JP4502704B2 - Industrial antiseptic and fungicides containing 1,2-benzisothiazolin-3-one and N-ethylaminoethylamine - Google Patents

Description

  The present invention relates to an industrial antiseptic and fungicidal agent used for adhesives, paints, latex and other various industrial products and materials, and industrial wastewater.

  Industrial products and materials such as adhesives, paints, and latex, as well as various processing water such as papermaking process water, starch slurry, and cooling water, and wastewater are spoiled and altered by the propagation of fungi such as bacteria, mold, and yeast. In order to prevent this, industrial antiseptic and fungicidal agents are used, and in recent years, industrial antiseptic and fungicidal agents containing various organic compounds as active ingredients have been used in place of metal compounds that are likely to be toxic.

  For example, thiazoline compounds are known that exhibit antiseptic and antifungal activity against various bacteria and fungi, and many derivatives have already been put into practical use. Among these, 1,2-benzoisothiazolin-3-one has excellent antiseptic and antifungal activity, and is therefore used as an industrial antiseptic and antifungal agent in the form of a water dispersion type or a solution type. In recent years, it is often used in a solution type in order to facilitate addition and mixing to industrial products that impart antiseptic and antifungal effects.

  Among the thiazoline-based compounds, 1,2-benzisothiazolin-3-one is known to have excellent antiseptic and fungicidal action, but itself is hardly soluble in water, so this is used as an aqueous solution. At the same time, it has been proposed to use it in the form of a water-soluble organic amine salt or alkali metal salt.

JP-A-8-193015

  For example, Patent Document 1 discloses an industrial antiseptic and fungicidal agent comprising a salt of a specific alkylalkanolamine of 1,2-benzisothiazolin-3-one and the like. It is described that it is excellent in compatibility with adhesives and detergents and has high storage and stability of the solution.

  However, it is regarded as a problem that formaldehyde is detected from industrial antiseptic and fungicides containing amine salts of 1,2-benzisothiazolin-3-one using such amines. When these are used for the formation of water-soluble amine salts, formaldehyde is detected, which is a problem to be addressed in the environment.

  For example, according to the “Guidelines for reducing formaldehyde concentration in indoor air in the workplace” (March 15, 2002) published by the Ministry of Health, Labor and Welfare, the formaldehyde in indoor air in the workplace is 0.08 ppm or less. It has been taken up as a guideline value, and for specific workplaces, when formaldehyde in indoor air exceeds 0.25 ppm, it is urged to take effective measures not to exceed the concentration, Therefore, there is a need to change to alternative substances that are less irritating and harmful, seal equipment, and improve ventilation conditions.

  Although the values of the above guidelines are extremely strict and it is not clear what they will be applied to, it is not clear that some laws and regulations will be imposed in the near future from the viewpoint of environmental protection. It is essential. For this reason, the industry has already begun to consider countermeasures, for example, some users who use paints / adhesives may be required to contain substantially no formaldehyde in the preservatives used in the product. is there.

  Thus, it has been found that formaldehyde is detected in the industrial antiseptic and fungicidal agent comprising 1,2-benzisothiazolin-3-one and alkylalkanolamines such as N-methylethanolamine. As a result, it is detected on the order of several tens to several hundred ppm.

  In addition, formaldehyde is detected without exception from amines conventionally used to increase the water solubility of 1,2-benzisothiazolin-3-one as the main ingredient in the composition, and the detected amount is What is essentially zero is not yet known. The reason why formaldehyde is detected from a composition containing such amines is, for example, the reaction in the process of producing these amine compounds, or the elimination or reaction of substituents (functional groups) in the amine compounds. Although it is estimated, the mechanism of action is not always clear.

  The inventors of the present invention have found that for amines for salt formation used in industrial antiseptic and fungicides based on 1,2-benzisothiazolin-3-one, In addition to the conditions necessary for the formulation such as reactivity with 2-benzisothiazolin-3-one, improved water solubility, and stabilization of the composition, the reduction of formaldehyde (substantially 0) as the subject of the present invention As a result of repeated experiments and research on possible amines, the present invention was completed by discovering that these problems could be achieved by using N-ethylaminoethylamine, which was not conventionally known as an antiseptic and fungicide application.

  That is, the present invention provides an industrial antiseptic and fungicidal agent containing 1,2-benzisothiazolin-3-one and N-ethylaminoethylamine and substantially free of formaldehyde (Claim 1).

  In the present invention, 1,2-benzisothiazolin-3-one may be blended in the range of 6 to 40% by weight and N-ethylaminoethylamine in the range of 7 to 47% by weight with respect to the industrial antiseptic and fungicide. Preferred (claim 2).

  The N-ethylaminoethylamine used in the present invention is used as an intermediate material for pharmaceuticals, and its use in an industrial antiseptic and fungicidal agent has not been known. The amines conventionally used to increase the water solubility of 1,2-benzisothiazolin-3-one are methyl groups or alcohols which are easily released from the reaction in the production process or in the compound of the prepared amine salt. Although it is presumed that formaldehyde is generated due to the characteristic OH group, the specific reason is not necessarily clear.

  In any case, the N-ethylaminoethylamine used in the present invention has a formaldehyde content of 0.1 ppm or less, and is an industrial antiseptic mold containing 1,2-benzisothiazolin-3-one and N-ethylaminoethylamine. Formaldehyde was not substantially detected from the agent, or it was well below its allowable amount when used for specific applications.

  On the other hand, an industrial antiseptic and fungicide containing 1,2-benzisothiazolin-3-one and N-ethylaminoethylamine can contain a high concentration of 1,2-benzisothiazolin-3-one amine salt and its The storage stability was high.

In the present invention, 1,2-benzisothiazolin-3-one is used in the form of a water-soluble amine salt combined with the N-ethylaminoethylamine, but the blending ratio thereof is 1 with respect to the industrial antiseptic and fungicide. , 2-benzisothiazolin-3-one in the range of 6 to 40% by weight, N-ethylaminoethylamine in the range of 7 to 47% by weight, preferably 1,2-benzisothiazolin-3-one in the range of 10 to 33%. The range is% by weight and N-ethylaminoethylamine is 11 to 36% by weight.
If the amount of 1,2-benzisothiazolin-3-one is 6% by weight or less, the desired effect of the antiseptic / antifungal composition cannot be obtained, while if it exceeds 40% by weight, the dissolved state of the amine salt is unstable. In particular, crystals and precipitates are likely to occur during storage at low temperatures.

  In the present invention, the stability of the water-soluble salt is obtained by adding 1 to 10% by weight of ethylene glycol or propylene glycol to 1,2-benzisothiazolin-3-one and N-ethylaminoethylamine. In particular, the stability during low-temperature storage is further improved.

  1,2-Benzisothiazolin-3-one (hereinafter referred to as BIT) and N-ethylaminoethylamine (hereinafter referred to as EAEA) were blended.

Formulation Example 1) BIT; 33%, EAEA; 30%, distilled water; 37%
Formulation Example 2) BIT; 10%, EAEA; 40%, propylene glycol; 10%, distilled water; 40%

  As a comparative composition, only EAEA among the components of the present invention formulated in Formulation Example 1 and Formulation Example 2 was replaced with other amines.

Comparative Example A) BIT; 33%, N-methylethanolamine; 30%, distilled water; 37%
Comparative Example B) BIT; 10%, diethanolamine; 40%, propylene glycol; 10%, distilled water; 40%

The formaldehyde content of EAEA, which is a component of the present invention, and the compositions obtained by Formulation Example 1, Formulation Example 2, Comparative Example A, and Comparative Example B were quantified by the acetylacetone method. Take 25 ml of each composition in a distillation flask, add 1 ml of 20% H ₃ PO ₄ , put 5-10 ml of water in a 200 ml graduated cylinder as a receiver, and steam the adapter so that the adapter of the cooler is immersed in water. Distill. When the distillate reaches about 190 ml, the distillation is stopped, water is added to make 200 ml, and this solution is used as a test solution. Take 5 ml of this solution in a stoppered test tube, stir 5 ml of acetylacetone solution, humidify in a boiling water bath for 10 minutes and then cool, and measure the absorbance at a measurement wavelength of 415 nm. At the same time, the same operation was performed for each of 5.0 ml of 0.5, 1.0, 2.0, 4.0, 6.0, and 8.0 μg / ml formaldehyde standard solutions, and a calibration curve was prepared and colorimetrically determined. .
The results are shown in Table 1.

(Table 1)

  EAEA, which is a component of the present invention, and the compositions prepared in Formulation Example 1 and Formulation Example 2 above were measured by a measurement method using a DNP-derivatized solid phase adsorption / solvent extraction-HPLC method. The results are shown in Table 2.

(Table 2)

  From the results of Table 1 and Table 2, formaldehyde is not substantially detected from industrial preservatives and fungicides of the present invention, or industrial products such as paints and adhesives used therefor, or used for specific applications. In that case, it was well below the permissible amount.

  Stability test of industrial antiseptic and fungicide of the present invention

  Stability was observed after the industrial antiseptic and fungicidal agents formulated in Formulation Example 1 and Formulation Example 2 were allowed to stand for 1 month at 40 ° C, 25 ° C, 0 ° C and -10 ° C. The results are shown in Table 3.

(Table 3)

Test example

The following acrylic emulsion collected at the emulsion production plant was dispensed in 50 ml culture bottles. Next, 0.1% of Formulation Example 1, Formulation Example 2 and Comparative Examples A and B were added to the sample, and after stirring, the viable cell count was measured 3 days later and 1 week later while storing at 30 ° C.
In addition, a mold resistance test was performed according to the method described in Japanese Industrial Standard (JIS Z 2911).
Acrylic emulsion [pH 7.5 Number of detected bacteria; 2.5 × 10 ⁴ (CFU / ml): Detected bacterial species; Alcaligenes faecalis (bacteria), Staphylococcus aureus (bacteria), number of detected molds: 7.0 × 10 ² (CFU / Ml): Detected mold species; Aspergillus niger (mold)

The test results are shown in Table 4.
(Table 4)

As shown in Table 4, the industrial antiseptic and fungicidal agent of the present invention shows the same antiseptic and fungicidal effect as the composition using conventional amines, and the antiseptic and antifungal agent of the present invention and the conventional amine are used. It was confirmed that there was no difference in antiseptic and antifungal activity among the antiseptic and antifungal agents.

Claims (2)

  An industrial antiseptic and fungicide containing 1,2-benzisothiazolin-3-one and N-ethylaminoethylamine and substantially free of formaldehyde. The 1,2-benzisothiazolin-3-one is blended in an amount of 6 to 40% by weight and N-ethylaminoethylamine is blended in an amount of 7 to 47% by weight with respect to an industrial antiseptic and fungicide. Industrial antiseptic and fungicide.