blend so that component (d) may become 10 to 50 weight part. Here, when the component (a) is 0.1 part by weight or less, or the component (b) is 1 part by weight or less,
When the amount of the active ingredient in the composition is small, it is not economically preferable in terms of space for transportation and storage, and when the component (a) is 15 parts by weight or more or the component (b) is 50 parts by weight or more Is not preferred in terms of storage stability.

When the amount of the component (c) is less than 10 parts by weight, the amount of the component (d) is substantially increased, which is not preferable in terms of safety. Conversely, when the amount of the component (c) is 88.9 parts by weight or more, the component (d) is 10 parts by weight. Parts or less, which is not preferable in terms of storage stability.

The amount of the component (d) is most important in terms of storage stability as described above, and is required to be at least 10 parts by weight or more.
This amount is a necessary amount in the composition regardless of the amount of the active ingredients (a) and (b) in the composition.

Further, even if the amount of the component (d) exceeds 50 parts by weight, the storage stabilizing effect does not change, which is not economically preferable. Further, as the amount of the component (d) increases, the amount of the component (c) decreases, and if the amount of the component (c) is 10 parts by weight or less, it is not preferable from the viewpoint of safety.

Among them, from the viewpoint of storage stability, components (a) 1 to 10
It is preferable to use 5 parts by weight, 5 to 45 parts by weight of component (b), 20 to 84 parts by weight of component (c), and 10 to 45 parts by weight of component (d).

The composition of the present invention can be prepared by stirring the respective amounts of the components (a), (b), (c) and (d). Of course, the components (a) and (b) may be prepared using the above-mentioned commercially available aqueous solution or a diluent thereof.

The composition of the present invention may contain other water-soluble organic solvents and surfactants that do not impair the effects of the present invention.

When the composition of the present invention is used, the amount of the active ingredient to be added to the target system for sterilization / bacteriostasis should be such that the weight ratio of component (a) :( b) is in the range of 2: 1 to 1:50. 0.1mg as the total amount of
/ ~ 1000mg / is sufficient.

(E) Examples Hereinafter, the present invention will be described with reference to Test Examples, but the present invention is not limited thereto.

Test Example Each formulation (composition) was prepared by mixing and stirring each component shown in Table 1, and the following tests were performed.

Storage stability test and water dispersibility test Each preparation was stored in a constant temperature bath at 40 ° C, a part of it was sampled daily to measure the bactericidal efficacy, and the appearance change was observed (storage stability) test). Further, at the time of measuring the bactericidal efficacy, the preparation was added to water and mixed, and the dispersion state was observed (water dispersibility test). The test results are shown in Table 1.

The method for measuring and evaluating the bactericidal efficacy in the storage stability test is as follows.

(Method of measuring bactericidal efficacy) Pseudomonas pre-cultured in bouillon medium in advance
Bacterial solution of Pseudomonas aeruginosa IAM1514 was added to physiological saline, and each formulation was added thereto.
For 1 hour, and then the number of surviving bacteria was measured, and the efficacy reduction rate (%) was calculated based on the following equation.

Then, on the fifth, tenth, twenty, thirty, thirty and sixty days after preparation of the preparation, whether or not this reduction rate is 20% or more is checked. Those who failed became the lowest evaluation 1 and those that became 20% or more for the first time on the 10th, 20th, and 30th days were evaluated 2, 3, and 4, respectively, and were less than 20% on the 60th day. Those were given the highest rating of 5.

(Water dispersibility test) 100 g of the preparation was added to water 1, and it was visually observed whether it dissolved uniformly or insoluble matter was formed in water within 3 minutes. Then, on the 5th, 10th, 20th, 30th and 60th days after preparation of the preparation, the insolubles were generated on the 5th day, and the lowest evaluation was 1, Those on which insoluble matter was formed on the 10th, 20th, and 30th days were evaluated as 2, 3, and 4, respectively. High rating 5
And

In addition, the above results were comprehensively determined, and the comprehensive evaluation as to whether or not they can be put to practical use according to the following evaluation method is also shown in the table.

…: No change in appearance and no decrease in bactericidal effect even when left at 40 ° C. for 60 days or more, good dispersion test in water, and sufficient use.

×: A decrease in the bactericidal effect was observed when left at 40 ° C. for 20 days, and when added to water, high-molecular-weight granules precipitated and could not withstand use.

The abbreviations and notes of the compound names in the table have the following meanings, respectively.

A.3-Isothiazolone complex content^{* 1}(weight
Part) is 2-methyl-5-chloro-3-isothiazolone
Magnesium chloride complex and 2-methyl-3-
Isothiazolone magnesium chloride complex
(Rohm and Haas)
Company caisson WT).

B. The meaning of each abbreviation is as follows.

DEG: diethylene glycol DPG: dipropylene glycol TEG: triethylene glycol TTEG: tetraethylene glycol PEG200: polyethylene glycol (average molecular weight, 190
~ 210) PPG250 ...... polypropylene glycol (average molecular weight approx. 25
0) EG: ethylene glycol PG: propylene glycol MDG: diethylene glycol monomethyl ether BDG: diethylene glycol monobutyl ether TPM: tripropylene glycol monomethyl ether 1,4-BD: 1,4-butanediol PC: propylene carbonate Solfit …… 3-Methyl-3-methoxybutanol DMF …… N, N-dimethylformamide PPG700 …… Polypropylene glycol (average molecular weight about 70
0) (Discussion) As shown in Table 1, the formulation of the present invention using an aqueous solvent composed of a specific amount of the compound of the general formula (II) and water produces insoluble matter even after 60 days from the addition of water. It can be seen that the compound is uniformly dissolved and dispersed (evaluation 5), and at the same time, exhibits an excellent bactericidal effect (evaluation 5) based on the synergistic effect of the 3-isothiazolone metal salt complex and glutardialdehyde.

In contrast, in a formulation using an aqueous solvent comprising water and a glycol compound (formulation Nos. 12, 13, 14, 23, etc.) relatively similar to the compound of the general formula (II), dispersibility,
It can be seen that the bactericidal effect decreases with time and is not suitable as a practical preparation.

Therefore, it is understood that the composition of the present invention is extremely excellent as a practical preparation using a 3-isothiazolone metal salt complex and glutardialdehyde in combination.

(F) Effects of the Invention The composition stabilized by the method of the present invention is extremely excellent in stability as a preparation containing a 3-isothiazolone derivative metal salt complex and glutardialdehyde, Also exhibit excellent bactericidal and bacteriostatic effects by the above active ingredients. And since it is an aqueous one-pack preparation, it is excellent in dissolution and dispersibility in a system to be sterilized and bacteriostatic, and can be safely handled and used without flammability.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Sakae Katayama 2-10-15 Higashiawaji, Higashi-Yodogawa-ku, Osaka-shi, Osaka Inside Katayama Chemical Industry Laboratory Co., Ltd. (56) References JP-A-1-272506 (JP, A (58) Field surveyed (Int. Cl. ⁶ , DB name) A01N 43/80 A01N 35/02 A01N 31/02 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. An aqueous preparation containing a 3-isothizolone derivative metal salt complex as a bactericidal / bacteriostatic active ingredient and glutardialdehyde has a general formula (I): HO (C _n H
_2n O) _m H (wherein n is 2 or 3 and m is an integer of 2 to 5).
A method for stabilizing an industrial bactericidal / bacteriostatic composition, which is blended in an amount of 0 to 50 parts by weight to impart long-term storage stability to an aqueous preparation.