JPH0244802B2 - NOYAKUSUIWAZAIYOBUNSANZAI - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a dispersant for use in agrochemical wettable powders, which has excellent hydration properties and suspension properties, and has low foaming properties. Surfactants conventionally used as dispersants for agrochemical wettable powders include alkyl sulfates, alkylaryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl (or alkyl phenol) ether sulfates, lignin sulfonates, and Anionic surfactants such as naphthalene sulfonate condensates or nonionic surfactants such as polyoxyethylene alkyl (or alkylphenol) ethers, polyoxyethylene sorbitan alkylate and polyoxyalkylene glycol, as well as polyvinyl alcohol and carboxymethyl cellulose. and water-soluble polymer compounds such as sodium alginate.However, in recent years, agricultural mechanization has progressed, and speed sprayers and helicopter sprayers are being used to spray hydrating powders, and the spraying liquid is vigorously agitated inside the sprayer. This causes problems such as excessive foaming, which interferes with spraying operations, and the development of a dispersant for wettable powders that produces less foaming has been strongly desired by all concerned parties. Methods for suppressing such foaming include adding an antifoaming agent to the diluted wettable powder solution, or using a low-foaming surfactant as a wettable powder component. Pesticide wettable powders using foaming surfactants have not achieved satisfactory results in terms of physical properties such as hydration or suspension. The present inventors have conducted extensive research on dispersants for pesticide hydration powders that are suitable for such purposes, and have found that the general formula MO ₃ SO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c SO ₃ M
…[1] The surfactant represented by the formula (where b is 15 to 80, a+c is 2 to 50, and M is an alkali metal, ammonium, or amine) is effective as a dispersant for agricultural chemical wettable powders. Yes, when added to a pesticide wettable powder, the wettable powder has excellent physical properties such as hydration and suspension, and exhibits extremely low foaming properties, so it can be used for power spraying such as speed sprayers and helicopter spraying. The present invention was completed based on the discovery that the workability can be greatly improved even in the case of the above-mentioned method, without the problem of foaming. Furthermore, we have discovered that when a hydrating powder using the dispersant of the present invention is used in combination with an existing agrochemical emulsion or sol (flowable agent), it exhibits an antifoaming effect without adversely affecting the stability of the system. As a result, the present invention has been completed. The surfactant represented by the general formula [1] of the present invention is a sulfate ester salt of a block polymer in which ethylene oxide is added to both ends of the hydrophobic group of polypropylene glycol obtained by addition polymerizing propylene oxide, Among these, the average molecular weight of polypropylene glycol is
850 to 5000, add ethylene oxide to this
After sulfuric acid esterification of the end of the addition polymerized by 50 moles, alkali metals such as Na and K, ammonium or monomers are added. It is a salt neutralized with amines such as di- and triethanolamine. The above technical idea according to the present invention is based on the general formula [1]
Further modified structures such as sulfate of a polymer obtained by adding propylene oxide and then ethylene oxide to glycerin, sulfate of a polymer obtained by adding propylene oxide and then ethylene oxide to ethylenediamine or propylene diamine, etc. In some cases, the monosulfate derivative in the above general formula [1] may be used to obtain a preferable effect, and in some cases, a good dispersant may be obtained by using it as a monosulfate derivative in the above general formula [1]. The dispersant of the present invention is a conventionally used alkyl sulfate, alkylaryl sulfonate, dialkyl sulfoxinate, polyoxyethylene alkyl (or alkyl phenol) ether sulfate, lignin sulfonate, and naphthalene sulfonate formalin condensate. It is also possible to use anionic surfactants such as, and nonionic surfactants such as polyoxyethylene alkyl (or alkyl phenol) ether, polyoxyethylene sorbitan alkylate, polyoxyalkylene glycol, etc. In particular, lignin sulfone Even better effects may be obtained when used in combination with an acid salt or a naphthalene sulfonate formalin condensate. Another feature of the present invention is that it can be applied to a wide range of target pesticides, such as carbamate, organic phosphorus, and chlorine. Next, a production example of the surfactant represented by the general formula [1] in the present invention will be shown. Production example 1 Process for producing polyoxyethylene (5) polyoxypropylene (30) block polymer sulfate ester ammonium salt (The numbers in parentheses indicate the number of moles (the same applies hereinafter). 76 g of propylene glycol in an autoclave.
Add 4g of caustic potassium as a catalyst and completely replace the air in the autoclave with nitrogen gas, then raise the temperature to 130-160℃ and produce 1682g of propylene oxide.
Addition polymerize 220 g of ethylene oxide, then neutralize caustic potash with acid to add 1980 g of polyoxyethylene (5) polyoxypropylene (30) block polymer to a nitrogen inlet tube, thermometer, and stirrer. Transferred to a flask equipped with a nitrogen gas, mixed with 60g of urea and heated to 90℃, added 194g of sulfamic acid, reacted at 110-120℃ for 2 hours, and purified by filtration. A polyoxyethylene (5) polyoxypropylene (30) block polymer sulfate ammonium salt is obtained. Production Example 2 Method for producing polyoxyethylene (20) polyoxypropylene (55) block polymer sulfate ester sodium salt. 76g of propylene glycol in autoclave
Add 4g of KOH and completely replace the air in the autoclave with nitrogen gas, then raise the temperature to 130-160℃.
Addition polymerization of 880 g of propylene oxide is carried out.
Thereafter, 4093 g of polyoxyethylene (20) polyoxypropylene (55) block polymer obtained by neutralizing KOH with acid was transferred to a flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer, and dissolved in an equal weight of methylene chloride. While stirring while introducing nitrogen gas, 280 g of chlorsulfonic acid was added dropwise at 10 to 20°C, and the reaction was carried out for 2 hours. The reaction product was neutralized with an aqueous NaOH solution, the solvent was distilled off, and polyoxyethylene (20 ) Polyoxypropylene (55) block polymer sulfate ester sodium salt is obtained. Production Example 3 Process for producing polyoxyethylene (45) polyoxypropylene (16) block polymer sulfate ester amine salt. 2928g of polymer produced in the same manner as Production Example 1
Add an equal amount of methylene chloride to dissolve and stir while introducing nitrogen gas to dissolve chlorosulfonic acid.
280g was added dropwise at 10-20°C and reacted for 2 hours. The reaction product was neutralized with triethanolamine and the solvent was distilled off to obtain polyoxyethylene (45) polyoxypropylene (16) block polymer sulfate ester amine salt. get. Production Example 4 Method for producing polyoxyethylene (25) polyoxypropylene (75) block polymer sulfate ester ammonium salt. 5476g of polymer produced in the same manner as Production Example 1
Mix 60g of urea while introducing nitrogen gas into the
Heat to 110℃ and add 194g of sulfamic acid.
After reacting at 120°C for 2 hours, the mixture is filtered to obtain polyoxyethylene (25) polyoxypropylene (75) block polymer sulfate ammonium salt. Production Example 5 Method for producing polyoxyethylene (20) polyoxypropylene (40) block polymer sulfate ester amine salt. Polymer produced in the same manner as Production Example 2
After sulfating 3200 g, it was neutralized with triethanolamine to obtain polyoxyethylene (20) polyoxypropylene (40) block polymer sulfate ester amine salt. The specific performance of the wettable powder using the dispersant made of the product of the present invention obtained in the above production example will be tested for the following examples and a comparative product (conventional product).The results are shown below. Example 1 77 parts of Manganese ethylene bisdithiocarbamate (maneb), 10 parts of white carbon, 8 parts of clay, 5 parts of dispersant (Production Example 1) are parts by weight, and the same ingredients are mixed and ground to form a wettable powder. obtain. Example 2 In the formulation of Example 1, the dispersant was replaced with the dispersant shown in Production Example 2, and a wettable powder was obtained in the same manner. Example 3 In the formulation of Example 1, the dispersant was replaced with the dispersant shown in Production Example 3, and a wettable powder was obtained in the same manner. Example 4 In the formulation of Example 1, the dispersant was replaced with the dispersant shown in Production Example 4, and a wettable powder was obtained in the same manner. Example 5 88 parts of 1-naphthyl-N-methylcarbamate,
A wettable powder is obtained by mixing and pulverizing 7 parts of white carbon and 5 parts of a dispersant (Production Example 1). Example 6 72 parts of 1,2-bis(3-methoxycarbonyl-2-thiouredo)benzene, 10 parts of white carbon
part, 8 parts of diatomaceous earth, 3 parts of dispersant (Production Example 1),
Two parts of the naphthalene sulfonic acid formalin condensate are mixed and ground to obtain a wettable powder. Comparative Example 1 In the formulation of Example 1, the dispersant was replaced with lignin sulfonate, and the mixture was mixed and ground to obtain a wettable powder. Comparative Example 2 In the formulation of Example 1, the dispersant was replaced with sodium dodecylbenzenesulfonate, and the mixture was mixed and ground to obtain a wettable powder. Comparative Example 3 In the formulation of Example 1, the dispersant was replaced with a polyoxyethylene (5) polyoxypropylene (30) block polymer, mixed and pulverized to obtain a wettable powder. Next, Table 1 shows the results of testing the physical properties of the hydrating agents shown in each example using the test method below.
Shown below. Test method 1 Hydration… 200ml of 3 degree hard water at 20°C in a 500ml beaker
ml and gently drop 5g of the hydrating agent into it from about 10cm above the water surface so that it spreads thinly. Measure the time (seconds) from when the sample (hydrating agent) is dropped until it submerges under the water surface. 2 Suspension property...hydration powder sample 0.5g (active ingredient Ag)
Weigh it into a beaker and heat it to 20℃.
Add 50ml of hard water, mix well to disperse thoroughly, transfer to a 250ml graduated cylinder with a stopper (Figure 1), add the same 20℃ water as above to make 250ml,
After letting it stand for a minute, shake the mixture vigorously by standing it upside down 30 times per minute and let it stand for 15 minutes. Next, place a 25ml whole PET into the liquid, keep the tip in the center of the liquid, and gently suck up 25ml of the test liquid.
Determine the content of active ingredient (Bg).
Calculate the suspension rate using the following formula Suspension rate (%) = B x 10 / A x 100 3 Foaming property...Pour 0.5g of the wettable powder sample into a 250ml stoppered cylinder containing a fixed amount of distilled water at 20℃ and invert 10 times. After that, let it stand and measure the foam height (mm) after 1 minute. Measurement was performed using the method shown in Figure 1.

【table】

[Table] As is clear from the test results shown in Table 1, the dispersant for agricultural chemical wettable powders of the present invention has excellent hydration and suspension properties, which are not found in conventional dispersants, as well as low foaming properties. It was confirmed that

[Brief explanation of the drawing]

Figure 1 shows the foamability test using a 250ml stoppered graduated cylinder. The reading value (mm) of h after 1 minute of standing is taken as the foam height.

Claims (1)

[Claims] 1 The following general formula MO ₃ SO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c SO ₃ M
…[1] A hydrated agricultural chemical characterized by containing a surfactant represented by the formula (where b is 15 to 80, a+c is 2 to 50, and M represents an alkali metal, ammonium, or amines) Dispersant for pharmaceuticals.