JP5211274B2 - Triazine preparation and aqueous preparation thereof - Google Patents

Description

BACKGROUND OF THE INVENTION
The present invention relates to a triazine preparation and an aqueous preparation thereof . More specifically, the present invention relates to a uniform preparation of a poorly water-soluble triazine compound suitable for use in a circulating water system such as a cooling water system and an aqueous preparation thereof .
In the present specification, a “triazine preparation” not containing water and a “triazine aqueous preparation” containing water are also collectively referred to as “triazine aqueous preparation”.

  In various industrial water systems, their drainage systems, various water storage systems, and more specifically in various water systems that are exposed to sunlight such as cooling towers, water storage pits, swimming pools, open water storage tanks, and amusement facilities , The algae and cyanobacteria represented by the genus Chlorella and Anabaena are bred, causing problems such as deterioration of water quality, generation of bad odor, and loss of aesthetics. In particular, in the cooling tower, various obstacles are brought about such as a decrease in cooling efficiency, induction of corrosion of the metal material, and detached algae blocking the strainer of the cooling water system.

  In addition, cooling water for air conditioning equipment and industrial equipment is usually heated by heat exchange, then cooled by contact with air in a cooling device such as a cooling tower, and circulated and used again as cooling water. Metals (iron, steel, cast iron, etc.) constituting these devices are always in contact with water, and corrosion of metal surfaces in contact with water is likely to occur. Furthermore, due to the cyclic use as described above, the salts contained in the cooling water are gradually condensed to a high concentration, not only the hardness components in the water are precipitated, but also the growth of microorganisms and the formation of slime are induced. Various obstacles are caused.

Slime is formed by microorganisms such as bacteria and fungi adhering to tube walls and vessel walls in the cooling water system and secreting adhesive substances. This slime not only adheres to the pipe wall and vessel wall, especially heat exchangers, deteriorates the heat exchange performance, corrodes the tube wall and vessel wall, and causes sanitary problems such as the spread of pathogenic bacteria. I also do it.
Therefore, it has been conventionally performed to prevent the above-described obstacles by adding various chemicals to various water systems such as cooling water.
When a drug is added to an aqueous system, it is desired to be used as an aqueous preparation in consideration of dispersibility in the target aqueous system, flammability and economy.

  Component (A) 2-methylthio-4-cyclopropylamino-6-tert-butylamino-1,3,5-triazine ["N'-tert-butyl-N-cyclopropyl-" in the aqueous triazine preparation of the present invention 6- (Methylthio) -1,3,5-triazine-2,4-diamine ”is a protective coating that protects materials such as hulls and fish nets that algae grow all over in contact with seawater. It is known as an active ingredient for algaecide (see, for example, JP-A No. 54-115386).

  Thus, since 2-methylthio-4-cyclopropylamino-6-tert-butylamino-1,3,5-triazine has an excellent algicidal effect, the addition of a paint containing an organic solvent as a main solvent It has been used as an ingredient. However, since this triazine compound is hardly soluble in water, it has been difficult to obtain a uniform aqueous preparation. Even if the content of the organic solvent is increased and a uniform aqueous triazine preparation is obtained, when this preparation is added to the aqueous system, water becomes cloudy, crystals precipitate and the active ingredient concentration decreases, and further precipitation occurs. There was a problem that the crystal was attached to the piping of the cooling water system and induced scale failure.

Problems to be solved by the invention

  An object of the present invention is to provide a uniform aqueous preparation of a water-insoluble triazine compound, and to provide an aqueous triazine preparation that does not cause turbidity of water or crystal precipitation even when the preparation is added to an aqueous system. To do.

Means for solving the problem

  The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, 2-methylthio-4-cyclopropylamino-6-tert-butylamino-1,3,5-triazine or 2- ( tert-butylamino) -4-chloro-6-ethylamino-1,3,5-triazine is 2-phosphonobutane-1,2,4-tricarboxylic acid) and a glycol-based hydrophilic organic solvent or an amide-based hydrophilic organic The fact that an aqueous preparation can be obtained that dissolves in a solvent in combination with water and does not cause crystal precipitation even when water is added to this, and even when this aqueous preparation is added to an aqueous system, it may cause turbidity of water or crystal precipitation. However, the present inventors have found the fact that it can be used in a circulating water system such as a cooling water system, and have completed the present invention.

Thus, according to the present invention,
(A) 2-methylthio-4-cyclopropylamino-6-tert-butylamino-1,3,5-triazine or 2- (tert-butylamino) -4-chloro-6-ethylamino-1,3 5-triazine,
(B) 2-tricarboxylic acid, and (C) contains a glycol-based hydrophilic organic Solvent <br/>, component (B) is component (A) to component (C) triazine emissions made agent characterized by comprising contained as a solubilizing agent.
According to the present invention, there is provided an aqueous triazine preparation characterized in that the above triazine preparation further comprises water.

  As 2-methylthio-4-cyclopropylamino-6-tert-butylamino-1,3,5-triazine as the component (A) in the aqueous triazine preparation of the present invention, for example, manufactured by Ciba Specialty Chemicals Co., Ltd. Irgarol 1051 is mentioned. Irgarol 1051 is commercially available as a powdered algicidal agent.

  In addition, examples of 2- (tert-butylamino) -4-chloro-6-ethylamino-1,3,5-triazine include Bellaside (registered trademark) 325 manufactured by BioLab. This veraside is commercially available as an algae / fungicide.

  The component (B) 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) of the present invention acts as a solubilizer for the component (A) with respect to the component (C). Moreover, a component (B) acts also as an anti-corrosion and / or scale prevention component by the compounding quantity. As this PBTC, a commercially available product can be used as it is as an anticorrosive of iron-based metal and as a scale inhibitor.

Component (C) of the present invention is an aqueous solvent comprising a glycol-based hydrophilic organic solvent or an amide-based hydrophilic organic solvent and water.
Examples of glycol-based hydrophilic organic solvents include diethylene glycol monoethyl ether (MDG), diethylene glycol monobutyl ether (BDG), ethylene glycol (EG), diethylene glycol (DEG), polyethylene glycol (PEG), propylene glycol (PG), and dipropylene glycol. , Tripropylene glycol, polypropylene glycol and the like. Among these, MDG and BDG are particularly preferable.

Examples of the amide-based hydrophilic organic solvent include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide (DMAC) and the like. Two or more of these glycol-based and amide-based hydrophilic organic solvents may be used in combination.
In general, the content of the organic solvent in the aqueous preparation is preferably small in consideration of flammability and economy. The blending ratio of the hydrophilic organic solvent and water in the component (C) is appropriately determined depending on the type and combination of the hydrophilic organic solvent in consideration of the amount of the hydrophilic organic solvent sufficient to dissolve the component (A). Just decide.

In the aqueous triazine preparation of the present invention, component (B) is contained as a solubilizer for component (A) with respect to component (C).
The mixing ratio of components (A) and (B) in the aqueous triazine preparation of the present invention, that is, the amount of component (B) necessary for dissolving component (A) is at least relative to 1 part by weight of component (A). 1.25 parts by weight (preferably at least 2.5 parts by weight).

When the component (B) is less than 1.25 parts by weight relative to 1 part by weight of the component (A), the component (A) is recrystallized in the aqueous preparation, and the effective algaecidal concentration of the component (A) decreases. This is not preferable.
The upper limit of the amount of component (B) is not particularly limited, but depends on whether the effect expected from the aqueous triazine preparation of the present invention is only an algicidal effect or an algicidal effect and anticorrosive and / or antiscaling effect. What is necessary is just to determine suitably. Usually, in order to obtain an anticorrosion and / or scale prevention effect, it may be about 10 parts by weight per 1 part by weight of the component (A).

  The algicidal effective amount of the component (A) in the aqueous triazine preparation of the present invention is 0.1 to 10% by weight, preferably 1 to 3% by weight.

  In the triazine aqueous preparation of the present invention, when the preparation is 100 parts by weight, a sufficient amount of the hydrophilic organic solvent capable of dissolving the component (A), the component (B) and the component (A) is mixed with the remaining water. Can be obtained.

When the triazine aqueous preparation of the present invention is used as a cooling water-based water treatment agent, it is preferable to add a known bactericidal component as long as the effects of the present invention are not particularly impaired.
As such a bactericidal component, a bactericidal agent that is water-soluble and does not have an oxidizing action or a reducing action is preferable. Moreover, when adding the scale prevention component mentioned later to the triazine aqueous formulation of this invention, the disinfectant which is not a cationic polymer is preferable.

  Examples of such bactericides include 2-bromo-2-nitropropane-1,3-diol (BNPK), 2,2-dibromo-2-nitro-1-ethanol (DBNE), and 5-chloro-2. -Methyl-4-isothiazolin-3-one, sodium 2-pyridylthio-1-oxide, and the like, among which BNPK and DBNE are preferable.

When the aqueous triazine preparation of the present invention is used as a cooling water-based water treatment agent, an anticorrosion and / or scale preventive component other than the component (B) is further added within the range that does not impair the effects of the present invention, particularly the preparation stability. It may be added.
Examples of such anticorrosive ingredients include known metal anticorrosives such as azole compounds, nitrites, oxycarboxylates, saccharides, organic phosphonic acids other than component (B), zinc salts, molybdates, and the like. Can be mentioned. Of these, azole compounds such as benzotriazole and tolyltriazole are preferable from the viewpoint of having an anticorrosive effect on copper metals.

  Moreover, as a scale prevention component other than a component (B), well-known scale inhibitors, for example, organic phosphonic acids other than a component (B), etc. are mentioned. This organic phosphonic acid is particularly preferable because it has a corrosion prevention effect as well as a scale prevention effect.

  The aqueous triazine preparation of the present invention can be suitably used as a cooling water-based water treatment agent. When used in a cooling water system, the active ingredient concentration of the component (A) and the component (B) may be 100 to 500 mg / l, preferably 200 to 400 mg / l. The amount of addition of can be appropriately increased or decreased depending on the state of the target aqueous system.

  The present invention will be specifically described with reference to test examples, but the present invention is not limited to these test examples.

The compounds of the respective components used in the test examples are shown below together with their abbreviations or abbreviations.
Ingredient (A)
Irgarol: N′-tert-butyl-N-cyclopropyl-6
(Methylthio) -1,3,5-triazine-2,4-diamine (Ciba Specialty Chemicals Co., Ltd.,
Product name: Irgarol 1051)
Ingredient (B)
PBTC: 2-phosphonobutane-1,2,4-tricarboxylic acid (manufactured by Bayer, Germany, trade name: Baihibit AM)

Component (C), hydrophilic organic solvent MDG: Diethylene glycol monoethyl ether (trade name: Hisolv DM, manufactured by Toho Chemical Co., Ltd.)
BDG: Diethylene glycol monobutyl ether (Nippon Emulsifier Co., Ltd., butyl diglycol)

Test Example 1 (Solubility test 1 of component (A))
The components shown in Table 1 and each drug 0.1 g blended at the ratio were added to 1 liter of tap water, and the appearance of tap water immediately after that was visually observed. Next, this tap water was stirred for about 1 minute, and the appearance of the tap water after stirring was visually observed.
In the appearance observation, evaluation was performed as follows.
○: No precipitation or turbidity was observed ×: Precipitation or turbidity was observed Table 1 shows the obtained results.

  No. including PBTC 1 and no. In No. 3, no precipitation was observed even when added to tap water, and no turbidity was observed in the tap water after stirring. On the other hand, No. which does not include PBTC. 2 and no. In No. 4, precipitates were observed immediately after addition to tap water, and the tap water after stirring became cloudy. Moreover, when the deposit was analyzed, it was found to be Irgarol.

Test Example 2 (Solubility test 2 of component (A))
The components shown in Table 2 and 0.1 g of each chemical compounded in the ratio were added to 1 liter of tap water, and the appearance of tap water immediately after that was visually observed. Next, this tap water was stirred for about 1 minute, and the appearance of the tap water after stirring was visually observed.
In the appearance observation, evaluation was performed as follows.
○: No turbidity was observed Δ: Slight turbidity was observed ×: Turbidity was observed Table 2 shows the obtained results.

No. 7 and no. In No. 8, no precipitation was observed even when added to tap water, and no turbidity was observed in the tap water after stirring. On the other hand, no. 5 and no. In 6, a slight turbidity was observed immediately after adding to tap water. No. In No. 5, slightly turbidity was observed in the tap water after stirring. It was not observed in 6.
From this, it can be seen that when preparing a preparation consisting of irgarol and PBTC that does not become turbid when added to water, at least about 2.5 g of PBTC is required for 2 g of irgarol.

Comparative Test Example 1 (Solubility test 3 of component (A))
2 g of irgarol as component (A), 5 g of iron corrosion inhibitor (anticorrosive) shown below as component (B) and 20 g of BDG as a hydrophilic organic solvent of component (C) are mixed, and the appearance of the resulting mixture is visually observed. Observed.

Phase separation was observed in the mixture using the iron corrosion inhibitors 1 to 9 as the component (B), and white turbidity was observed in the mixture using the iron corrosion inhibitor 10.

Reference Example 1 (Scaling prevention and anticorrosion effect confirmation test as water treatment agent)
Using the apparatus shown in FIG. 1, 100 mg / l of the following formulation was added to the test water shown in Table 3, and a confirmation test of scale prevention and anticorrosion effect was performed under the following conditions. For comparison, the same test was performed for the case where no drug was added.

  As for the operation, the test water 11 was put in the test water pit 2 and circulated by the magnet pump 6, the pure water 12 was put in the hot water pit 10 and circulated by the magnet pump 6, and the test was started when the circulation was started. As the test tube, an iron tube was used. The test portion 8 has a double tube structure, in which test water 11 flows outside, warm water 12 flows inside, and the tube portion serves as a heat transfer surface. The water temperature of the test water 11 was adjusted by the cooling water pit 1, the temperature sensor 3, the temperature controller 4 and the electromagnetic valve 5, and the hot water 12 was adjusted by the temperature sensor 3 and the heater 9. In the figure, reference numeral 13 denotes a power supply (AC 100 V) for the temperature controller 4 and the heater 9. In other words, the heat source of the test water 11 is only the heat transfer from the test tube of the test portion 8. Further, the flow rates of the test water 11 and the hot water 12 were adjusted by the respective flow meters 7 and solenoid valves (not shown).

After completion of the test, the test tube was pickled and its weight was measured to determine the weight difference Wf between this measured value and the weight of the test tube measured in advance before the test. The corrosion rate [MDD (mg / day · dm ² )] was determined from the obtained weight difference Wf and the following equation.
MDD = [weight difference Wf (mg)] / [period (day) × surface area ^* (dm ² )]
* Surface area means the surface area of the test tube.

After completion of the test, the test tube was pickled and its weight was measured, and a weight difference Wc between the measured value and the weight of the test tube measured in advance before pickling was determined. The scale adhesion rate [MCM (mg / month · cm ² )] was determined from the obtained weight difference Wc and the following equation.
MCM = [weight difference Wc (mg)] / [period (month) × surface area ^* (cm ² )]
* Surface area means the surface area of the test tube.
Table 4 shows the obtained results.

  From the results in Table 4, it can be seen that the one-component water treatment agent of the present invention has an excellent scale prevention effect and has low corrosiveness to metal materials.

Reference example 2 (algae growth inhibitory effect confirmation test)
Water containing algae (green algae cocci) was collected from a certain cooling tower as test water, and 10 ml of this test water was dispensed into test tubes. 100 mg / l of the same chemical as the formulation of Test Example 4 was added and stirred well, and the test tube was capped with a silicone rubber sponge and allowed to stand in a bright place away from direct sunlight. One week later, the appearance of the test water was visually observed. For comparison, the same test was performed for the case where no drug was added.
The results obtained are shown in Table 5.

Effect of the invention

The aqueous triazine preparation of the present invention is a uniform preparation and does not cause water turbidity or crystal precipitation even when added to an aqueous system.
Therefore, the aqueous triazine preparation of the present invention can provide an algicidal agent that can be added to an aqueous system, and 2-phosphonobutane-1,2,4-tricarboxylic acid contained in the preparation as a solubilizing agent for triazine. By increasing the blending amount, it is possible to provide an aqueous preparation having anticorrosive and scale preventive actions in addition to the algicidal action.
Furthermore, the aqueous triazine preparation of the present invention can provide a comprehensive water treatment agent by blending with other active ingredients such as a bactericidal agent, and is extremely useful industrially.

  It is a schematic diagram of the apparatus used for the scale prevention and anticorrosion effect confirmation test in Reference Example 1.

DESCRIPTION OF SYMBOLS 1 Cooling water pit 2 Inspection water pit 3 Temperature sensor 4 Temperature controller 5 Solenoid valve 6 Magnet pump 7 Flow meter 8 Test part 9 Heater 10 Hot water pit 11 Test water 12 Hot water (pure water)
13 Power supply

Claims (5)

(A) 2-methylthio-4-cyclopropylamino-6-tert-butylamino-1,3,5-triazine or 2- (tert-butylamino) -4-chloro-6-ethylamino-1,3 5-triazine,
(B) 2-tricarboxylic acid, and (C) contains a glycol-based hydrophilic organic Solvent <br/>, component (B) is component (A) to component (C) triazine emissions made agent characterized by comprising contained as a solubilizing agent.
Triazine emissions made agent as claimed in claim 1, wherein component (A) is made is contained 0.1 to 10 wt% in the formulation.
Component (B), the component (A) with respect to 1 part by weight, triazine emissions made agent according to claim 1 or 2 formed by containing at least 1.25 parts by weight.
Component (B), triazine emissions made agent according to any one of claims 1 to 3 comprising contained as corrosion and / or scale prevention component.
The triazine preparation according to any one of claims 1 to 4, further comprising water.

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