JP2010275262A - Aqueous pesticide composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous pesticide composition capable of enhancing retentive properties by more rationally and highly efficiently, preventing a water-diluted liquid from exfoliating and running off of an active constituent by weather or the like after spraying, than the one by a conventional method. <P>SOLUTION: The aqueous pesticide composition contains a solid material having a melting point of 40-110°C including an esterified compound of an alcohol and fatty acid, a surfactant, and an active constituent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a water-based agrochemical composition that can enhance the retention of an active ingredient with respect to an object when spraying a stock solution or a water-diluted solution.

  When the raw solution is diluted or dispersed in water and sprayed, and the active ingredients such as marking agents and agricultural chemicals are retained on the object, separation and runoff due to wind and rain after spraying become a problem. Of course, if it is a marking agent, it is necessary to maintain the marking effect for a necessary period of time, and for active ingredients such as agricultural chemicals, especially those that do not have osmotic transferability, to obtain a sufficient effect on the solid surface for a certain period of time. There is a need to hold. Therefore, in order to obtain a necessary effect, the application person sprays an excessive amount and number of times, resulting in a great amount of labor, economic burden and environmental problems.

  There is a spreading agent added to a water-diluted spray for the purpose of enhancing the retention of active ingredients on animals and plants. Such spreaders generally improve the retention by lowering the surface tension of the spray liquid and making it easier to spread evenly on the surfaces of animals and plants that are difficult to get wet. In addition, since highly hydrophilic polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, and the like are used, not only can the runoff due to rain not be suppressed, but there may be an adverse effect. In addition, spreaders that increase the penetration of active ingredients into plants by blending with specific surfactants are also commercially available, but the effective ingredients that can be effective are limited or non-penetrating. No effect can be expected for migratory agricultural chemical active ingredients and auxiliary ingredients. In addition, there are spreaders mainly composed of polyoxyalkylene resin acid esters and paraffin, but they contain a relatively large amount of emulsifiers or may use solvents due to their ease of production. Later spreaders can easily re-emulsify and run away with active ingredients. Such a spreading agent is not necessarily effective in preventing runoff due to rainfall, and may be restricted in use from the viewpoint of chemical damage, residual, and the like. Moreover, in actual use situations, there are many situations where it is required to incorporate a component that enhances retention in the preparation in advance because of its complexity. However, it is also not appropriate to commercialize a commercial spreader as it is in the preparation as it has various problems.

  On the other hand, various ingenuity in formulation design for enhancing the retention of active ingredients in the form of incorporating a third substance into the formulation has been studied and reported. For example, granule wettable powder containing carboxymethyl cellulose or a salt thereof having a 2% aqueous solution viscosity of 10 to 2,000 mPa · s (see Patent Document 1), granule hydration whose surface is coated with a specific water-soluble substance Agents (see Patent Document 2). In the case of a granular wettable powder, a water-soluble substance is used because it is required to have the ability to disintegrate granules at the same time. However, the water-soluble substance cannot suppress runoff due to rainfall or the like and is not an optimal substance. In addition, a wettable powder containing a partially saponified polyvinyl alcohol aqueous solution (see Patent Document 3), an emulsion containing a sorbitan trioleate, a wettable powder, a flowable powder, a granular wettable powder (see Patent Document 4), Although there is a description of a flowable agent (see Patent Document 5) containing HLB 2 to 13 polyoxyethylene resin acid ester or liquid paraffin, polyvinyl alcohol has a performance limit of rain resistance, and sorbitan triolate. In the case of lipophilic surfactants with low HLB such as polyoxyethylene resin acid esters and liquid paraffin, liquid paraffin lacks compatibility and causes separation and thickening that may cause problems in physical properties depending on the amount added. There is a fear. Moreover, it is possible to stably incorporate these water-insoluble substances into the preparation in an emulsified state using an appropriate emulsifier, but it is difficult to obtain a stable emulsion unless a large amount of emulsifier is used. In the first place, even after adherence and drying, it is easy to re-emulsify if the substance that exhibits rain resistance is in a liquid state, but the emulsifier used to obtain a stable emulsion further promotes re-emulsification due to rainfall. Retention in animals and plants is insufficient.

JP 2005-132741 A Japanese Patent No. 2694926 JP-A-8-217604 WO97 / 46092 WO2005 / 006863 publication

  The present invention provides a method for obtaining an aqueous pesticide composition capable of preventing separation and loss of active ingredients due to wind and rain after spraying a water dilution solution, and preventing retention of the loss more efficiently and enhancing retention than conventional methods. The purpose is to find out. Moreover, this composition needs to be excellent in terms of handling and environmental load.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a surfactant having a melting point of 40 to 110 ° C. containing an esterified product of alcohol and fatty acid, which is less than usual with respect to the solid content. By making it an aqueous dispersion, we succeeded in simplifying the blending into the aqueous agrochemical composition, and surprisingly, compared with the case where the existing spreader was blended in the composition, It was found that there is a clear advantage in the retention of active ingredients on the surface of animals and plants.

  That is, the present invention relates to an aqueous pesticide composition characterized by containing a solid substance having a melting point of 40 to 110 ° C. containing an esterified product of an alcohol and a fatty acid, a surfactant and an active ingredient.

  According to the present invention, it is possible to improve the retention of the active ingredient with respect to the object, so that the effect is expected to continue over a long period of time, leading to the reduction of the number of times of application, the amount of application, the concentration of application, the labor of the user, the cost It can solve problems such as environmental load and chemical damage.

  Specific examples of solids having an melting point of 40 to 110 ° C. containing an esterified product of alcohol and fatty acid used in the present invention include beeswax, wood wax, white wax, carbana wax, canderia wax, montan wax, nuka wax, rice Examples thereof include wax, lanolin wax, beef tallow hardened oil, beef tallow extremely hardened oil, rapeseed extremely hardened oil, palm extremely hardened oil, hardened castor oil, and coconut hardened oil. The solid is preferably a wax derived from a natural animal or plant having an acid value of 0.1 to 50 and a saponification value of 50 to 250 in terms of obtaining high retainability, an acid value of 3 to 20, and a saponification value of 50 to 150. It is more preferable that the acid value is 5 to 20, and the saponification value 70 to 150 is particularly preferable. The alcohol may be a monohydric alcohol or a polyhydric alcohol, but is preferably a monohydric higher alcohol, especially a higher alcohol having 8 to 40 carbon atoms. The fatty acid is preferably a higher fatty acid, especially a higher fatty acid having 8 to 40 carbon atoms. In addition, although the said solid substance may contain a free fatty acid, a free alcohol, a hydrocarbon etc. in an esterified substance, for example, it is that the solidified substance contains 5-100 mass% of esterified substances. Preferably, the content is 20 to 95% by mass, more preferably 60 to 90% by mass.

  The solid substance having a melting point of 40 to 110 ° C. containing the esterified product of alcohol and fatty acid used in the present invention is made into an aqueous dispersion with a small amount of surfactant using a mechanical emulsifier and incorporated into the aqueous agricultural chemical composition. be able to. The mechanical emulsifier that can be used may be either a batch type or a continuous type, and examples thereof include a commercially available ultra-high speed emulsifying disperser, a media type emulsifying disperser, and a high-pressure jet emulsifying disperser, but are not limited thereto. . The median diameter of the aqueous dispersion is preferably from 1 nm to 1 μm, more preferably from 10 nm to 500 nm, and particularly preferably from 30 nm to 300 nm in that high retention and dispersion stability can be obtained.

  Specific examples of the surfactant used in preparing the aqueous dispersion include polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxyethylene sorbitan ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene resin acid ester, Polyoxyalkylene glycol, polyoxyalkylene styryl (1-3 mol) phenyl ether, polyoxyalkylene alkyl aryl ether, polyoxyalkylene castor oil ether, sorbitan fatty acid ester, polyoxyethylene alkylamine, polyoxyalkylene hardened castor oil ether, polyvalent Nonionic surfactants such as alcohol fatty acid esters and polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyalkylene alkyl sulfates, alcohols Kill sulfate, (mono and di) alkyl sulfosuccinate, alkylbenzene sulfonate, polyoxyalkylene alkylaryl ether sulfate, polyoxyalkylene styryl (1-3 mol) phenyl ether sulfate, fatty acid salt, fatty acid alkyl taurine salt , Polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkyl aryl ether phosphate, alkyl phosphate, polyoxyalkylene styryl (1-3 mol) phenyl ether phosphate, polycarboxylate, funnel oil, poly Anionic surfactants such as alkylene glycol sulfates, cationic surfactants such as alkyltrimethylammonium chloride and benzalkonium chloride, dialkylaminoethyl betaines, alkylbetaines, fatty acid amides Kirubetain, although amphoteric surfactants such as alkyl sulfo betaine, not as far as these. 0.1-3 mass% is preferable with respect to solid content, and, as for the usage-amount of surfactant used at the time of aqueous dispersion preparation, 0.2-2 mass% is still more preferable, 0.3-1.5 mass % Is particularly preferred.

  The active ingredient according to the present invention includes agrochemical bactericidal ingredient, agrochemical insecticidal ingredient, agrochemical herbicidal ingredient and the like, ingredients used in general pesticides, marking (coloring) ingredients, etc., and is particularly restricted regardless of liquid or solid. It is not a thing.

  In addition to this, the agrochemical water-based composition of the present invention may further contain a dispersant, an emulsifier, a spreader, an antiseptic, an antifoaming agent, a thickener, an antifreezing agent, an anti-decomposition agent, and the like as necessary. I can do it.

  Next, the best mode for carrying out the present invention will be described by way of examples. In addition, this invention is not limited to these.

Example 1
After dissolving 200 g of purified beeswax (Yokoseki Yushi Kogyo Co., Ltd., melting point 64 ° C., acid value 17, saponification value 91), 10 g of Solpol 7509 (anionic surfactant ai 20%, manufactured by Toho Chemical Co., Ltd.), 290 g of ion-exchanged water Was added and premixed, and then a beeswax aqueous dispersion (ai 40%, Median diameter 290 nm) was prepared with a high-pressure jet type emulsifying disperser. 12.5 parts of the prepared aqueous dispersion (5 parts of solid pure content), 3.75 parts of marking component (colorant Rio Fresh), Pegnol ST-9 (nonionic surfactant manufactured by Toho Chemical Co., Ltd.) 1 Part and 82.75 parts of water were mixed to obtain an aqueous composition.
Example 2
12.5 parts of beeswax aqueous dispersion of Example 1 (5 parts of solid pure content), 0.38 parts of marking component (coloring agent rhodamine B), pegnol ST-9 (nonionic surface activity produced by Toho Chemical Co., Ltd.) Agent) 1 part and 86.12 parts of water were mixed to obtain an aqueous composition.
Example 3
43.75 parts (17.5 parts of solid pure content) of the beeswax aqueous dispersion of Example 1, 50 parts of an agrochemical component (bactericide quinone dough flowable), Pegnol ST-9 (nonionic interface manufactured by Toho Chemical Co., Ltd.) 1 part of activator) and 6.25 parts of water were mixed to obtain an aqueous composition.
Example 4
The purified beeswax of Example 1 was changed to hard lanolin (manufactured by Nippon Seika Co., Ltd., melting point 48 ° C., acid value 0.3, saponification value 102) and converted into an aqueous dispersion (Median diameter 400 nm) by the same method. 12.5 parts of the prepared aqueous dispersion (5 parts of solid pure content), 3.75 parts of marking component (colorant Rio Fresh), Pegnol ST-9 (nonionic surfactant manufactured by Toho Chemical Co., Ltd.) 1 Part and 82.75 parts of water were mixed to obtain an aqueous composition.
Example 5
The refined beeswax of Example 1 was changed to candelilla wax (manufactured by Yokoseki Yushi Kogyo Co., Ltd., melting point 71 ° C., acid value 18, saponification value 58) to prepare an aqueous dispersion (Median diameter 340 nm) by the same method. 12.5 parts of the resulting aqueous dispersion (5 parts of solid pure content), 3.75 parts of marking component (colorant Rio Fresh), 1 part of Pegnol ST-9 (nonionic surfactant manufactured by Toho Chemical Co., Ltd.) Then, 82.75 parts of water was mixed to obtain an aqueous composition.
Example 6
The purified beeswax of Example 1 was changed to carnauba wax (manufactured by Yokoseki Yushi Kogyo Co., Ltd., melting point 80 ° C., acid value 4, saponification value 80) to obtain an aqueous dispersion by the same method. 5 parts (solid pure 5 parts), marking component (colorant Rio Fresh) 3.75 parts, Pegnol ST-9 (nonionic surfactant manufactured by Toho Chemical Co., Ltd.), water 82.75 parts Were mixed to obtain an aqueous composition.
Comparative Example 1
3.75 parts of marking components (colorant Rio Fresh), 1 part of Pegnol ST-9 (nonionic surfactant manufactured by Toho Chemical Industry Co., Ltd.) and 96.25 parts of water were mixed to obtain an aqueous composition.
Comparative Example 2
Avion E (paraffin emulsion spreading agent ai 24%, manufactured by Avion Corporation) 20.8 parts (solid pure 5 parts), marking component (colorant Rio Fresh) 3.75 parts, Pegnol ST-9 (Toho Chemical Co., Ltd.) 1 part of nonionic surfactant (made by company) and 74.45 parts of water were mixed to obtain an aqueous composition.
Comparative Example 3
The purified beeswax of Example 1 was changed to rapeseed oil (reagent melting point -5 ° C., acid value 0.1 or less, saponification value 175, manufactured by Showa Chemical Co., Ltd.) to prepare a rapeseed oil-based dispersion (ai 40%). 12.5 parts (5 parts of solid pure content) of the produced aqueous dispersion, 3.75 parts of marking component (colorant Rio Fresh), Pegnol ST-9 (nonionic surfactant manufactured by Toho Chemical Co., Ltd.) 1 Part and 82.75 parts of water were mixed to obtain an aqueous composition.

  The particle size of the aqueous dispersion was measured with a dynamic light scattering particle size analyzer Microtrac UPA (manufactured by HONEY WELL). Next, a method for evaluating the retention of the obtained composition will be described with reference to test examples.

Test example 1
The compositions obtained in Examples 1, 2, and 4 and Comparative Examples 1, 2, and 4 were coated on a white wax-coated plate having a melting point of 52 ° C. and held at 40 ° C. for 72 hours. After immersing the plate in water for 5 minutes, the plate was removed and the absorbance of the immersed water was measured. Taking into account the amount applied for each sample and the concentration of the marking component, the retention rate (%) of the active component on the plate was calculated from a calibration curve prepared in advance. The results are shown in Table 1.
Retention rate (%) = 100− (measured colorant concentration / colorant concentration when the applied amount is all washed away in immersed water) * 100
Test example 2
Water in which the composition obtained in Example 3 was immersed in the same manner as in Test Example 1 was obtained, and the copper ion concentration was measured by atomic absorption. The retention rate (%) of the active ingredient on the plate was calculated from a calibration curve prepared in advance, taking into account the amount applied for each sample and the copper ion concentration. The results are shown in Table 1.
Retention rate (%) = 100− (measured copper ion concentration / copper ion concentration when the applied amount is all washed away in soaked water) * 100

From Table 1, blending an aqueous dispersion of a solid matter having a melting point of 40 to 110 ° C. containing an esterified product of alcohol and fatty acid with a reduced amount of surfactant used during preparation of the aqueous dispersion into the aqueous agrochemical composition, It is clear that the retention of active ingredients is enhanced. Among them, the acid value of 5 to 20 containing a higher alcohol having 8 to 40 carbon atoms and a higher fatty acid ester having 8 to 40 carbon atoms and a saponification value of 70 to 150, which are represented mainly by myricyl palmitate, The effect of blending an aqueous dispersion of beeswax, which is a solid substance, is remarkable.

Claims (3)

A water-based agrochemical composition comprising a solid substance having a melting point of 40 to 110 ° C. containing an esterified product of alcohol and fatty acid, a surfactant and an active ingredient. The aqueous pesticide composition according to claim 1, wherein the esterified product of alcohol and fatty acid is an esterified product of higher alcohol and higher fatty acid. The aqueous pesticide composition according to claim 1 or 2, wherein the solid has an acid value of 0.1 to 50 and a saponification value of 50 to 250.