KR20010001860A - Pin-Shaped Pesticide Formulation - Google Patents

Abstract

The present invention relates to a pesticide preparation in which a pesticide is contained in a biodegradable polymer so that the pesticide component is released in an effective amount for a long time, and the composition comprises 10 to 90% by weight of biodegradable resin, 90 to 10% by weight of starch or calcium carbonate and pesticide. This compounding is characterized in that it is molded in the form of a pin (pin), the pesticide formulation is slowly disintegrating the resin in a single treatment and at the same time the pesticide is slowly eluted to maintain the effect of the pesticide, home, small garden Pesticide poisoning risk to workers due to scattering of pesticides, which is pointed out as a problem of existing diluent pesticides used for pest control of various flowers and crops grown in facility houses, etc. It is possible to solve the environmental pollution problem caused by biodegradable resin used in pesticide manufacturing. Fully degraded, it can lead to the development of environmentally friendly pesticides.

Description

Pin-Shaped Pesticide Formulation

The present invention relates to a pin-type pesticide preparation that allows the pesticide component to be released in the soil in a long-term effective amount.

Conventionally, pesticides used in home and facility horticultural pest control have to be sprayed in excessive amounts several times to see the pesticide effect. However, spraying excessive amounts of pesticides may adversely affect other crops, may cause pesticide poisoning to the human body, and may cause environmental pollution and spraying pesticides, requiring labor and excessive labor. There was a problem.

In an attempt to solve this problem, Japanese Patent Application Laid-open No. Hei 6-116103 proposes to inject a biodegradable resin into a plate and then dissolve the pesticide in a solvent and then introduce it into the resin plate. A method of copolymerizing agrochemicals and polyesters with an acid, dissolving in chloroform, adsorbing to granular zeolite, heating and evaporating chloroform is shown. However, these conventional pesticides are pointed out as a problem in that the manufacturing method is complicated and the manufacturing environment is harmful and the manufacturing cost is high due to the use of acid and solvent in the manufacturing.

In order to solve this problem, the present inventors have suggested that in the Republic of Korea Patent Publication No. 96-57351, a pesticide is physically compounded into a biodegradable polymer and manufactured in the form of a plate with a melt extruder. This is mainly agricultural pesticides, and because it is manufactured in a string form, it is difficult to use for home and gardening.

Therefore, the present invention can see the long-term pesticide effect in a single treatment, the pesticide is released by the amount necessary to control pests to reduce the damage caused by the abuse of pesticides, suitable for use in pots, etc., economical easy to manufacture It is a task to provide new pesticide preparation.

In order to solve the above problems, the present inventors compounded biodegradable resins and pesticides, which can be completely decomposed in a natural environment, and manufactured in the form of pins. After application, the biodegradable resin was slowly decomposed and at the same time, the pesticide was slowly released in an effective amount necessary for controlling pests, so that it was possible to achieve a continuous pesticide administration effect with a single treatment.

1, 2, 3 and 4 illustrate the preferred form of the pin-type pesticide preparation according to the present invention.

Hereinafter, the present invention will be described.

The present invention provides a pin-shaped pesticide formulation compounded in the form of a pin by compounding the following compositions:

(a) biodegradable resin, 10 to 90% by weight,

(b) starch or calcium carbonate, 90 to 10% by weight and

(c) an effective amount of pesticide.

Hereinafter, the preferred embodiment of the present invention will be described in more detail.

Examples of preferred biodegradable resins for use in the present invention include dicarboxylic acids of the formula (1), Formula 3 having a number average molecular weight of 10,000 to 100,000 and a melting point of 50 to 120 ° C. prepared by polymerizing one or more selected from the group consisting of alkyl esters and anhydrides, and one or more diols of the following general formula (2) as alcohol component monomers Thermoplastic aliphatic polyester.

<Formula 1>

(Wherein R ₁ is a substituted or unsubstituted alkylene group having 0 to 30 carbon atoms)

<Formula 2>

(Wherein R ₂ is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms)

<Formula 3>

Where n is a repeating unit and R ₁ and R ₂ are as defined in Formulas 1 and 2

If the number-average molecular weight of the biodegradable thermoplastic aliphatic polyester is less than 10,000, the decomposition rate is too fast, which is inappropriate to give a continuous release effect and poor molding of the product. If the speed is affected and the melting point is less than 50 ° C., poor work and storage problems occur, and thermoplastic aliphatic polyester having a number average molecular weight of 10,000 to 100,000 and a melting point of 50 to 120 ° C. is preferable.

Although not particularly limited, the acid component monomers constituting the biodegradable aliphatic polyester include dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid, and their At least one selected from the group consisting of dicarboxylic acid alkyl esters such as methyl ester, ethyl ester and propyl ester, or anhydrides of the above dicarboxylic acids is preferred. Among these, particularly preferable acid component monomers are one or more selected from the group consisting of succinic acid, adipic acid, methyl succinate, methyl adipic acid, succinic anhydride, adipic acid anhydride.

Preferred examples of the alcohol component monomer constituting the biodegradable aliphatic polyester are one or more selected from the group consisting of substituted or unsubstituted ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol and octanediol. . In the case of substituted diols, lower alkyl groups and / or hydroxy groups are preferred as substituents. Especially preferred alcohol component monomers are ethylene glycol, 1,4-butanediol or mixtures thereof.

In addition, the biodegradable resin of the present invention may be a polymer produced by introducing polyethyleneglycol, isocyanate, polyfunctional alcohol and / or polyfunctional carboxylic acid having a molecular weight of 100 to 9,000 as a third component, in addition to the above-mentioned monomers, and polybutylene Succinate, polybutylene succinate adipate copolymer, polycaprolactone, polylactide, polyamide copolymer and aromatic / aliphatic copolymer may be used alone or in combination. Suitable resins may be selected to suit the purpose and the object of the present invention is not limited to specific resins.

In the present invention, the pesticide compounded with the biodegradable resin should be considered the following physicochemical properties of the active ingredient of the pesticide.

In terms of physical properties, the properties of the compound of the pesticide active ingredient to be compounded should be in powder form, and in the chemical properties, the melting point of the active ingredient of the pesticide is 70-150 ° C., and the active ingredient is heated by heating at 100-250 ° C. There should be no decomposition.

Examples of pesticides that satisfy these characteristics include acephate, carbofuran, diazinon, acetamiprid, imidacloprid, and propoxur. .

The formulation of the present invention contains starch or calcium carbonate in addition to biodegradable resins and pesticides as essential components. The addition amount of starch or calcium carbonate (b) is from 9: 1 to 1: 9, preferably 6: 4 to 4: 6, in terms of weight ratio (a: b) to biodegradable resin (a).

In this case, when the content of the resin is less than 1, the workability is poor, and when it exceeds 9, there is a problem that the decomposition rate is lowered.

Preferred examples of starch that can be formulated in the formulation include corn, rice, tapioca, potatoes, rye, oats, wheat, high amylose starch with an amylose content of at least 25%, waxy starch and starch with 100% amylose. There is one or a mixture of two or more selected from the group consisting of derivatives.

Examples of starch derivatives include crosslinking of starch substituted with hydroxy ethyl starch, hydroxy propyl starch, acetate starch, oxidized starch, acid treated starch, positive starch, negative starch, compound having a double bond.

In addition, the present composition may be blended with additives which are usually formulated for plastic molding, such as lubricants, plasticizers and the like.

Examples of suitable lubricants for blending into the composition include one selected from the group consisting of aluminum stearate, calcium, magnesium or tin salts, free acids, unsaturated fatty acid amides, waxes and N, N'-ethylene-bisstearamids, or There are two or more mixtures. The content of such lubricants in the present composition is 10 parts by weight or less, preferably 0.2 to 3 parts by weight, most preferably 0.5 parts by weight per 100 parts by weight of starch.

Examples of suitable plasticizers for blending into the composition include one or two selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, low molecular weight polyethylene oxide with a molecular weight of 1,000 or less, glycerin, polyglycerol, sorbitol and mannitol There are mixtures of species or more, of which glycerin or triethylene glycol are particularly preferred. The preferred amount of plasticizer is about 0.1 to 30%, preferably 0.5 to 20% by weight of the composition.

Hereinafter, an example of a method of molding the pin-type pesticide preparation according to the present invention will be described.

First, in consideration of the degradability and physical properties of the biodegradable resin, starch or calcium carbonate, a lubricant and a plasticizer are mixed with the resin to prepare a master chip, and the master chip and the pesticides of the above-described characteristics and the remaining biodegradable resin are single. It can be prepared by compounding with an extruder equipped with a single or twin screw and injection molding into a pin shape. In compounding, the temperature range of the cylinder varies depending on the melting point of the pesticide, but the temperature range of the cylinder portion is preferably 60 to 150 ° C. Pesticides having a melting point of less than 70 ℃, considering the coefficient of friction of the screw, since the actual cylinder temperature is 70 ℃ or more, there is a fear that carbonization and decomposition phenomenon occurs to lose the characteristics as a pesticide. The preferred mixing ratio of resin to pesticide is 50 to 99.9: 50 to 0.1, more preferably 90 to 99: 10 to 1 by weight. When the mixed weight ratio of the resin is less than 50% by weight, compounding is difficult and workability is poor, and when the mixed weight ratio of the pesticide is less than 0.1% by weight, the effect as a pesticide is inferior.

1 to 4 illustrate various forms of pin-type pesticides, ie golf tee, cylindrical and plate shapes, each having a V-shaped cross section. Of course, the present invention is not limited to the form shown is intended to illustrate the invention. Preferred dimensions of the pin are 2 to 5.5 cm in length, 0.3 to 1.5 cm in diameter, 1.5 to 3 mm in thickness, and 0.5 to 1.5 cm in width.

In this way, when the formulation is formed into a pin shape, the pesticide treatment can be completed by holding the formulation by hand and pressing it lightly against the soil.The pesticide is released from the plugged formulation for a long time as needed to control the pest, and is treated once. It will be possible to complete the desired pest control.

Features and other advantages of the invention as described above will become more apparent by the non-limiting examples described below. In the following examples, the molecular weight of the aliphatic polyester was measured by gel chromatography (GPC) using chloroform as a solvent, and the melting point was measured by a differential scanning calorimetry (DSC) at a temperature rising rate of 10 ° C. per minute.

Example 1

The biodegradable aliphatic polyester having a melting point of 115 ° C and a number average molecular weight of 25,000 and starch are mixed at a weight ratio of 6: 3, and then glycerin is added as a plasticizer and calcium stearate is added as a lubricant to prepare a master chip (M / C) and then evenly mixed 1181.52 g of the M / C, 787.68 g of the aliphatic polyester and 30.8 g of imidacloprid, and evenly mix the injection pressure of 30 kg / cm 2 and the injection temperature of 80 ° C., the die ( die) was injected to 100 ℃ to produce a golf tee prototype as shown in Figure 3, the formulation efficiency of this prototype was measured and the results are shown in Table 1 below.

Example 2

The same procedure as in Example 1 was repeated except that M / C with a weight ratio of biodegradable aliphatic polyester to starch was 6: 4. Formulation efficiency of the prototype is shown in Table 1 below.

Example 3

The same procedure as in Example 1 was repeated except that M / C with a 5: 5 weight ratio of biodegradable aliphatic polyester to starch was used. Formulation efficiency of the prototype is shown in Table 1 below.

Example 4

The same procedure as in Example 1 was repeated except that the same amount of calcium carbonate was used instead of starch. Formulation efficiency of the prototype is shown in Table 1 below.

Example 5

The same procedure as in Example 2 was repeated except that the same amount of calcium carbonate was used instead of starch. Formulation efficiency of the prototype is shown in Table 1 below.

Example 6

The same procedure as in Example 3 was repeated except that the same amount of calcium carbonate was used instead of starch. Formulation efficiency of the prototype is shown in Table 1 below.

Formulation Rate Evaluation of Prototype

About 5 g of each of the prototypes of Examples 1 to 6 was ground and crushed with a freeze mill, and then accurately weighed a milled sample corresponding to 0.01 g as an active ingredient of pesticide, and a 125 ml cap-stoppered Erlenmeyer flask. 10 ml of acetonitrile + H ₂ O (1: 1, v / v) mixed solvent containing an internal standard solution (1000 ppm dimethyl phthalate) was added, followed by filtration to filter the high performance liquid chromatograph. HPLC). Formulation efficiency of the prototype was calculated by expressing it as a ratio of the pesticide injection rate at the time of manufacture, and the results are shown in Table 1.

division Formulation efficiency of prototype Insertion value (%) % Of analysis Formulation rate (%) Example 1 1.52 1.52 100.00 Example 2 1.52 1.51 99.32 Example 3 1.52 1.52 100.00 Example 4 1.52 1.50 98.68 Example 5 1.52 1.52 100.00 Example 6 1.52 1.52 100.00

Pesticide Validation Test of Active Pesticides in Prototypes

After placing a certain amount of the prototypes of Examples 1 to 6 in an aluminum wrapping paper and sealing the product, the contents of the pesticide active ingredient were analyzed in the same manner as in the formulation efficiency analysis method over time, while keeping the temperature in a constant temperature at 54 ° C. The decomposition rate was calculated. Calculation results are shown in Table 2 below.

division Degradation rate of pesticide active ingredient over time (%) 2 weeks after treatment 4 weeks after treatment 6 weeks after treatment Example 1 0 0.1 0.2 Example 2 0 0.1 0.2 Example 3 0 0.2 0.3 Example 4 0 0.1 0.2 Example 5 0 0 0.1 Example 6 0 0 0.1

Degradation test of soil in prototype

After treating the prototypes of Examples 1 to 4 in a rosette (1/5000) jar, the samples were taken every 1 month, washed with water, dried, and then dried. The degree of decomposition was investigated. At this time, the water during the experiment period was sufficiently replenished two to three times a week. The analysis results are shown in Table 3.

division % Degradation of soil in prototype 1 month later 2 months later 3 months later 4 months later 5 months later Example 1 4.0 8.7 18.5 39.4 68.6 Example 2 - - - - - Example 3 - - - - - Example 4 3.3 8.5 12.2 19.4 39.1 Example 5 - - - - - Example 6 - - - -. -

Dissolution of Pesticides in Water

100 ml of distilled water was added to a 125 ml test tube, and each of the prototypes of Examples 1 to 6 (about 1.6 to 1.8 g) was treated, and the active ingredient of the pesticide eluted in water over time was analyzed by HPLC. Replenish with fresh distilled water again. The analysis results are shown in Table 4 below.

division Dissolution rate of pesticide active ingredient in water (%) in prototype 7 days later 14 days later 21 days later 35 days later 70 days later Example 1 12.4 16.8 20.1 24.8 36.8 Example 2 13.5 18.1 21.8 27.3 41.0 Example 3 12.7 18.2 22.7 29.2 44.4 Example 4 13.6 18.0 21.2 26.1 36.8 Example 5 14.4 18.9 22.3 27.5 39.1 Example 6 12.9 17.3 20.7 25.4 37.8

Drug test of prototype

The prototypes of Examples 1 to 6 were treated to facility house packaging with roses as the test variety. After treatment, aphids were tested as pests for each day. Test subjects and treatment conditions are as follows, and the control effects are shown in Table 5 below.

-Species varieties: roses (saffia)

-Testimonials: Brier aphid (Sitobion ibarae)

-Investigation period: Survey of live animals after 15, 34, 70, 110, 145 days of drug treatment

division Aphid control effect by days after treatment (%) Weak (0-5) 15th 34 days 70 days 110 days 145 days Example 1 87.9 96.8 99.0 100.0 98.6 0 Example 2 85.3 97.0 99.5 100.0 99.0 0 Example 3 88.0 97.6 99.5 100.0 99.3 0 Example 4 85.6 95.3 97.6 99.3 98.5 0 Example 5 84.5 95.0 96.8 98.9 99.0 0 Example 6 85.7 94.8 96.8 99.0 98.6 0 contrast 99.7 99.3 99.6 100.0 99.6 0 Untreated (mari / 10 leaves) 99.3 200.4 110.6 96.5 78.6 -

* Contrast: 10 times sprayed acitra hydrant

As can be seen from the above embodiment, the preparation of the prototype in the form of a pin by mixing the pesticide with a certain component ratio of the resin of the present invention and starch or calcium carbonate, the formulation efficiency of the prototype, time-lapse stability of the active ingredient of the pesticide in the prototype, prototype As a result of testing the degradability in soil, the water dissolution of the active ingredient of the pesticide, the physical properties and the efficacy of the prototype, the formulation efficiency of the prototype was over 99%, and the biodegradable resin and the pesticide were well mixed. The degradation rate of the active ingredient over time at 54 ° C. was less than 0.5%, resulting in a stable pesticide active ingredient in the prototype. On the other hand, the degradation rate of the prototype in soil was minimal until 3 months of treatment, but after 4 months of treatment, the decomposition proceeded rapidly. As a result of investigating the control effect on the aphids of the roses of Example 1 to 6, the control effect of 90% or more was observed from 34 days after treatment to 145 days.

As described above, the pin-type pesticide preparation of the present invention is easy to handle, and the biodegradable resin is slowly decomposed with only one spray, and the pesticide is gradually eluted, so that the pesticide effect is continuously maintained in homes, small gardens, and facility houses. It can solve the trouble of spraying pesticide several times, which is pointed out as a problem of existing diluent pesticide, which is used for pest control of various flowers and crops in cultivation, risks to workers when spraying pesticides, and environmental pollution due to excessive pesticide spraying. Biodegradable resins used to make pesticides are completely decomposed in the soil, leading to the development of environmentally friendly pesticides.

Claims (7)

A pin-type pesticide formulation, characterized in that the composition containing the following components are compounded and shaped into pins: (a) 10 to 90% by weight of a biodegradable resin, (b) 90 to 10% by weight of starch or calcium carbonate and (c) an effective amount of pesticide. The biodegradable resin (a) according to claim 1, wherein the biodegradable resin (a) is an acid component monomer, Formula (3) having a number average molecular weight of 10,000 to 100,000, and a melting point of 50 to 120 ° C, prepared by polymerizing one or more selected from the group consisting of alkyl esters and anhydrides, and one or more diols of the following general formula (2) as alcohol component monomers It is a thermoplastic aliphatic polyester of the pin type pesticide preparation. <Formula 1> (Wherein R ₁ is a substituted or unsubstituted alkylene group having 0 to 30 carbon atoms) <Formula 2> (Wherein R ₂ is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms) <Formula 3> Where n is a repeating unit and R ₁ and R ₂ are as defined in Formulas 1 and 2 The method of claim 2, wherein the biodegradable resin is prepared by introducing a polyethylene glycol, an isocyanate, a polyfunctional alcohol, a polyfunctional carboxylic acid or a mixture thereof having a molecular weight of 100 to 9,000 as a third component in addition to the monomers of the formulas (1) and (2). Pin-type pesticide formulation, characterized in that one. The pin type pesticide preparation according to claim 1, wherein the pesticide is one or a mixture of two or more selected from the group consisting of acetate, carbofuran, diazinon, acetamiprid, imidacloprid, and propoxy. The pin type pesticide preparation according to claim 1, wherein the mixing ratio (a: c) of the biodegradable resin (a) to the pesticide (c) is 50:50 to 99.9: 0.1 by weight. 6. The pin type pesticide preparation according to claim 5, wherein the pesticide has a melting point of 70 to 150 deg. C and no decomposition of the active ingredient at 100 to 250 deg. In the preparation of the pin-type pesticide preparation according to claim 1 to 6, by using a melt injection molding machine for molding, the temperature range of the cylinder portion during the compounding of the aliphatic polyester resin and the pesticide is controlled to 60 to 250 ℃ Method for producing a pin-type pesticide preparation.