KR102278422B1 - Pesticide composition comprising nanoscale encapsulation formulation of active ingredient chemicals using multicomponent polymer system - Google Patents

Abstract

The present invention provides an agrochemical composition comprising an active ingredient compound and an encapsulated formulation comprising a specific polymer complex of Polymer 1, Polymer 2 and Polymer 3.
The agrochemical composition comprising a nano-level encapsulation formulation of an active ingredient compound using the multi-component polymer system of the present invention can be usefully used as a technique for efficiently using a minimum amount of active ingredient in the agrochemical industry.

Description

Pesticide composition comprising nanoscale encapsulation formulation of active ingredient chemicals using multicomponent polymer system

The present invention relates to an agrochemical composition comprising a nano-level encapsulated formulation, and more particularly, to an agrochemical composition comprising a nano-level encapsulated formulation of an active ingredient compound using a multicomponent polymer system.

In relation to controlled-release pesticides or sustained-release pesticides, Korean Patent Laid-Open No. 10-2011-0035617 discloses a sustained-release pesticide comprising a carrier composed of a mixture of three types of chitosan having different molecular weights and a pesticide active ingredient adsorbed on the carrier. Korean Patent Laid-Open Publication No. 2003-0064310 discloses a sustained-release biologically active composition containing biologically active substances such as pesticides or fertilizers, coating agents, and release controlling agents on a porous carrier.

However, to date, an encapsulation formulation that efficiently increases the activity of an active ingredient compound has not been developed, and a new formulation designed to sufficiently exhibit the activity of the active ingredient compound with a minimum amount in terms of economic utilization and environmental protection of the active ingredient compound. development is required.

Korean Patent Publication No. 10-2011-0035617 (2011.04.06.) Korean Patent Publication No. 2003-0064310 (July 31, 2003) Korean Patent Publication No. 10-2009-0065616 (June 23, 2009) Korean Patent Registration No. 10-0837558 (2008.06.04.)

Nanomaterials 2016, 6, 26

The inventors of the present invention, while researching a formulation that efficiently increases the activity of the active ingredient compound, when encapsulating the active ingredient compound using a multi-component system of a specific polymer, the active ingredient compound is effective against insects (pests) and pests. It was confirmed that the insecticidal effective concentration was lowered by 10-100 times to reduce the insecticidal amount of the active ingredient compound.

Accordingly, an object of the present invention is to provide an agrochemical composition comprising an active ingredient compound and an encapsulated formulation comprising a specific polymer complex of Polymer 1, Polymer 2 and Polymer 3.

According to one aspect of the present invention, an insecticide, poly(methyl methacrylate-co-methacrylic acid) or poly(methyl methacrylate-co-ethyl acrylate) as polymer 1, polycaprolactone as polymer 2 and polymer As 3, there is provided an agrochemical composition comprising an encapsulated formulation comprising a polymer complex of polyvinyl alcohol.

In one embodiment, the pesticide may be included in an amount of 9 to 14% by weight based on the total weight of the encapsulation formulation.

In one embodiment, the polymer 1 may be included in an amount of 17 to 22% by weight based on the total weight of the encapsulation formulation.

In one embodiment, the polymer 2 may be included in an amount of 28 to 35% by weight based on the total weight of the encapsulation formulation.

In one embodiment, the polymer 3 may be included in an amount of 9 to 14% by weight based on the total weight of the encapsulation formulation.

In one embodiment, the encapsulation formulation comprises (a) an insecticide in an organic solvent, poly(methyl methacrylate-co-methacrylic acid) or poly(methyl methacrylate-co-ethyl acrylate) and polymer 2 as polymer 1 preparing a first dispersion by dispersing polycaprolactone as a solvent, and dispersing polyvinyl alcohol as polymer 3 in water to prepare a second dispersion; (b) preparing a mixed dispersion by mixing the first dispersion with the second dispersion while shear mixing; and (c) evaporating the organic solvent from the mixed dispersion.

According to the present invention, the insecticidal effective concentration of the active ingredient compound against insects (pests) is reduced by 10-100 times by an encapsulation formulation comprising an active ingredient compound and a specific polymer complex of Polymer 1, Polymer 2 and Polymer 3, so that the active ingredient It has been found that the pesticidal requirement of the compound is reduced.

Therefore, the agrochemical composition comprising the nano-level encapsulation formulation of the active ingredient compound using the multi-component polymer system of the present invention can be usefully used as a technique for efficiently using a minimum amount of active ingredient in the agrochemical industry.

1 is a schematic diagram of the encapsulation formulation of the present invention (AI: active ingredient, active ingredient).
2 is a micrograph of a lambda nanosample (PCL:PMMA-PMAA 3:2).

The present invention relates to an insecticide, poly(methyl methacrylate-co-methacrylic acid) or poly(methyl methacrylate-co-ethyl acrylate) as polymer 1, polycaprolactone as polymer 2 and polyvinyl alcohol as polymer 3 It provides an agrochemical composition comprising an encapsulated formulation comprising a polymer composite of

The present invention involves encapsulating an active ingredient (AI) in nano-level form within various types of polymer composites.

The active ingredient compound may be an insecticide or pesticide, for example, deltamethrin, lambda-cyhalothrin, acetamiprid, and their One selected from the group consisting of mixtures, but is not limited thereto.

In one embodiment, the active ingredient compound may be included in an amount of 9 to 14% by weight based on the total weight of the encapsulation formulation.

Polymer 1 is more hydrophilic than Polymer 2, preferably slightly amphiphilic in nature, and less hydrophilic than Polymer 3. The role of polymer 1 is to help encapsulate and solvate the AI-polymer complex through interaction with polymer 3 during the encapsulation process. Polymer 1 is an amphiphilic copolymer comprising more than 1% by weight and less than 50% by weight of a hydrophilic block based on the total weight of polymer 1, for example, poly (lactic-co-glycol) acid [poly(lactic-co-glycolic) acid], poly(methyl methacrylate-co-methacrylic acid), PMMA-PMAA -Ethyl acrylate) [poly(methyl methacrylate-co-ethyl acrylate), PMMA-EA], and one selected from the group consisting of mixtures thereof, but is not limited thereto.

In one embodiment, the polymer 1 may be included in an amount of 17 to 22% by weight based on the total weight of the encapsulation formulation.

The polymer 2 is a material that is hydrophobic and has good affinity for AI. The role of Polymer 2 is to provide a tunable structural support in the polymer composite to control the release behavior of AI. Polymer 2 is an aliphatic, hydrophobic polyester, for example, polycaprolactone, polyglycolic acid, polylactic acid, polyhydroxyalkanoate ( polyhydroxyalkanoate), polyhydroxybutyrate, and one selected from the group consisting of mixtures thereof, but is not limited thereto.

In one embodiment, the polymer 2 may be included in an amount of 28 to 35% by weight based on the total weight of the encapsulation formulation.

Polymer 3 is amphiphilic and has surfactant capabilities. The role of polymer 3 is to stabilize the polymer-A1 complex during the encapsulation process. Polymer 3 is a compound with an HLB value (hydrophilic-lipophilic balance) of 18 or more, for example, one selected from the group consisting of polyvinyl alcohol, polyethylene glycol, and mixtures thereof, but limited thereto doesn't happen

In one embodiment, the polymer 3 may be included in an amount of 9 to 14% by weight based on the total weight of the encapsulation formulation.

In one embodiment, the encapsulation formulation comprises (a) an insecticide in an organic solvent, poly(methyl methacrylate-co-methacrylic acid) or poly(methyl methacrylate-co-ethyl acrylate) and polymer 2 as polymer 1 preparing a first dispersion by dispersing polycaprolactone as a solvent, and dispersing polyvinyl alcohol as polymer 3 in water to prepare a second dispersion; (b) preparing a mixed dispersion by mixing the first dispersion with the second dispersion while shear mixing; and (c) evaporating the organic solvent from the mixed dispersion.

The step (a) is a step of preparing a first dispersion and a second dispersion. The first dispersion is prepared by dispersing the active ingredient compound, polymer 1, and polymer 2 in an organic solvent, and the second dispersion is prepared by dispersing polymer 3 in water.

After the prepared encapsulation formulation is in contact with the target, the release rate of AI is by diffusion through the polymer complex, which is modulated by the molecular weight of Polymer 2. To achieve shorter release times in the application, design rapid release of AI using low molecular weight Polymer 2 (<10 kDa) and, if more sustained release is desired, higher molecular weight Polymer 2 (> 10 kDa) to design a sustained release of AI.

The step (b) is a step of mixing the prepared first dispersion with the prepared second dispersion. At this time, at the time of mixing, the capsule particles contained in the mixed dispersion obtained by mixing while shearing can be adjusted to a nano level.

That is, a high-energy shear mixer (750 W) should be used to obtain the nano-level (1 - 100 nm) size of the AI compound contained in the polymer composite. At this time, the active ingredient compound is nanosized to a size of 1-100 nm and encapsulated in a polymer complex, and the polymer complex itself forms a formulation having a size of about 1-6 μm (see FIG. 2).

By increasing the effective surface area of the AI prepared as described above and thus increasing exposure to the surrounding environment, the concentration of AI required in the final product was reduced to 10 while preserving effectiveness as demonstrated in spray tests using live insect samples. -100 times reduced. This reduction in AI concentration could provide economic benefits to manufacturers and minimize the environmental impact of their products.

Hereinafter, the present invention will be described in more detail through Examples and Test Examples. However, the following examples and test examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1. lambda thyhalosrin Encapsulation of compounds

(1) Lambda thyhalosrin (50 mg/ml), poly(methyl methacrylate-co-methacrylic acid) [molecular weight 34 in dichloromethane (DCM) using a water bath ultrasonicator at 40 ° C. water bath temperature kDa, PMMA-PMAA (MMA:MAA = 1:0.016)] (80 mg/ml) and polycaprolactone [molecular weight 10 kDa, PCL] (160 mg/ml) were completely dispersed.

(2) Polyvinyl alcohol (2.5 mg/ml) was dispersed in water.

(3) 150 mL of a dispersion of lambdathyhalosrin / poly(methyl methacrylate-co-methacrylic acid) / polycaprolactone in DCM is added to 3,000 mL of aqueous polyvinyl alcohol solution at a rate of 10 ml/min at 30 rpm at 9000 rpm Mix (about 3 L volume) while mixing with a shear mixer (Silverson L5M-A) for minutes.

(4) Evaporate DCM at room temperature with stirring at 550 rpm for at least 72 hours. Encapsulation occurs during the evaporation of DCM, in which the hydrophobic AI, polymer 2 and the hydrophobic component of polymer 1 form a micellar-like structure, which is stabilized by the hydrophilic component of polymer 3 and polymer 1. The size of the prepared polymer composite was about 1 to 6 μm (FIG. 2).

(5) A piperonyl butoxide (PBO)-based emulsion was dispersed as follows.

(5.1) PBO was dispersed in dibutyl hydroxyl toluene (22.5 mg/ml).

(5.2) The dispersion obtained in (5.1) and ethoxylated Castor oil were mixed in a weight ratio of 4.72:1.

(5.3) The dispersion obtained in (5.2) and silicone oil (Silica filled, silicone oil) were mixed in a weight ratio of 571.67:1.

(5.4) 38.61 mL of water was added dropwise to the dispersion obtained in (5.3) while stirring.

(6) the dispersion obtained in (4), the dispersion obtained in (5), Silwet408 [Polyalkyleneoxide modified heptamethyltrisiloxane] and EP-1A [Ethyl acrylate-methacrylic acid copolymer ( Ethyl acrylate-methacrylic acid copolymer)] was mixed in a weight ratio of 20:3:0.025:1.

(7) The dispersion obtained in (6) was mixed with triethanolamine in a weight ratio of 24:1.

(8) The final composition of the nano-encapsulated emulsion is as follows: 79.90% by weight of nano-encapsulated AI, 0.10% by weight of Silwet408, 4.00% by weight of EP-1A, 4.00% by weight of triethanolamine, 5.40% by weight of piperonyl butoxide , 1.20% by weight of ethoxylated castor oil, 0.24% by weight of dibutyl hydroxy toluene, 0.012% by weight of silicone oil, 5.148% by weight of water.

Example 2. Deltamethrin Encapsulation of compounds

A nanoemulsion was prepared in the same manner as in Example 1 using deltamethrin instead of lambda thyhalosrin.

Test Example 1-1. for cockroaches lambda thyhalosrin of nano-emulsions. Efficacy test (1st)

(1) Test date: May 10, 2017

(2) Sample: A sample (A, B, C) diluted with lambda thyhalosrin nanoemulsion prepared in Example 1 and a sample (D) diluted with lambdakill MC, a commercially available insecticide, were prepared according to the composition of Table 1 below. diluted.

sample stock solution concentration
(weight%) undiluted solution
(mL) final volume
(mL) dilution multiple Final lambdathyhalosrin concentration (wt%) D Ratio of dilution to sample* A 0.21 0.3 100 333 0.00063 20 B 0.21 0.6 100 167 0.00126 10 C 0.21 1.2 100 83 0.0025 5 D 2.5 ** 0.5 100 200 0.0125 One *: Lambda thyhalosrin concentration of D sample / Lambda thyhalosrin concentration of each sample
**: lambdakill MC 2.5%, cockroach direct spray 200 times diluted 12.0 mL/m ²

(3) Test method

① Each of the above samples was placed in a 250 mL spray container, and about 1.4 mL of the sample was sprayed during one spray.

② Put 20 cockroaches in the exposure field, spray the sample 8 times (about 11 mL) with the spray container, leave it for about 10 minutes, and then transfer it to a paper box and supply water for observation. [The above test method is carried out in accordance with the 『Guidelines for Efficacy Test Methods for Infectious Disease Prevention Insecticides, etc.』

(4) test results

elapsed time
(time) Number of lethal populations (mari) A B C D 0.5 19 18 20 20 2 20 20 20 20 24 (1 day) 15 19 20 20 48 (2 days) 16 19 19 20 120 (5 days) 12 18 19 20

As shown in Table 2, the efficacy of the product was confirmed through a comparative test for each concentration of lambda thyhalosrin nanoemulsion (the higher the concentration, the higher the effect), and compared with the lambdakill MC, 5 times and 10 times lower It was confirmed that a similar insecticidal effect was exhibited even at the concentration.

Test Example 1-2. for cockroaches lambda thyhalosrin of nano-emulsions. Efficacy Test (Secondary)

(1) Test date: June 29, 2017

(2) Sample: Each of the following samples was diluted with the composition shown in Table 3 below.

A. Lambda thyhalosrin 0.2% (Lambdakill MC diluted 2.5%)

B. Lambda thyhalosrin 0.2% (PCL:PMMA-EA = 3:2, weight ratio)

C. Lambda thyhalosrin 0.2% (PCL:PMMA-PMAA = 1:4, weight ratio)

D. Lambda thyhalosrin 0.2% (PCL:PMMA-PMAA = 3:2, weight ratio)

E. Lambdakill MC 2.5% (200-fold dilution of direct cockroach spray 12.0 mL/m ² )

sample stock solution concentration
(weight%) undiluted solution
(mL) final volume
(mL) dilution multiple Final lambdathyhalosrin concentration (wt%) E Ratio of dilution to sample* A 0.2 0.625 100 160 0.00125 10 B 0.2 0.625 100 160 0.00125 10 C 0.2 0.625 100 160 0.00125 10 D 0.2 0.625 100 160 0.00125 10 E 2.5 0.5 100 200 0.0125 One *: Lambda thyhalosrin concentration of E sample / Lambda thyhalosrin concentration of each sample

(3) Test method

① Each of the above samples was placed in a 250 mL spray container, and about 1.4 mL of the sample was sprayed during one spray.

② Put 25 cockroaches in the exposure field, spray the sample 8 times (about 11 mL) with the spray container, leave it for about 10 minutes, and then transfer it to a plastic container and supply water for observation. [The above test method is carried out in accordance with the 『Guidelines for Efficacy Test Methods for Infectious Disease Prevention Insecticides, etc.』

(4) test results

elapsed time
(time) Number of lethal populations (mari) A B C D E 0.5 24 25 25 25 25 4 23 25 25 25 25 24 (1 day) 14 25 25 25 25 48 (2 days) 13 25 25 25 25

As shown in Table 4, it was confirmed that the efficacy of the B(EA18), C(AA24), and D(PCL18, AA12) samples received secondarily was superior to that of the existing samples.

Test Example 1-3. for cockroaches lambda thyhalosrin of nano-emulsions. Efficacy Test (3rd)

(1) Test date: June 30, 2017

(2) Samples: Each of the following samples was diluted with the composition shown in Table 5 below.

A. Lambda thyhalosrin 0.2% (Lambdakill MC diluted 2.5%)

B. Lambda thyhalosrin 0.2% (PCL:PMMA-EA 3:2, weight ratio)

C. Lambda thyhalosrin 0.2% (PCL:PMMA-PMAA 1:4, weight ratio)

D. Lambda thyhalosrin 0.2% (PCL:PMMA-PMAA 3:2, weight ratio)

sample stock solution concentration
(weight%) undiluted solution
(mL) final volume
(mL) dilution multiple Final lambdathyhalosrin concentration (wt%) remark A 0.2 0.625 100 160 0.00125 equal dilution ratio B 0.2 0.625 100 160 0.00125 equal dilution ratio C 0.2 0.625 100 160 0.00125 equal dilution ratio D 0.2 0.625 100 160 0.00125 equal dilution ratio

(3) Test method

① Each of the above samples was placed in a 250 mL spray container, and about 1.4 mL of the sample was sprayed during one spray.

② Put 25 cockroaches in the exposure field, spray the sample 4 times (about 6 mL) with the spray container, leave it for about 10 minutes, and then transfer it to a plastic container and supply water for observation. [The above test method is carried out in accordance with the 『Guidelines for Efficacy Test Methods for Infectious Disease Prevention Insecticides, etc.』

(4) test results

elapsed time
(time) Number of lethal populations (mari) A B C D 6 13 25 25 25 24 (1 day) 11 25 25 25

As shown in Table 6, the injection amount was reduced by 1/2 compared to Test Example 1-2, but showed similar effects in B (EA18), C (AA24), and D (PCL18, AA12).

Test Example 2. For cockroaches Deltamethrin of nano-emulsions. potency test

(1) Test date: July 05, 2017

(2) Sample: Each of the following samples was diluted with the composition shown in Table 7 below.

A. Deltamethrin 0.2% (Diluted Long Down Plus)

B. Deltamethrin 0.2% (PCL:PMMA-PMAA 1:4)

C. Deltamethrin 0.2% (PCL:PMMA-PMAA 3:2)

D. Long Down Plus (Deltamethrin 2.5%) [Control]

sample stock solution concentration
(weight%) undiluted solution
(mL) final volume
(mL) dilution multiple Final deltamethrin concentration (wt%) D Ratio of dilution to sample* A 0.2 0.625 100 160 0.00125 10 B 0.2 0.625 100 160 0.00125 10 C 0.2 0.625 100 160 0.00125 10 D 2.5 ** 0.5 100 200 0.0125 One *: Deltamethrin concentration of D sample / Deltamethrin concentration of each sample
**: Long Down Plus 2.5%, direct cockroach spray 200 times diluted

(3) Test method

① Each of the above samples was placed in a 250 mL spray container, and about 1.4 mL of the sample was sprayed during one spray.

② Put 25 cockroaches in the exposure field, spray the sample 4 times (about 6 mL) with the spray container, leave it for about 10 minutes, and then transfer it to a plastic container and supply water for observation. [The above test method is carried out in accordance with the 『Guidelines for Efficacy Test Methods for Infectious Disease Prevention Insecticides, etc.』

(4) test results

elapsed time
(time) lethal population (mari) A B C D 1.5 25 25 25 25 5 25 25 25 25 24 (1 day) 25 18 25 25 48 (2 days) 25 22 25 25

As shown in Table 8, although samples A, B, and C were diluted 1/10 than the control group D (Long Down Plus), samples A and C showed the same effect as D, and B had a similar effect to D. , it was confirmed that the effect increase was excellent by the nanoemulsion formulation.

Claims (6)

Polymer composite of pesticide with poly(methyl methacrylate-co-methacrylic acid) or poly(methyl methacrylate-co-ethyl acrylate) as polymer 1, polycaprolactone as polymer 2 and polyvinyl alcohol as polymer 3 Agrochemical composition comprising an encapsulated formulation comprising a. The agrochemical composition according to claim 1, wherein the pesticide is included in an amount of 9 to 14% by weight based on the total weight of the encapsulated formulation. The agrochemical composition according to claim 1, wherein the polymer 1 is contained in an amount of 17 to 22% by weight based on the total weight of the encapsulation formulation. The agrochemical composition according to claim 1, wherein the polymer 2 is contained in an amount of 28 to 35 wt% based on the total weight of the encapsulation formulation. The agrochemical composition according to claim 1, wherein the polymer 3 is contained in an amount of 9 to 14% by weight based on the total weight of the encapsulation formulation. The method of claim 1 , wherein the encapsulated formulation is
(a) Dispersing a pesticide, poly(methyl methacrylate-co-methacrylic acid) or poly(methyl methacrylate-co-ethyl acrylate) as polymer 1 and polycaprolactone as polymer 2 in an organic solvent to first preparing a dispersion and dispersing polyvinyl alcohol as polymer 3 in water to prepare a second dispersion;
(b) preparing a mixed dispersion by mixing the first dispersion with the second dispersion while shear mixing; and
(c) evaporating the organic solvent from the mixed dispersion.
Agrochemical composition, characterized in that it is prepared by a manufacturing method comprising a.

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