JP4514212B2 - Agrochemical active ingredient controlled release agricultural chemical composition - Google Patents

Description

  The present invention relates to an agricultural chemical active ingredient release control type agricultural chemical composition. When pesticide granules are sprayed on the soil, the pesticide granules are disintegrated due to moisture or rain in the soil, and the pesticide active ingredients contained in this are released, showing medicinal properties, but are included in the pesticide granules In the case where the pesticidal active ingredient is highly water-soluble, it is necessary to control the release of the pesticidal active ingredient in order to reduce the phytotoxicity that may occur temporarily or temporarily. The present invention is a pesticidal composition containing a highly water-soluble pesticidal active ingredient, and the pesticidal active ingredient release control type capable of gradually releasing the pesticidal active ingredient when the pesticidal granules obtained therefrom are sprayed on the soil The present invention relates to an agrochemical composition.

  Conventionally, it has been proposed to coat or microencapsulate an agrochemical active ingredient as a means of maintaining the medicinal effect of the agrochemical active ingredient. However, such a conventional proposal requires a coating process and a microencapsulation process of an agrochemical active ingredient, which not only increases the number of processes, but also requires a correspondingly large facility. The work is complicated and uneconomical.

Conventionally, as another means for maintaining the medicinal effect of an agrochemical active ingredient, it has been proposed to form a matrix by kneading the agrochemical active ingredient with a wax or a resinous material. In this proposal, in the formation of the matrix, an example using an emulsion of a water-insoluble resin such as an ethylene vinyl acetate copolymer (for example, see Patent Document 1), an example using a water-soluble organic acid salt (for example, see Patent Document 2) ), An example using a thermoplastic material at a temperature not lower than the freezing point and lower than the melting point (for example, see Patent Document 3), an example using carboxymethyl cellulose or a salt thereof (for example, see Patent Document 4), an example using an alcohol type wax (for example, Patent Document 5). However, these conventional proposals have the advantage of not requiring the coating process and the microencapsulation process as described above, but produce agricultural chemical granules from those in which the agricultural chemical active ingredients are kneaded with wax or resinous materials. As a result, there are problems such as poor productivity, poor shape retention and wear resistance of the resulting agrochemical granule, and insufficient sustained release of the agrochemical active ingredient in the first place.
JP 2001-55303 A JP-A-8-175903 JP 2003-252702 A JP 2001-233706 A Japanese Patent Laid-Open No. 11-292706

  The problem to be solved by the present invention is to provide an agricultural chemical active ingredient release control type agricultural chemical composition capable of easily and economically producing an agricultural chemical granule having excellent physical properties that gradually releases a highly water-soluble agricultural chemical active ingredient after spraying. It is in the place to provide things.

  Accordingly, as a result of studies conducted by the present inventors to solve the above-mentioned problems, it has been found that a specific agrochemical active ingredient release control agent, a specific agrochemical active ingredient, and a bulking agent are contained in a predetermined ratio. I found out.

  That is, the present invention contains 95 to 100% by mass of the following pesticidal active ingredient release control agent, the following pesticidal active ingredient and bulking agent in mass% in terms of solid content, and contains 5 pesticide active ingredient release control agent. It relates to a pesticidal active ingredient release control type pesticidal composition comprising -15% by weight, 1-30% by weight of the pesticidal active ingredient and 50-85% by weight of the extender.

  Pesticide active ingredient release controlling agent: composed of the following organic phosphate ester and the following aqueous resin emulsion, and the organic phosphate ester / the aqueous resin emulsion = 93/7 to 60/40 (mass ratio in terms of solid content) Agrochemical active ingredient release control agent

  Organophosphate: Organophosphate represented by the following chemical formula 1

In chemical formula 1,
R ¹ : Aliphatic hydrocarbon group having 18 to 22 carbon atoms M ⁺ : Potassium ion, sodium ion, diethanolammonium or triethanolammonium q, r: 1 or 2 and satisfying q + r = 3

  Aqueous resin emulsion: one or more selected from vinyl acetate resin emulsion, acrylic resin emulsion and fluororesin emulsion

  Pesticide active ingredient: Agrochemical active ingredient having a common logarithm log P of octanol-water partition coefficient P of -5 to 2 and / or water solubility at 20 ° C of 0.1 to 80 g / 100 ml

  The agrochemical active ingredient release control agent used in the present invention comprises an organic phosphate represented by Chemical Formula 1 and a specific aqueous resin emulsion.

The organic phosphate ester represented by Chemical Formula 1 includes an organic phosphoric acid monoester when q in Chemical Formula 1 is 1, and an organic phosphoric diester when q in Chemical Formula 1 is 2. Such organic phosphoric acid monoesters include those in which M ^{+ in} Chemical Formula 1 is the same at the same time and those in which M ⁺ are different at the same time. ^The case where ¹ is the same at the same time and the case where ¹ are different at the same time are included. Among these organic phosphates, one or more of these can be used.

In the organic phosphate ester represented by Chemical Formula ¹ , R ^{1 in} Chemical Formula ¹ is an aliphatic hydrocarbon group having 18 to 22 carbon atoms. Examples of the aliphatic hydrocarbon group include 1) a saturated aliphatic hydrocarbon group such as a stearyl group, an eicosyl group, a behenyl group, and an isostearyl group, and 2) an unsaturated aliphatic hydrocarbon group such as an oleyl group and an eicosenyl group. It is done.

In the organic phosphate ester represented by Chemical Formula 1, M ^{+ in} Chemical Formula 1 is potassium ion, sodium ion, diethanolammonium or triethanolammonium.

  Among the organic phosphates represented by Chemical Formula 1 described above, specific examples of the organic phosphate monoesters include monostearyl dipotassium phosphate, monoeicosyl dipotassium phosphate, monobehenyl dipotassium phosphate, and monooleyl dipotassium phosphate. And organic phosphoric acid monoester dipotassium such as monoeicosenyl dipotassium phosphate.

  Specific examples of organic phosphate diesters include 1) organic phosphate diester potassiums such as distearyl potassium phosphate, dieicosyl potassium phosphate, dibehenyl potassium phosphate, etc. 2) distearyl sodium phosphate, diphosphate phosphate Organophosphate diester sodium such as eicosyl sodium and dibehenyl sodium phosphate 3) Organophosphate diester ammonium diphosphate ammonium such as distearyl diethanolammonium phosphate, diecosyl diethanolammonium phosphate and dibehenyl diethanolammonium phosphate, 4 ) Organic phosphate diester triethanolammonium such as distearyl triethanolammonium phosphate, dieicosyl triethanolammonium phosphate, dibehenyl triethanolammonium phosphate .

  The organic phosphoric acid ester used as one component of the agrochemical active ingredient release control agent is 1) a single or mixture of organic phosphoric acid monoesters when q in Chemical Formula 1 is 1, and 2) q in Chemical Formula 1 2) A mixture of an organic phosphoric acid monoester and an organic phosphoric acid diester as described above is included.

  The organophosphate ester represented by Chemical Formula 1 can be synthesized by a known method. For example, after adding a predetermined amount of phosphoric anhydride to an aliphatic monohydric alcohol and reacting it to make an acidic organic phosphoric ester, this acidic organic phosphoric ester is converted into a predetermined proportion of organic amine, ammonia or alkali metal. Examples include a method of neutralizing with a hydroxide to form an organic phosphate ester salt.

  The aqueous resin emulsion used as another component of the agrochemical active ingredient release control agent is one or more selected from vinyl acetate resin emulsion, acrylic resin emulsion, and fluorine resin emulsion. preferable.

  The agrochemical active ingredient release controlling agent to be used in the present invention comprises the above-described specific organic phosphate ester and a specific aqueous resin emulsion, and the organic phosphate ester / the aqueous resin emulsion = 93/7 to 60/40. It is contained at a ratio of (mass ratio in terms of solid content).

  The agrochemical active ingredient used in the present invention is 1) an agrochemical active ingredient having a common logarithm log P of octanol-water partition coefficient P of -5 to 2, and 2) water solubility at 20 ° C. of 0.1 to 80 g / 100 ml. Pesticide active ingredient, 3) Pesticide active ingredient that satisfies the log P of 1) and the water solubility of 2) at the same time is included. Specific examples of the pesticidal active ingredient in 1) include carbofuran (water solubility = 0.07, log P = 1.23), imidacloprid (water solubility = 0.05, log P = 0.57), mesomil (water solubility = Insecticides such as 0.005, log P = 0.09), herbicides such as simazine (water solubility = 0.005, log P = 1.96), alloxidim (water solubility = 200, log P = −0.2), Examples include plant growth regulators such as dichlorprop (water solubility = 0.035, log P = 1.77). In addition, as the agrochemical active ingredient of the above 2), an insecticide such as etiophencarb (water solubility = 0.18, log P = 2.04), a fungicide such as simoxanil (water solubility = 0.1, log P = 4.7) And herbicides such as dimetachlor (water solubility = 0.2, log P = 2.62). Furthermore, as the pesticidal active ingredient of 3), acephate (water solubility = 79.0, log P = 0.13), dimethoate (water solubility = 2.5, log P = 0.22), thiocyclam (water solubility = 8. Insecticides such as 0 g / 100 ml, log P = 0.85), pyrimi curve (water solubility = 0.3, log P = 1.7), oxamyl (water solubility = 28.0, log P = −0.44), hydroxyiso Xazole (water solubility = 8.5, log P = 0.22), metalaxyl (water solubility = 0.71, log P = 1.75), fosetyl aluminum (water solubility = 12.0, log P = −2.70) , Iminotadine acetate (water solubility = 76.4, log P = −1.33), tricyclazole (water solubility = 0.16, log P = 1.40), dazomet (water solubility = 0.0.1). , Log P = 1.4), dimethylylmol (water solubility = 0.12, log P = 1.9), pyroxylone (water solubility = 0.4, log P = 1.57) and the like, bactericides such as cetoxydim (water solubility = 0) .47, log P = 1.65), Nicosulfuron (water solubility = 1.22, log P = 0.02), diquat (water solubility = 70, log P = -4.6) and other herbicides, daminogit (water solubility) = 10, logP = 0.031) and the like. As the pesticidal active ingredient, one or two or more selected from the pesticidal active ingredients as exemplified above can be used, but it is preferable to use the pesticidal active ingredient of the above 3).

  As the extender used in the present invention, 1) inorganic fine powders such as bentonite, talc, clay, diatomaceous earth, amorphous silicon dioxide, calcium carbonate, magnesium carbonate, etc. 2) low molecular weight compounds such as sodium sulfate, ammonium sulfate, potassium chloride, urea Water-soluble compounds, 3) Resin powders such as vinyl chloride, chlorinated polyethylene, chlorinated polypropylene, 4) Sugars such as glucose, fructose, sucrose, and lactose, carboxymethylcellulose and salts thereof, starch and derivatives thereof, microcrystalline cellulose, wood Organic powders such as flour, rice bran, bran, and rice bran are listed. Of these, inorganic fine powder is preferable.

  The agricultural chemical active ingredient release control type agricultural chemical composition of the present invention contains 95 to 100 mass% in total of the agricultural chemical active ingredient release controlling agent, the agricultural chemical active ingredient and the bulking agent described above in mass% in terms of solid content, and It contains 5 to 15% by mass of the agricultural chemical active ingredient release control agent, 1 to 30% by mass of the agricultural chemical active ingredient, and 50 to 85% by mass of the extender.

  The pesticidal active ingredient release control type pesticidal composition of the present invention can appropriately contain other components in a proportion of less than 5% by mass in terms of solid content. This includes, for example, disintegrators, spreaders, dispersants, binders, stabilizers, preservatives and the like that are all known per se. Disintegrating agents, spreading agents, and dispersing agents include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl mono fatty acid ester, polyoxypropylene glycol mono fatty acid ester, polyoxy Ethylene sorbitol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene fatty acid ester, higher fatty acid glycerin ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene fatty acid amide, alkylol amide , Nonionic surfactants such as polyoxyethylene alkylamine, alkylamine hydrochlorides such as dodecylamine hydrochloride, Ammonium salts, alkyltrimethyl quaternary ammonium salts such as dodecyltrimethylammonium salt, alkyldimethylbenzylammonium salts, alkylpyrimidinium salts, fatty acid sodium such as sodium palmitate, sodium ether carboxylates such as sodium polyoxyethylene lauryl ether carboxylate Amino acid condensates of higher fatty acids such as sodium lauroyl sarcosine and sodium N-lauroyl glutamate, higher fatty acid ester sulfonates such as higher alkyl sulfonates and lauric ester sulfonates, and dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate , Higher fatty acid amide sulfonic acid such as oleic acid amide sulfonate, dodecylbenzene sulfonate, diisopropyl naphthalene Phosphonate, alkylallylsulfonate formalin condensate, polyoxyethylene alkyl ether sulfate such as sodium polyoxyethylene dodecyl ether sulfate, styrene-maleic acid copolymer, N-laurylalanine, N, N, N- Examples include trimethylaminopropionic acid, N, N, N-trihydroxyethylaminopropionic acid, N-hexyl-N, N-dimethylaminoacetic acid, 1- (2-carboxyethyl) pyridinium betaine, and the like. Examples of the binder include dextrin, polyvinyl alcohol, pregelatinized starch, gum arabic, sodium alginate, polyvinyl pyrrolidone, glucose, sucrose, mannitol, sorbitol and the like. Further, examples of the stabilizer include epoxidized linseed oil, epoxidized tung oil, epoxidized soybean oil, dibutylhydroxytoluene, butylhydroxyanisole, isopropyl citrate, sodium tripolyphosphate and the like. Furthermore, examples of preservatives include butyl paraben, sorbic acid, potassium sorbate and the like.

  The agricultural chemical active ingredient release control type agricultural chemical composition of the present invention can be made into agricultural chemical granules by a known method. This includes, for example, 1) kneading an organic phosphate ester, aqueous resin emulsion, agrochemical active ingredient, extender and water using a stirring mixer, and granulating the kneaded product using a granulator. 2) Organophosphate ester, extender and water are kneaded using a stirrer and the kneaded product is granulated using a granulator, and then granulated. Examples include a method of impregnating and adsorbing an agrochemical active ingredient to a product and drying. Here, as the stirring mixer, a nauta mixer, a ribbon blender, a rotary blender, a V-type mixer, etc. can be applied, and as a granulator, an extrusion granulator, a mixing granulator, a rolling granulator, a fluidizer A layer granulator or the like can be applied.

  According to the agricultural chemical active ingredient release control type agricultural chemical composition of the present invention, it is possible to easily and economically produce an agricultural chemical granule having excellent physical properties that gradually releases a highly water-soluble agricultural chemical active ingredient after spraying.

  Hereinafter, examples and the like will be given to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.

Test Category 1 (Preparation of agricultural chemical active ingredient release control type agricultural chemical composition and manufacture of agricultural chemical granules)
Example 1
34 parts (10.2 parts in terms of solid content) of a 30% aqueous solution of the organic phosphate ester (A-1) listed in Table 1, 10 parts of oxamyl as an agrochemical active ingredient, and a fluororesin emulsion as an aqueous resin emulsion (Daikin Industries) 6 parts (trade name Unidyne TG-470B) manufactured by the company and 78 parts of a mixture of bentonite / clay = 20/80 (mass ratio) as a bulking agent are mixed to control the release of agrochemical active ingredients. Type pesticide composition (Example 1) was prepared. To this was added 15 parts of water and kneaded sufficiently, and the kneaded product was subjected to a basket type granulator (DG-L1 type manufactured by Fuji Powder Co., Ltd.) equipped with a 1.0 mm screen and motor inverter frequency 20 Hz. Shaft rotation speed 32r. p. It was extruded through a screen under the conditions of m. The extruded product was cut to a length of 2 to 4 mm, and then dried for 15 minutes with a fluidized bed dryer (MDA-200, manufactured by Fuji Paudal Co., Ltd.) to produce agrochemical granules.

Examples or Reference Examples 2 to 23 and Comparative Examples 1 to 11
In the same manner as in Example 1, the agricultural chemical active ingredient release control type agricultural chemical compositions of Examples or Reference Examples 2 to 23 and Comparative Examples 1 to 11 were prepared to produce agricultural chemical granules. Table 1 summarizes the compositions of the pesticidal active ingredient release control type pesticidal compositions prepared above.

Test Category 2 (Evaluation of agricultural chemical active ingredient release control type agricultural chemical composition)
The agrochemical active ingredient controlled release agricultural chemical composition prepared in Test Category 1 was evaluated for productivity, shape retention, abrasion resistance and sustained release as follows. The results are summarized in Table 1.

-Evaluation of productivity In Test Category 1, the following criteria were evaluated from the amount of current of the motor of the basket type granulator at the time of extrusion molding, the presence or absence of squeaking noise, and the screenability of the kneaded product.
A: The current amount of the motor is stable at an average of 1.6 to 1.7 amperes, there is no squeaking noise at the time of extrusion, and the kneaded material has passed 95% or more. O: The average amount of the motor current is 1.7. Although stable at ˜2.0 amperes, there was a slight squeaking noise during extrusion, and the passing amount of the kneaded product was 85% or more and less than 95% △: The motor current amount averaged from 2.0 to 2 .4 ampere, the squeaking noise during extrusion was considerably loud, and the amount of kneaded material passed was less than 85%. X: The motor current amount exceeded 2.4 amperes on average, resulting in continuous operation. Could not be granulated, and the amount of kneaded material passed was less than 85%

-Evaluation of shape retention The external appearance of the extruded product extruded into noodles from an extruder was evaluated according to the following criteria.
◎: Uniform cylindrical shape, smooth surface, good shape retention ○: Although the cylinder is non-uniform, the overall shape is cylindrical, and shape retention is relatively good △: The cylinder is non-uniform, Many surfaces are rough and do not become cylindrical, and shape retention is poor. X: Not cylindrical, shape retention is poor.

・ Evaluation of abrasion resistance Measure the dry mass of dust generated during drying, and use a low-tap sieving machine (type A manufactured by CMTT) to dry the dried pesticides into the desired pesticide granules and crushed materials. Using 156 taps / minute, 290 r. p. The sieving was carried out for 5 minutes under the conditions of m, and the dry masses of the sieving were measured. From these measured values, the crushing rate was calculated by the following formula 1, and the following criteria were used to evaluate the calculated crushing rate.
◎: Crushing rate is less than 3% ○: Crushing rate is 3% or more and less than 5% △: Crushing rate is 5% or more and less than 10% ×: Crushing rate is 10% or more

In Equation 1,
D: Dry mass of dust Tp: Dry mass of target agrochemical granule Tr: Dry mass of crushed material

-Evaluation of sustained release property 800 ml of tap water (water depth: 4 cm) was put in a cylindrical container with a capacity of 1000 ml, and the agrochemical granules produced in Test Category 1 were uniformly sprayed there and allowed to stand at 20 ° C. The amount applied was 90% of the water-saturated solubility of the pesticidal active ingredient. Water was collected from a depth of 2 cm at the center of the container at regular intervals, the concentration of the pesticidal active ingredient in the collected water was measured by liquid chromatography, and the amount of the pesticidal active ingredient eluted in 800 ml of tap water was calculated. Calculate the elution rate with the concentration when the pesticide active ingredient in the test pesticide granules completely eluted as 100% elution rate, and calculate the number of days required for elution of the pesticide active ingredient over 50%. Evaluated by criteria.
◎: 10 days or more ○: 5 days or more and less than 10 days △: 2 days or more and less than 5 days ×: Less than 2 days

In Table 1,
A-1 to A-12, a-1 and a-2: Organophosphates described in Table 2 B-1: Fluorine resin emulsion (trade name Unidyne TG-470B, manufactured by Daikin Industries, Ltd., solid content 30 %)
B-2: Fluorine resin emulsion (trade name Asahi Guard AG-8095 manufactured by Asahi Glass Co., Ltd., solid content 30%)
B-3: Vinyl acetate emulsion (trade name Mobile DC02 manufactured by Hoechst Chemical Co., Ltd., solid content 60%)
B-4: Acrylic resin emulsion (trade name Yodosol AD57 manufactured by NSC Japan, solid content 30%)
B-5: Carnauba wax emulsion (trade name Emaster 0164 manufactured by Nippon Seiwa Co., Ltd., solid content 30%)
C-1: Oxamyl (water solubility 28, log P = −0.4)
C-2: Metalaxyl (water solubility 0.71, log P = 1.75)
C-3: Nicosulfuron (water solubility 1.22, log P = 0.22)
C-4: Dimetachlor (water solubility 0.2, log P = 2.62)
C-5: Imidacloprid (water solubility 0.05, log P = 0.57)
D-1: Mixture of bentonite (trade name Kunigel V1 manufactured by Kunimine Kogyo Co., Ltd.) / Clay (trade name Showa fine powder clay manufactured by Showa Mining Co., Ltd.) = 20/80 (mass ratio) D-2: clay (manufactured by Showa Mining Co., Ltd.) Product name Showa fine clay)
D-3: Lactose E-1: Gum arabic E-2: Dioctylsulfosuccinate sodium salt

In Table 2,
R ¹ , q, M, r: symbols in chemical formula 1 D / M: ratio of diester / monoester (molar ratio)

Claims (3)

In% by mass of the solid content basis, agrochemical active ingredient release control agents described below, has a total of 95 to 100 wt% including a pesticidal active ingredient and bulking agents described below, and the pesticide active ingredient release control agent 5-15 wt% A pesticidal active ingredient release control type pesticidal composition comprising 1 to 30 % by mass of the pesticidal active ingredient and 50 to 85% by mass of the extender.
Pesticide active ingredient release controlling agent: composed of the following organic phosphate ester and the following aqueous resin emulsion, and the organic phosphate ester / the aqueous resin emulsion = 93/7 to 60/40 (mass ratio in terms of solid content) Agrochemical active ingredient release control agent contained in a proportion of organic phosphate ester: organophosphate ester represented by the following chemical formula 1

(In chemical formula 1,
R ¹ : Aliphatic hydrocarbon group having 18 to 22 carbon atoms M ⁺ : Potassium ion, sodium ion, diethanolammonium or triethanolammonium q, r: 1 or 2, an integer satisfying q + r = 3)
Aqueous resin emulsion: one or two or more agricultural chemical active ingredients selected from vinyl acetate resin emulsion, acrylic resin emulsion and fluororesin emulsion : common logarithm log P of octanol-water partition coefficient P is -5 to 2 and / or 20 Agrochemical active ingredient having water solubility at 0.1 ° C. of 0.1 to 80 g / 100 ml The agricultural chemical active ingredient release control type agricultural chemical composition according to claim 1 , wherein the aqueous resin emulsion is a fluororesin emulsion . The agricultural chemical active ingredient release control type agricultural chemical composition according to claim 1 or 2 , wherein the extender is an inorganic fine powder .