KR100643445B1 - Pin-Shaped Pesticide Formulation - Google Patents

Abstract

The present invention relates to a pesticide preparation in which the pesticide is contained in a biodegradable polymer so that the pesticide component is released in an effective amount for a long time. In particular, the biodegradable resin 10 to 90% by weight, starch or calcium carbonate 90 to 10% by weight and vapor pressure of 1m A composition containing a pesticide having a solubility in water of less than 20 ° C. and having a solubility in water of 30 mg / L (20 ° C.) or more is compounded and molded into a pin shape. It relates to a pin-type pesticide formulation that satisfies the characteristics of 300㎏ / ㎠, impact strength 1.0㎏ / ㎠ or more, specific gravity 1.0 or more, this pesticide formulation is the effect of pesticides by slowly dissolving the resin and at the same time eluting the pesticide slowly Of pesticides during spraying, which is pointed out as a problem of conventional diluent pesticides used for pest control of various flowers and crops grown in homes, small gardens and facility houses. It can solve the danger of pesticide poisoning to workers by acid, the trouble of spraying pesticide several times and the environmental pollution caused by excessive pesticide spraying, and the biodegradable resin used in the manufacture of pesticide is completely decomposed in the soil. Can lead to development.

Description

Pin-Shaped Pesticide Formulation             

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

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. Also, after application, the biodegradable resin was gradually degraded and at the same time, the pesticide was slowly released to the effective amount necessary for controlling pests, and it was found that it was possible to achieve a sustained pesticide administration effect by a single treatment.

Hereinafter, the present invention will be described.

According to the present invention, a biodegradable resin (a), starch or calcium carbonate (b) and an effective amount of pesticide (c) are contained, and the mixing ratio of the biodegradable resin (a) and starch or calcium carbonate (b) is 10 to 90% by weight of the resin (a), 90 to 10% by weight of starch or calcium carbonate (b), the pesticide has a vapor pressure of 1 mPa (20 ℃) or less and solubility in water of 30 mg / l (20 ℃) or more Pin type pesticides are provided.

In addition, the present invention provides a pin-type pesticide formulation that satisfies the characteristics of the flexural strength 150 ~ 300kg / ㎠, impact strength 1.0kg / ㎠ or more, specific gravity 1.0 or more.

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

알킬 에스테르 및 무수물로 이루어진 군에서 선택되는 1종 이상과, 알코올성분 단량체로서 하기 화학식 2의 디올 1종 이상을 중합하는 것에 의해 제조되는 수평균분자량 10,000∼100,000, 융점 50∼120℃인 화학식 3의 열가소성 지방족 폴리에스테르이다.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 may occur. Thus, 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. It is necessary to select appropriate resins to meet the purpose of the present invention also does not limit the specific resin.

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.

In addition, the vapor pressure should be less than 1m㎩ (20 ℃) to prevent worker safety and loss of volatilization of active ingredient during product manufacturing, and the solubility of water of active ingredient in pesticide is more than 30mg / ℓ (20 ℃) Should be Pesticide ingredients must have the above properties to be used in the manufacture of biodegradable resins and pesticides.

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 addition, preferred physical properties are flexural strength of 150 to 300kg / ㎠, impact strength of 1.0kg / ㎠ or more, specific gravity 1.0 or more.

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 pulverized 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 Efficiency (%) 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. It was replenished with fresh distilled water again. The analysis results are shown in Table 4 below.

division Dissolution rate of pesticide active ingredient in water (%) 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

Physical property test of prototype

Flexural strength, flexural modulus, impact strength and specific gravity of the prototypes of Examples 1 to 6 were measured using a universal testing machine (UTM), and the measurement results are shown in Table 6 below.

division Physical characteristics of the prototype Tensile Strength (㎏ / ㎠) % Elongation Flexural Strength (㎏ / ㎠) Flexural Modulus (㎏ / ㎠) Impact Strength (㎏ / ㎠) importance Example 1 148 18 222 4407 2.6 1.24 Example 2 124 60 206 5136 1.7 1.25 Example 3 106 20 183 6208 1.3 1.28 Example 4 150 18 256 4576 3.2 1.40 Example 5 144 5 250 5289 3.2 1.51 Example 6 107 3 217 6432 2.6 1.60

As can be seen from the above-described 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 production efficiency of the prototype, time-lapse stability of the active ingredient of the pesticide in the prototype, As a result of testing the degradability in the soil of the prototype, 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 pesticide were well mixed. Degradation rate of the pesticide active ingredient was degraded less than 0.5% after 6 weeks at 54 ℃, so the pesticide active ingredient was stable 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 Example 1 to 6 for the rose aphid, more than 90% control effect 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 the existing diluent pesticide, which is used for pest control of various flowers and crops in cultivation; Biodegradable resins used to make pesticides are completely decomposed in the soil, leading to the development of environmentally friendly pesticides.                     

Claims (2)

Biodegradable resin, starch or calcium carbonate and an effective amount of pesticide, the weight ratio of the biodegradable resin and starch or calcium carbonate is 10 to 90% by weight of the biodegradable resin, 90 to 10% by weight starch or calcium carbonate, The mixing ratio of the resin to the pesticide is 50% by weight to 99.9: 50 to 0.1, the pesticide is characterized in that the pesticide is a pesticide with a vapor pressure of 1 mPa (20 ℃) or less and water solubility of 30 mg / l (20 ℃) or more. Pesticides. The pin type pesticide preparation according to claim 1, wherein the formulation satisfies flexural strength of 150 to 300 kg / cm 2, impact strength of 1.0 kg / cm 2 or more, and specific gravity of 1.0 or more.

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