JPH04169504A - Isothiazolone aqueous formulation - Google Patents

Abstract

PURPOSE:To obtain an aqueous formulation, composed of an isothiazolone compound, a mixed solvent of water and a hydrophilic organic solvent and a bistrihalomethyl sulfone as a stabilizing ingredient and useful for antiseptic and antifungal treatment of synthetic polymer emulsions. CONSTITUTION:An aqueous formulation is composed of (A) a compound expressed by the formula (X is H or halogen; Y is alkyl) (e.g. 2-methyl-5- chloro-1,2-isothiazolon-3-one), (B) a mixed solvent of water and a hydrophilic organic solvent and (C) a bistrihalomethyl sulfone (e.g. bistribromomethyl sulfone). The ingredients are regulated to 1-20wt.% (especially 1-10wt.% ingredient (A), 0.05-5wt.% (especially 0.2-4wt.%) ingredient (C) and 10-90wt.% moisture content. Ethylene glycol, DMF and others can be cited as the hydrophilic organic solvent in the ingredient (B) and the content of the organic solvent in the mixed solvent is preferably below 50wt.%. The aforementioned formulation is inexpensive without using polyvalent metals and causing any inconvenience for handling such as inflammability.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to stabilized aqueous isothiazolone formulations. More specifically, the present invention relates to an aqueous preparation containing an isothiazolin-3-one compound useful as a non-medical disinfectant, and particularly useful for antiseptic and antifungal treatment of various synthetic polymer emulsions.

(b) Prior art Isothiazolone compounds such as 5-chloro-2-methyl-isothiazolin-3-one and 2-methyl-isothiazolin-3-one have traditionally been used as non-medical disinfectants, preservatives and
It is known as a fungicide, and is particularly useful as a preservative and fungicide for synthetic polymer emulsions such as NBR latex, SBR latex, and acrylic resin emulsions.

Since this isothiazolone compound is easily soluble in water, it is desirable to use it as an aqueous solution formulation in consideration of dispersion in the target system, flammability of the product, and economic efficiency. Especially regarding flammability, products formulated only with glycol-based solvents are flammable.

The storage and transportation of flammable products must be regulated under the Fire Service Act and municipal fire prevention ordinances.

Therefore, with regard to flammable products, sufficient caution must be taken to prevent fire accidents.

Therefore, flammable products are difficult to handle, and non-flammable disinfectants are desired. but,
Since isothiazolone compounds are hydrolyzed in water in a short time, a mere aqueous solution is extremely unstable as a preparation and cannot be used separately.

Therefore, conventionally, aqueous formulations have been developed in which stability is obtained by dissolving an isothiazolone compound as a complex with a metal salt such as a calcium salt or a magnesium salt in water or an aqueous solvent, or by dissolving an isothiazolone compound in a large amount of an organic solvent. Organic solvent formulation with significantly reduced amount of water (Unexamined Japanese Patent Publication No. 61-5
No. 8174 and No. 61-212576) have been proposed.

(c) Problems to be Solved by the Invention However, if an effective amount of the above-mentioned conventional aqueous preparation is directly added to a synthetic polymer emulsion as a preservative/antifungal agent, calcium, magnesium, etc. contained in the preparation may be There is a problem in that the emulsion phase is destroyed by the action of polyvalent metal ions, resulting in phase separation and coagulation (so-called emulsion failure).

Therefore, when using such an aqueous preparation, it is necessary to sufficiently dilute it before adding it, but this causes inconveniences such as fluctuations in the latex concentration of the synthetic polymer emulsion to which it is added, leading to deterioration in quality. In addition, even when used diluted, coagulation sometimes occurred. There is also a proposal to use this aqueous preparation in a synthetic polymer emulsion without diluting it, but in this case it was necessary to add a specific anionic surfactant (Japanese Patent Application Laid-open No. 80-85042, 60-98652).

On the other hand, when the above-described organic solvent preparation is added to a synthetic polymer emulsion, a high concentration of the organic solvent may be partially introduced into the system, resulting in shock.

This invention was made under such circumstances, and is particularly characterized by excellent formulation stability, no flammability problem, and economical low cost, and which can be added directly to synthetic polymer emulsions. The present invention aims to provide an isothiazolone compound formulation that does not cause shock.

(d) Means for Solving the Problems From the above viewpoint, the present inventors conducted intensive research and examination, and found that a specific bistrihalomethylsulfone compound was The fact is that by adding a specific amount of this aqueous preparation to a polymer emulsion, its stability is significantly improved without the use of metal salts, and that even if an effective amount of this aqueous preparation is added to a polymer emulsion for antiseptic and antifungal effects, there are no adverse effects such as so-called "shock". I discovered a fact that does not occur.

Thus, according to the invention, (a) general formula (■).

(However, in the formula, X represents a hydrogen atom or a halogen atom, and Y represents an alkyl group.) and (b) an amount sufficient to at least dissolve the compound of the above general formula (I). It consists of a mixed solvent of water and a hydrophilic organic solvent, and (c) bistrihalomethylsulfone blended as a stabilizing component, containing 1 to 20% by weight of the isothiazolone compound of component (a) and component (b). An aqueous isothiazolone preparation containing 0.05 to 5% by weight of bistrihalomethylsulfone and having a water content adjusted to 10 to 90% by weight is provided.

The aqueous formulation of the present invention is an aqueous solution formulation that is endowed with excellent formulation stability without substantially containing calcium or magnesium salts that have been conventionally used for stabilization. In particular, this invention was made based on the unexpected fact that bistrihalomethylsulfone compounds act as stabilizers.

Here, it is known that some of the above bistrihalomethylsulfones are used in combination with isothiazolone compounds for the purpose of synergistic slime control effect (Japanese Patent Publication No. 61
(Refer to Publication No.-25004). However, this publication specifically discloses a non-aqueous formulation using these in combination, and does not suggest a water-containing formulation such as the one of the present invention. In particular, there is no evidence or suggestion that stabilization of an aqueous preparation of an isothiazolone compound can be achieved by incorporating a very small amount of the above-mentioned sulfone compound.

Examples of the halogen atom of the substituent X of the isothiazolone compound of formula (I) used in this invention include a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred. On the other hand, the lower alkyl group of the substituent Y is an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, butyl,
octyl, etc.). Preferred is a methyl group.

Preferred representative examples of these isothiazolone compounds of formula (I) are 2-methyl-5-chloro-1,2-ythiazolin-3-one and 2-methyl-1,2-isothiazolin-3-one.

These isothiazolone compounds are disclosed in Japanese Patent Publication No. 46-1, for example.
It can be produced according to the synthesis method described in Japanese Patent No. 2723, and is usually obtained as a mixture of the above compounds. Mixtures of these are also suitably used in the present invention.

As the bistrihalomethylsulfone which is a stabilizing component used in this invention, bistribromomethylsulfone (BTBMS) represented by the following formula (II) and bistrichloromethylsulfone (BTCMS) represented by the following formula (I[I) are used.
is suitable.

Br, C-5-CBrs ---・--(I[
) C1sCS CCl5 ・・・・・・(I
II) The aqueous preparation of the present invention is prepared by preparing an aqueous solution of the compound of formula (I), and adding a predetermined amount of the stabilizing component and a hydrophilic organic solvent in an amount sufficient to dissolve the stabilizing component to this solution. It can be produced by

However, they can also be produced without particular regard to order.

Examples of the water used as a solvent include ordinary water such as tap water, soft water, and pure water, and industrial water can also be used. Examples of the hydrophilic organic solvent include ethylene glycol, noethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,4-butanediol, 1,5-bentanediol, and ethylene glycol monomethyl. Various known polyols or polyol ether liquid compounds such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, N-dimethylformamide, N, N-diethylformamide, N,N-dimethylacetamide, X-
Methyl-2-pyrrolidone and the like can be used. However, from the viewpoint of preventing shock in the synthetic polymer emulsion, the content of the organic solvent in the mixed solvent is preferably less than 50% by weight.

It is also possible to prepare a preparation by adding a predetermined amount of the stabilizing component to the organic solvent solution of formula (1) and dilute it with water before use. In this case, economical advantages in terms of transportation can be obtained.

Note that the organic solvent used in the above mixed solvent formulation includes N
, N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, or a mixed solvent of these amide compounds and the glycol solvent is used. is preferable from the viewpoint of storage stability of the formulation.

The amount of the compound of formula (I) in the aqueous preparation of this invention is:
The content is 1 to 20% by weight, and preferably 1 to 10% by weight from the viewpoint of storage stability.

The amount of bistrihalomethylsulfone as a stabilizing component in this invention is 0.05 to 5% by weight in the formulation. If it is less than 0.05% by weight, the storage stability will be insufficient, and if it exceeds 5% by weight, there is a risk that halomethylsulfone crystals will precipitate at low temperatures, which is not suitable. Especially 0.
It is preferable to set it to 2 to 4% by weight.

On the other hand, the water content in the aqueous preparation of this invention is 10 to 9
0% by weight, preferably 30 to 70% by weight. If it exceeds 90% by weight, it is not suitable in terms of storage stability, and 1
If it is less than 0% by weight, it is not suitable for the purpose of the present invention because it may cause shock in the emulsion when added to a synthetic polymer emulsion.

Since the aqueous preparation of the present invention does not use polyvalent metals and uses a significantly reduced amount of organic solvent, shock upon addition of a synthetic polymer emulsion can be prevented or suppressed.

Moreover, it is free from inconveniences in handling such as flammability, is economically inexpensive, and exhibits excellent stability as an aqueous preparation.

(e) As an example isothiazolone compound, a mixture of 2-methyl-5-chloro-isothiazolin-3-one and 2-methyl-isothiazolin-3-one (weight ratio 9:l), hereinafter MI
T) was dissolved in various solvents listed in Table 1, and a stable component [bistribromomethylsulfone (BTBMS) or bistrichloromethylsulfone (BTBMS)] was used.
TCMS) and mixed and stirred to prepare Example B1-8.
23. A formulation of Comparative Example Al-A21 was obtained. (All numbers in the table indicate parts by weight.) The following tests were conducted on each of these coated products.

[Storage stability test method...Put each formulation in a glass container for 40 minutes.
It was left under conditions of °C. Observe the condition over time, and if there is no change in appearance and no decomposition is observed as a result of HPLC (high performance liquid chromatography) measurement, those with a slightly cloudy O1 appearance and an MIT decomposition rate of less than 10% by HPLC measurement are classified as △, the appearance shows a large amount of crystals precipitated and cloudy, and the decomposition rate is 10%.
The above items were marked as ×.

However, it is estimated from long-term test results that the 40°C stability of 2 months in this test is equivalent to 6 months or more at room temperature.

Shock test for polymer emulsion] Polymer emulsions (two types of SBR latex and acrylic resin emulsion) were placed in beakers with a capacity of 100 and 200, respectively, and 31 grams of the formulation were added.

After stirring with a magnetic stirrer for 3 minutes, the mixture was filtered through a 100 mm wire mesh. 01 for those that do not leave aggregates on the wire mesh
Those in which aggregates remained were designated as X.

From this result, the aqueous formulation of this invention has excellent stability and
It is also found to be an excellent product that does not have any adverse effects on the polymer emulsion.

(The following is a blank space) In addition, the abbreviations in the above table mean the following compounds.

(f) Effects of the Invention The aqueous isothiazolone preparation of the present invention has excellent stability, especially storage stability. Moreover, no adverse effects occur even when directly added to a polymer emulsion. Therefore, it is not only convenient to handle, but also allows the isothiazolone compound to be used in a wider range of applications, such as for deaf people.

Agent: Patent Attorney Shintabe Nogawa---6. Nilow 1 5-knee -・

Claims (1)

[Claims] 1. (a) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) (However, in the formula, X represents a hydrogen atom or a halogen atom, and Y represents an alkyl group.) and (b) an amount sufficient to at least dissolve the compound of the above general formula (I). , a mixed solvent of water and a hydrophilic organic solvent, and (c) bistrihalomethylsulfone blended as a stabilizing component, containing 1 to 20% by weight of the isothiazolone compound of component (a) and component (b). of bistrihalomethylsulfone to 0.
An aqueous isothiazolone preparation containing 05 to 5% by weight and having a water content adjusted to 10 to 90% by weight. 2. The aqueous preparation according to claim 1, which is used for preserving and preventing mold from synthetic polymer emulsions.