JPH049305A - Aqueous preparation of isothiazolone - Google Patents

Abstract

PURPOSE:To obtain a preparation consisting of an isothiazolone compound, water or aqueous solvent, nitrobromo based or cyanobromo based compound, useful in prevention of synthetic high polymer emulsion from putrefaction and mildew and having high storage stability. CONSTITUTION:The aimed aqueous preparation consisting of 1-20wt.% compound expressed by formula I (X is H or halogen; Y is alkyl), water or aqueous solvent (e.g. DMF) and compound expressed by formula II [X is NO2 or CN; Y1 and Y2 are Br, NO2, CN, aminocarbonyl, OH, etc., or either one of Y1 and Y2 is formula III (Y3 is H or halogen) A is H, halogen, NO2 or alkyl; m is 1-3) and the other is H or Y1 and Y2 together form formula IV]. The preparation can directly be added to a synthetic high polymer emulsion without causing defect of separation or solidification, etc.

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 isothiazolone-3 to ion compound useful as a non-medical disinfectant, and particularly useful for antiseptic and antifungal treatments of various synthetic polymer emulsions.

(b) Conventional technology 5-chloro-2-methyl-isothiazolin-3one and 2
- Isothiazolone compounds such as methyl-isothiazolin-3-one, which have traditionally been used as non-medical disinfectants, preservatives,
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 isothiazoline compound is easily soluble in water, it is desirable to use it as an aqueous solution cleavage agent 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 also desired. but,
Isothiazolone compound: Hydrolyzes in a short time in water, so a mere aqueous solution is extremely unstable as a formulation and cannot be used in practical use.

Therefore, conventionally, isothiazolone compounds are dissolved in water or aqueous solvents as a complex with metal salts such as calcium salts and magnesium salts to give stability, and isothiazogone compounds are dissolved in large amounts of organic solvents. organic solvent formulation with significantly reduced water content (Unexamined Japanese Patent Publication No. 61-5
No. 6174 and No. 61212576) have been proposed.

(c) Problems to be solved by the invention However, when an effective amount of the above-mentioned conventional aqueous preparation is directly added to a synthetic polymer emulsion as a preservative/preservative, it is difficult to remove the polyvalent components such as calcium and magnesium contained in the preparation. One problem is that the emulsion phase is destroyed by the action of 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 may lead to inconveniences such as quality deterioration such as fluctuations in the latex concentration of the synthetic polymer emulsion to which it is added. . There were also cases where coagulation occurred when diluted and used. There have also been proposals to use this aqueous preparation in synthetic polymer emulsions without diluting it, but in this case it was necessary to add a specific anionic surfactant (Japanese Patent Application Laid-open No. 60-65042, 60-96852).

On the other hand, when a previously treated organic solvent preparation was added to a synthetic polymer emulsion, the organic solvent was partially brought into the system to a high agglutination rate, resulting in the formation of smudges.

The present invention was made under such circumstances, and is especially excellent in formulation stability, has no flammability problem, is economically inexpensive, and can be added directly to synthetic polymer emulsions. The object of the present invention is to provide an isothiazolone compound formulation that does not cause

In addition, a part of component (a) and component (c) used in this invention
Is there any suggestion to combine some of them in non-aqueous preparations?
No. 6702), nothing is known about their combination in aqueous formulations and the effects thereof.

(d) Means for Solving the Problems From the above viewpoint, the present inventors conducted extensive research and examination, and found that a very small amount of a specific bromine-based compound was added to an aqueous solution of an unstable isothiazolone compound. We have discovered the fact that by adding this aqueous preparation to a polymer emulsion in an effective amount to preservative and prevent damage, it does not cause any adverse effects such as so-called shock. .

Thus, according to the present invention, (a) an isothiazolone compound represented by the general formula (I) 5 (in the formula, X is a hydrogen atom or a halogen atom, and Y is an alkyl group); and (b) the above general compound. Water or an aqueous solvent in an amount sufficient to dissolve at least the compound of formula (I), and (c) the following formula (It) r -C-Y2 ... (It) [ However, in the formula, X represents a nitro group or a cyano group, y,
Y is a bromine atom, a nitro group, a cyano group, an aminocarbonyl group, a hydroquinol group, a lower alkyl group substituted with a bromine atom or a cyano group, or a group represented by COR3 (lower alkyl group or hydrogen atom), or Y ,
Or, either one of Y2 is an atom or a bromine atom, or Y and Y2 are joint (
In the formula, Y3 is a hydrogen atom or a halogen atom, A is a hydrogen atom, a halogen atom, a nitro group or a lower alkyl group, and m is 1
An isothiazolone aqueous preparation comprising a nitrobromo or cyanobromo compound represented by: Ru.

The aqueous formulation of the present invention is a solution formulation that is endowed with excellent formulation stability without substantially containing dicalcium or magnesium salts that have been conventionally used for stabilization. In particular, this is based on the surprising fact that the above-mentioned bromine-based compounds act as stabilizers.

It is known that some of the above bromine compounds are used in combination with isothiazolone compounds for the purpose of synergistic bactericidal effect (see Japanese Patent Publication No. 6054281). However, this publication only specifically discloses a non-aqueous formulation using these in combination, and in particular the fact that stabilization of an aqueous formulation of an isothiazolone compound can be achieved by incorporating a very small amount of the above-mentioned bromine compound. There is no indication of any suggestion.

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-12isothiazolin-3-one and 2-methyl-1,2isothiapurin-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 compound of the above compound. Mixtures of these are also suitably used in the present invention.

In this invention, the compound of formula (n) is used as a stabilizer for the formulation. The lower alkyl group in the definition of compound (n) also includes the above-mentioned alkyl group having ~8 carbon atoms.

Specifically, the compound of formula (II) above includes tribromonitromethane, 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-2-nitroethanol, 1,1-dibromo-1- Nitro 2-propatur, 1,1-dibromo-1-nitro 2-acetoquinethane, 1,1-dibromo-1-nitro=2-acetoquinpropane, 2-bromo-2-nitro 13-ditro Acetoquinepropane, 2-bromo-2-nitro-1,3-diformyloquinepropane, 2-nitro-2-bromo-1,3
-propanediol, 1,2 dibromo-2,4-nocyanobutano, 2,3-dibromo-propionitrile, (
I,2-dibromo-2-nidoconithyl) Hensen, β-
Bromo-β-nitrostyrene, 1-(I,2-dibromo-2-nitroethyl)-4-chlorohenzene, β-bromo-4-chloro-β-nitrostyrene, β-bromo-
β, p-nonitrostyrene, β-bromo-4-methyl β
-nitrostyrene, 5-bromo-5-nitro-13-dioxane, 5-bromo-2-methyl-5-nitro-1,
Examples include 3-dioxane. These may be used not only alone but also in combination of two or more. Among these, 2nitro-2-bromo-1,3 has a stability imparting effect.
-Propanediol, 2bromo-2-nitro-1,3-
Diacetoxypronogne, 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitro-1,3-diformyluoquinepropane, 1,1-dibromo-1-nitro-2-proI Knol, 2,2-dibromo-3-nitrilopropionamide, tribromonitromethane, 1.2
-dibromo2,4-zinanobutene, β-bromo-β-
Nitrostyrene, 5-bromo-5-nitro-1,3-dioxane or 5-bromo-2-methyl-5-nitro-1
It is preferable to use 3-dioxane.

The aqueous preparation of the present invention can be produced by preparing an aqueous solution of the compound of formula (+) and adding a predetermined amount of the stabilizing component to this solution. 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. Note that instead of water, a hydrophilic organic solvent (e.g., ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1.4-butanediol, 1.5-
Various known polyol or polyol ether liquid compounds such as pentazineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glyfur monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tripropylene glycol monomethyl ether, N, It is also possible to use a dilute aqueous solvent by mixing N-dimethylformamide, N-verdiethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.) with water. Considering the flammability of the preparation, the water content in the preparation is preferably 5% by weight or more, and in order to prevent the shock of the synthetic polymer emulsion, the water content in the preparation should be 5% by weight or more. It is preferably at least 10% by weight, particularly preferably at least 50% by weight.

When using the above-mentioned organic solvent in the aqueous preparation of the present invention, a predetermined amount of the above-mentioned stabilizing component is added to the organic solvent solution of formula (I) to prepare a preparation, and the preparation is diluted with water before use. It is possible. In this case, economical advantages in terms of transportation can be obtained.

The organic solvent used in the above organic solvent formulation includes "iN-
trimethylformamide, N,N-noethylformamide, N,N-trimethylacetamide and seamethyl-2-
From the viewpoint of storage stability of the preparation, it is preferable to use an amide compound such as pyrrolidone alone or a mixed solvent of these amide compounds and the glycol solvent.

The content of the compound of formula (I) in the aqueous formulation of this invention is:
It is preferably 1 to 30% by weight in terms of storage stability.
It is particularly preferred that the content be 20% by weight.

The amount of the nitrobrome-based or nitrobrome-based compound as a stabilizing component is preferably 0.00 to 0.1 part by weight per 1 part by weight of the compound of formula (I) from the viewpoint of storage stability, and usually 0.004 parts by weight. Parts by weight or more are more preferred. However, since the stabilizing effect is generally the same even when the amount is 0.1 part by weight or more, there is no particular problem with adding more than that. If the amount is less than 0.001 part by weight, the isothiazolone compound is likely to decompose, making it impossible to obtain an aqueous preparation with good storage stability, which is undesirable.More than 1 part by weight of O may be added, but considering economic considerations. Then, it is preferably up to 0.1 part by weight.

The aqueous preparation of the present invention does not use polyvalent metals, does not use organic solvents at all, or uses them in significantly reduced amounts, and is used in small amounts to prevent sagging when adding synthetic polymer emulsions. Also: It will be very restrained. Moreover, it is free from inconveniences in handling such as flammability, is economically inexpensive, and exhibits excellent stability as an aqueous preparation.

(E) Example (Example 1) As an isothiazolone compound, a mixture of 2-methyl-5cucorisothiazolin-3-one and 2-methylisothiazolin-3-one (weight ratio 91), hereinafter abbreviated as MIT) was used. and dissolve it in various solvents listed in Table 1,
Furthermore, a stable component was added, mixed and stirred, and Example IB~
56B, the formulations of Comparative Examples IA to 75A were obtained f2. (All numbers in the table indicate parts by weight.) The following tests were conducted on these various formulations.

``Storage stability test method... Each formulation was placed in a glass container and left at 40°C, and the condition was observed over time, and changes in appearance were observed using HPLC (high performance liquid chromatography). ), MIT decomposition rate was less than 5% as determined by HPLC at low temperature. Those with a decomposition rate of 5% or more were rated x.

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 emulsions] Polymer emulsions (two types of SBR latex and acrylic resin emulsions) were placed in beakers each having a capacity of 100 m[, 2001β], and 31 grams of the formulation were added.

After stirring with a magnetic stirrer for 3 minutes, the mixture was filtered through a 100-mesh wire mesh. O1 that does not leave aggregates on the wire mesh
Mark the remaining aggregates as × and 1. The results are shown in Table 1.

From this result, the aqueous formulation of the present invention has excellent stability,
Moreover, it is found that it is an excellent product that does not have any adverse effect on the polymer emulsion.

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

Example 2 Conducted using the compounds shown in the table below as stabilizers. A test similar to Example 1 was conducted.

The results are shown in Table 2.

Example 3 Pronopol, DBNPA, B! as stabilizers. I
D.

Using BNS and DDB, the same test as in Example 1 was carried out.
':rtsuna. The results are shown in Table 3.

As shown in the above Examples and Comparative Examples, the isothiazolone aqueous 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 for handling, but also for the use of isothiazolone compounds.
This also makes it possible to expand the usage patterns.

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). Water or an aqueous solvent and (c) Formula (II) below, which is blended as a stabilizing component: ▲ Numerical formulas, chemical formulas, tables, etc.▼・・・・・・(II) [However, in the formula, X is nitro group or cyano group, Y_
1, Y_2 is a bromine atom, a nitro group, a cyano group, an aminocarbonyl group, a hydroxyl group, a lower alkyl group substituted with a bromine atom or a cyano group, or ▲a mathematical formula, a chemical formula, a table, etc.▼ (in the formula ,R_1,R
_2 and R_3 are each a group represented by a lower alkyl group or a hydrogen atom, or one of Y_1 or Y_2 is a group represented by ▲There is a numerical formula, chemical formula, table, etc. ▼, and the other is a hydrogen atom or a bromine atom. Or do Y_1 and Y_2 together form a group represented by ▲There is a mathematical formula, chemical formula, table, etc.▼ (in the formula, Y_3 is a hydrogen atom or a halogen atom; or a lower alkyl group,
m is an integer of 1 to 3), or a nitrobromo or cyanobromo compound represented by: . 2. The aqueous preparation according to claim 1, wherein the compound of general formula (I) is blended in an amount of 1 to 20% by weight. 3. The aqueous preparation according to claim 1, wherein the stabilizing component is blended in a weight ratio of 0.004 to 0.01 to 1 of the isothiazolone compound represented by general formula (I). 4. The aqueous preparation according to any one of claims 1 to 3, which is used for preserving and preventing mold of synthetic polymer emulsions.