JPH03112908A - Industrial sterilizing and bacteriostatic composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in stability of preparation by adding a specific glycol-based compound to an aqueous solution in which 3-isothiazolone derivative metal salt complex and glutaric dialdehyde are dissolved as sterilizing and bacteriostatic active ingredients. CONSTITUTION:(A) 3-Isothiazolone derivative metal salt complex and (B) glutaric dialdehyde are dissolved in an aqueous medium consisting of (C) a compound expressed by the formula HO(C2H2nO)nH (n is 2 or 3; m is integer of 2-5) having an amount sufficient to stabilize these sterilizing and bacteriostatic active ingredients and (D) water, preferably at ratios of 0.1-15 pts.wt. ingredient A, 1-50 pts.wt. ingredient B, 10-88.9 pts.wt. ingredient C and 10-50 pts.wt. ingredient D based on 100 pts.wt. composition to provide the title composition having excellent storage stability as well as excellent dissolving and dispersing properties to the objective system and safety in suppressed lowering of effects by decomposition of the above-mentioned active ingredients during long-term storage.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to a bactericidal and bacteriostatic composition with good storage stability. More specifically, it is an aqueous preparation containing 3-isothiazolone derivative metal salt complex and glutardialdehyde as bactericidal and bacteriostatic active ingredients. The present invention relates to a stable industrial bactericidal/bacteriostatic composition in which a decrease in oxidation is significantly suppressed.

(b) Conventional technology Slime caused by bacteria and fungi has traditionally been generated in the paper making process in the paper and pulp industry and in cooling water systems in various industries, causing a decline in the quality of products and production efficiency.
Many industrial products, such as heavy oil sludge, metal processing fluids,
Textile oils, paints, various latexes, glues, etc., are subject to decay and contamination due to bacteria and fungi, staining the products and reducing their value.

Many disinfectants have been used to prevent damage caused by these microorganisms. In the past, organic mercury compounds and chlorinated phenolic compounds were used, but these drugs are highly toxic to humans and seafood, and cause environmental pollution, so their use has become regulated, and their use has become relatively rare in recent years. Compounds of low toxicity are used.

3-isothiazolone derivatives and glutardialdehyde are each known as such low-toxic bactericidal and bacteriostatic agents, and furthermore, when used in combination, synergistic bactericidal and bacteriostatic effects can be achieved. It is known that (JP-A-58-189103).

(c) Problems to be Solved by the Invention When the above-mentioned 3-isothiazolone derivatives and glutardialdehyde are actually used together, for convenience of handling, it is difficult to improve the dispersibility in the system to which they are added and the stability as an industrial product. From the viewpoints of flammability, economic efficiency, etc., it is strongly desired that these be handled and used as a liquid aqueous solution preparation.

On the other hand, 3-isothiazolone derivatives are generally available as stable solutions in the form of aqueous solutions of their metal salt complexes, and glutardialdehyde is also available as stable solutions in the form of aqueous solutions.

Therefore, when using these two components together, it is conceivable to use an aqueous solution preparation prepared by mixing aqueous solutions of each of these components (aqueous solution of 3-isothiazolone derivative metal salt complex and aqueous solution of glutardialdehyde).

However, in an aqueous solution formulation in which the 3-isothiazolone derivative metal salt complex and glutardialdehyde are dissolved in water, the stability of the formulation is significantly lower than that of an aqueous solution of each component alone, and, for example, for a short period of time. However, there have been problems with the formation of insoluble crystals or the formation of precipitates in the system to which they are added. As a result, even when such aqueous solution preparations are used, the intended synergistic bactericidal and bacteriostatic effects, as well as the inherent bactericidal and bacteriostatic effects of each component, are often not achieved, and the period from manufacture to actual use is delayed. Considering this, it was extremely difficult to put it into practical use.

The present invention was made under these circumstances, and aims to provide a one-component aqueous solution formulation that has excellent formulation stability and does not inhibit the synergistic bactericidal and bacteriostatic effects of both of the above-mentioned components.

(d) Means for Solving the Problems Thus, according to the present invention, the 3-isothiazolone derivative metal salt complex and glutardialdehyde as bactericidal and bacteriostatic active ingredients stabilize these bactericidal and bacteriostatic active ingredients. A sufficient amount of general formula (I): HO
(CI, l(2,O),,)l (where n is 2 or 3
, m is an integer of 2 to 5) and water, there is provided an industrial bactericidal and bacteriostatic composition prepared by dissolving the compound in an aqueous solvent.

This invention provides the following method by coexisting a specific glycol compound in an aqueous solution in which a 3-isothiazolone derivative metal salt complex and glutardialdehyde are dissolved.
This is based on the discovery that formulation stability is significantly improved.

The 3-isothiazolone derivative metal salt complex used as the bactericidal and bacteriostatic active ingredient of this invention has the following general formula (■): (wherein, X represents a hydrogen atom or a chlorine atom, M represents a metal atom, Y represents an anion atom or group that forms a compound with the cation M having sufficient solubility to form a complex; P represents an integer of 1 or 2; q represents an anion when Y is a cation; The metal salt complex shown in (indicates the number satisfying the valence of M) is suitable,
Examples include 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 mixtures, usually 2-methyl-3
- Easily prepared in the form of a mixed aqueous solution containing a magnesium chloride complex of isothiazolone and a magnesium chloride complex of 2-methyl-5-chloro-3-isothiazolone in a weight ratio of 1:3, and further containing magnesium nitrate. It is preferable to use something that can be done manually.

Another bactericidal and bacteriostatic active ingredient of this invention is glutardialdehyde, and generally glutardialdehyde is
It is preferred to use those available as aqueous solutions containing up to % w/w.

In this invention, the following general formula (■); HO (C,, ■
7. ．． ,0)Total...(1) (However, n is 2 or 3, and m is an integer of 2 to 5.) A compound represented by the following formula is used as a stabilizer for the above-mentioned active ingredient. These compounds are known as a type of hydrophilic organic solvent, and may constitute a part of the solvent in the composition of the present invention. However, it is completely unknown that such specific organic solvents are effective in stabilizing the above-mentioned active ingredients. Preferred examples of the compound of the general formula ([) include diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol 200 (average molecular weight 190
~210) and polypropylene glycol 250 (average molecular weight approximately 250). These are, of course,
Two or more types may be used in combination.

The 3-isothiazolone derivative metal salt complex (
Hereinafter, component (a)) and glutardialdehyde (hereinafter component (b)) will be combined with water (hereinafter component (〕)) and the above formula (1).
The composition of the present invention can be obtained by dissolving the compound (hereinafter referred to as component (3)) in an aqueous solvent.

In this case, the amount of component (d) in the aqueous solvent is
The amount is sufficient to stabilize a) and (b) in the aqueous solvent.

Considering this point, in 100 parts by weight of the composition of the present invention, component (a) is 0.1 to 15 parts by weight, component <a) is 1 to 50 parts by weight, and component (c) is 10 to 15 parts by weight. 88.9 parts by weight,
Preferably, the amount of component (d) is 10 to 50 parts by weight. If component (a) is less than 0.1 part by weight, or component (b) is less than 1 part by weight, the amount of active ingredient in the composition will be small, resulting in space considerations for transportation and storage. If the amount of component (a) is 15 parts by weight or more, or if the amount of component (b) is 50 parts by weight or more, it is unfavorable from the viewpoint of storage stability.

If component (c) is less than 10 parts by weight, component (d) will substantially increase, which is unfavorable from a safety point of view;
If c) is more than 88.9 parts by weight, component (d) will be less than 10 parts by weight, which is unfavorable in terms of storage stability.

As mentioned above, the amount of component (d) is most important from the viewpoint of storage stability, and should be at least 10 parts by weight.

This amount is the amount necessary in the composition regardless of the amount of active ingredients (a) and (b) contained in the composition.

Furthermore, even if component (d) exceeds 50 parts by weight, the storage stabilizing effect remains unchanged, which is economically unfavorable. (f2) As the amount of component (d) increases, the amount of component (c) to be blended decreases, and if the amount of component (c) is less than 10 parts by weight, it is unfavorable from the point of view of safety.

Among these, in terms of storage stability, component (a) 1 to 10
Parts by weight, component (b) 5 to 45 parts by weight, component (c) 20 to
It is preferable to use 84 parts by weight and 10 to 45 parts by weight of component (d).

The composition of this invention can be prepared by mixing and stirring the respective amounts of components (a), (b), ()1) and (d). Of course, components (a) and (b) may be prepared using commercially available aqueous solutions or diluted solutions thereof as described above.

In addition, the composition of this invention may contain other water-soluble organic solvents and surfactants to the extent that they do not inhibit the effects of this invention.
I wish it was manufactured.

In addition, when using the composition of this invention, its sterilization and
The amount added to the bacteriostatic target system is sufficient if the weight ratio of components (a) and (b) is within the range of 2 = 1 to 1:50, and the total amount of active ingredients is 0.1 + ng/Q to 1000 mg/12. It is.

(E) Examples The present invention will be explained below using test examples, but the present invention is not limited thereby.

(Left below) Test Examples Each formulation (composition) shown in Table 1 was prepared by mixing and stirring the respective ingredients, and the following tests were conducted f2.

Storage stability test and water dispersibility test Each formulation was stored in a constant temperature bath at 40°C, and a portion of it was sampled over time to measure the bactericidal efficacy and observe changes in its appearance (storage stability test).

When measuring the bactericidal efficacy, the preparation was added to water and mixed, and the dispersion pattern was observed (water dispersibility test). These test results are also shown in Table 1.

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

(Method for measuring bactericidal efficacy) Pseudomonas aeruginosa precultured in a bouillon medium
osa) lAM1514 bacterial solution was added to physiological saline, each formulation was added to this, shaken at 37°C for 1 hour, the number of surviving bacteria was measured, and the efficacy reduction rate ( %) was calculated.

Bactericidal concentration after X days (ppm) - Bactericidal concentration immediately after formulation (p
pm) [Bactericidal concentration...Concentration required to sterilize 99.9% (ppm)] Then, on the 5th day after preparation of the preparation, the 10% Check on the 1st, 20th, 30th, and 60th days, and the one that reaches 20% or higher for the first time on the 5th day is given the lowest rating, and the 10th, 20th, and 30th days are checked. Those that reached 20% or more for the first time were given a rating of 2°3 and 4, respectively, and those that remained 20% yellow on the 60th day were given the highest rating of 5.

(Water dispersibility test) 100 g of the preparation was added to water lσ, and it was visually observed whether it dissolved uniformly within 3 minutes in water or whether insoluble matter was generated. Then, on the 5th day and 10th day after preparation of the preparation,
Check on the 20th, 30th, and 60th days, and the one with the lowest rating of 1 is the one in which insoluble matter was generated on the 5th day.
Those in which insoluble matters were formed on the 10th, 20th, and 30th days were rated 2.3 and 4, respectively, and those in which insoluble matters were not generated and were uniformly dissolved and dispersed on the 60th day. It was given the highest rating of 5.

The above results are comprehensively judged and a comprehensive evaluation of whether or not it can be put to practical use is also shown in the table according to the evaluation method below.

O: Even after being left at 40°C for 60 days or more, there is no change in appearance, no decrease in bactericidal efficacy is observed, and the water dispersion test is good, so it can be used satisfactorily.

×: When left at 40°C for 20 days, a decrease in bactericidal efficacy is observed, and when added to water, polymeric particles precipitate, making it unusable.

In addition, the abbreviations and notes for compounds in the table each represent the following meanings.

The amount of 3-isothiazolone complex (parts by weight) is 2-methyl-5-chloro-3=isothiazolone magnesium chloride complex and 2-methyl-3-
This is the blending amount of a mixture of isothiazolone and magnesium chloride complex (weight ratio: 3:1) (using Caisson 0WT manufactured by Rohm and Haas).

B. The meaning of each abbreviation is shown below.

DEC...Diethylene glycol DPG...
... Dipropylene glycol TEG ... Triethylene glycol TTEG ... Tetraethylene glycol PEG 200 ... Polyethylene glycol (average molecular weight, 190-210) P P G 250 ...Polypropylene glycol (average molecular weight 250) EG...Ethylene glycol PG...Propylene glycol MDG...
...Diethylene glycol monomethyl ether BDG...Diethylene glycol monobutyl ether TP? Vt...Tripropylene glycol monomethyl ether 1.4-B D...14-butanediol P
C...Propylene carbonate turfitz
...3-methyl-3-methoxybutanol D~1F...N,N-dimethylformamide P
PG 700...Polypropylene glycol (average molecular summary 700) (Left in the margin below) (Discussion) As shown in Table 1, an aqueous solvent consisting of a specific amount of the compound of general formula (II) and water is used. After 60 days, the formulation of this invention can be uniformly dissolved and dispersed without producing insoluble matter when water is added (rating 5), and the formulation is based on the synergistic effect of the 3-isothiazolone metal salt complex and glutardialdehyde. It can be seen that it exhibits an excellent bactericidal effect (rating 5).

On the other hand, a glycol compound (preparation No. 12.13.14.23) that is relatively similar to the compound of general formula (■)
For formulations using an aqueous solvent consisting of (e.g.) and water,
It can be seen that both the dispersibility and the bactericidal effect deteriorate over time, making it unsuitable as a practical formulation.

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

(F) Effects of the Invention The composition of the present invention has extremely excellent stability as a preparation containing a 3-isothiazolone derivative metal salt complex and glutardialdehyde, and even over a long period of time, the composition has excellent stability due to the above-mentioned active ingredients. It exhibits bactericidal and bacteriostatic effects.

Since it is an aqueous one-component formulation, it has excellent dispersibility in sterilizing and bacteriostatic target systems, is not flammable, and is safe to handle.
It can be used.

Claims (1)

[Claims] 1. The 3-isothiazolone derivative metal salt complex and glutardialdehyde as bactericidal and bacteriostatic active ingredients are contained in an amount of the general formula (I): HO (C_nH_2_nO)_mH sufficient to stabilize these bactericidal and bacteriostatic active ingredients.
An industrial bactericidal and bacteriostatic composition prepared by dissolving the compound represented by the formula (wherein n is 2 or 3, and m is an integer of 2 to 5) in an aqueous solvent consisting of water.