TWI343239B - - Google Patents

Description

1343239 IX. Description of the Invention: [Technical Field] The present invention relates to an insect growth control pesticide preparation which can obtain long-term storage stability at a normal temperature and a good emulsified state by inhibiting moisture absorption, and enhances insects. The basic activity of the growth control (hereinafter referred to as IGR) agent enhances the effect on the IGR-resistant drug-resistant pest. [Prior Art] A formulation which has been extensively studied for adding animal and vegetable oils and/or mineral oils to a pesticide preparation to enhance insecticidal and herbicidal effects. For the effect enhancer of the drug-resistant pest, it is known to be brewed by the common name ringworm (chemical name: N·-t-butyl-N'-(3,5-dimethylbenzhydryl)_5· A pesticide preparation containing a methyl _6_ (color carbonyl ruthenium) as an active ingredient (Japanese Laid-Open Patent Publication No. 2003-63908; Patent Document 1) and an agent other than a worm-inducing cockroach as an active ingredient (Special Open 2003- [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-63908 (Patent Documents 1 to 1 and Example 1 and Example 11) [Patent Document 2] JP-A-2003-63901 ( [Table 12] [Invention] However, the present inventors have found that the emulsions of Patent Document 专利 and Patent Document 2 have crystal precipitation during long-term storage at room temperature (for example, storage for 3 years), and their preservation stability is problematic. Also, its active ingredient, cyclosporin, is highly hydrophobic and can only dissolve about 1.12 ppm in water, and is insoluble in solvents such as xylene, which are often used in emulsions. In order to avoid the risk of crystal precipitation, it is necessary to use an aprotic polar solvent. And 100690.doc 1343239 It is not easy to make a stable emulsion. When an aprotic polar solvent is used for the circumstance, a polyethylene container which is generally recommended for use in an aprotic polar solvent is found to be leaky or the like, and the present inventors have found that the above problems have been solved. 'As an active ingredient of the pesticide, the active ingredient of the IGR-based pesticide is 丨, and the specific ratio of 1,3-dimethyl-2-imidazolidinone is 2.5 to 4, which can be used for long-term storage stability at room temperature and good. The present invention is completed in an emulsified state and a pesticide emulsion which exerts a good effect on a drug-resistant pest. That is, the present invention relates to (1) a pesticide emulsion comprising an insect growth control (IGR)-based pesticide active ingredient and , a 3-hydroxy-2-imidazolidinone having a weight ratio of 1:2 5 to 1:4; (2) A pesticide emulsion according to the above item (1), which further comprises an emulsifying and dispersing surfactant, an imidazoline The surfactant and the castor oil; (3) The pesticide emulsion according to the above item (2), which comprises an active ingredient of the IGR-based pesticide of 1.25 to 12% by weight; and the ι,3-dimethyl-2-imidazolidinone is 3.125. ~48 weight / 〇, milk The dispersing surfactant is 4,5~15.5 wt〇/〇; the imidazoline surfactant is 2~8 wt%; and the hemp oil is 3〇~8〇% by weight; (4) as in the above item (2) or (3) A pesticide emulsion, wherein the surfactant for emulsification and dispersion is a nonionic surfactant; (5) The agricultural emulsion according to any one of the items (1) to (4), which is used for insect growth control (6) A pesticide emulsion according to any one of the items (1), wherein the active ingredient of the IGr-based pesticide is a ringworm; 100690.doc 0 1343239 (7) as described above (1) The agricultural chemical emulsion according to any one of (6), which is filled in a multi-layer nylon bottle having an outer layer composed of high-density polyethylene containing calcium carbonate and an inner layer composed of nylon; A container filled with the agricultural chemical emulsion according to any one of the above items (1) to (6); wherein the container is a multi-layer nylon bottle having calcium carbonate containing the same; The high-density polyethylene constitutes an outer layer and an inner layer composed of nylon. [Embodiment] Hereinafter, the present invention will be described in detail. Although the components of the agricultural chemical preparation (agrochemical emulsion) of the present invention are described, the present invention is not limited to these. The agricultural chemical emulsion of the present invention comprises an IGR-based pesticide active ingredient and hydrazine, 3-dimethyl-2-imidazoline, in a weight ratio of 1:2.5 to 1:4. The IGR-based pesticide active ingredient used in the present invention acts as an ecdysone agonist on the lepidopteran larvae, a highly safe pesticide insecticidal component which is forced to promote the peel to be repelled outside the appropriate age. The active ingredient of the IGR-based pesticide can be exemplified by 'for example, N,-t-butyl-N,-(3,5-dimethylbenzimidyl)-5-methyl-6-chromancarbonyl oxime (common name) : Cyclosporin), N_Terbutyl-N, _(4-ethylbenzhydryl)_3,5·dimethylbenzoquinone (common name: Defenol), and >1 a quercetin-active compound such as tert-butyl-1^'-(3-methoxy-indole-indolyl phenyl)_3,5-diindolinoquinone (common name: methoxy oxime); Third butyl-imino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-min (common name: buffing), hydrazine-cyclopropyl-1,3, 5-triazine = triamine or 2_cyclopropylamine 100690.doc _ 7 _ 1343239 ke -4'6. Diamino _s • triterpenoid (common name: 赛灭净), and (10))· %二Π1'2 '3'3'3-hexafluoropropoxyphenyl]·3-(2,7·difluorobenzyl) urea (common name: Lufenlong) and other insect-resistant epidermis formation

a hindrance agent; and 2·(4·phenoxyphenoxy)ethylaminoacetic acid: (Insegar) (common name: Fenoke), 2.nm (4 • phenoxy oxyethoxy) ratio The postal name: π lipifene) and other juvenile hormone compounds. Its second Ν'-T-butyl Ν'·(3,5. dimethyl benzoyl) _5 methyl _6• color full base 醯 醯 (common name: ringworm brewing 肼), Ν • Tributyl Ν, _(4·ethyl benzoyl)-3,5-dimercaptobenzene ugly (common name: Defeno), and swimming third butyl group (3_methoxy-oxime)醯 激素 ) -3 俗 俗 俗 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Mercapto)-5-methyl-6-chroman carbonyl (common name: ringworm) is preferred.

The active ingredient can be set to an appropriate content, but usually it is 1.25 to 12 parts by weight. /. The content is preferably. 1>25% by weight or less, assuming that the amount of the drug is constant, it is not preferable for economic reasons, and if it is 12% by weight or more, aggregation or significant precipitation occurs when diluted with water. The agricultural chemical emulsion of the present invention may be mixed with an active ingredient other than the IGR-based pesticide as long as it does not affect long-term room temperature storage stability, low-temperature stability, emulsification, potentiation of the base of the drug, IGR-resistant drug-resistant pests, and phytotoxicity. The active ingredient. Specific examples of the above are as follows, but are not limited thereto. As an active ingredient of the insecticidal and acaricide, 丨-naphthyl-N-methylaminoformate (common name: NAC), 2·(ethylthiomethyl) stupyl=aminocarbamate Ester (common name: Affinck), and S-4-phenoxybutyl group = dimethylthioamine group I00690.doc 1343239

Aminoformate active ingredient such as formate (common name: phenanthrene); 〇, 〇_diethyl-0-3,5,6-trisyl·2·pyridyl phosphorothioate (common name: Taosson), 3-diethoxyphosphonium methylsulfate·6_gas benzoxazolone (common name: Yubisong), and 2-methoxy-4Η-1,3,2-benzodioxan Organophosphorus active ingredient such as phosphorus heterocyclohexyl-2-sulphide (common name: chlorpyrifos); (R, s) _a • cyano _3_ phenyloxy butyl (lRS, 3RS)-(lRS'3SR )-3-(2,2-divinyl)-2,2-dimethylcyclopropane

Burning carboxylic acid S 曰 (common name. Sai Ning Ning), a • cyano _3 · (2, 2 · two gas vinyl) _ 2 '2 · dimercaptocyclopropane carboxylate (common name: α_赛灭Ning), (s)_a_cyano-3_phenoxybenzyl=(111,38)-2,2-dimethyl-3-(1,1,2,2-tetrabromoethyl)cyclopropane Carboxylic ester (common name: Taining), (RSpa • cyano·3_phenoxybenzyl = (RS)-2-(4-phenylphenyl)-3·methylbutyric acid g (common name: Synthetic pyrethroids are active ingredients; and 2_(4-ethoxyphenyl)-2-methylpropyl=3-phenoxybenzyl ether (common name: fenfenine); Trans·5_(4_gasphenyl)_N_cyclohexyl-4-indolyl-2-oxothiazoline-3-carboxamide (common name: Hesaidu), 1-(4-qiqiji)- 3-(2,6-Difluorobenzamide) urea (common name: Erfulong), and 1-[3,5-digas·4-(3-gas-5-trifluoromethyl·2· 〇 咬 oxy) phenyl]_3_ (2,6-difluorobenzhydryl) urea (common name: kefulong) and other urea-based active ingredients; 1-(6-gas-3-pyridyl fluorenyl) - Ν-nitroimidazolinium iminoamine (common name: idadamine) and other new active components of the test system. Among them, 赛赛宁, α_赛灭宁The combination of edaramine is preferred. As an active ingredient of the fungicide, 0-2,6-di-gastolyl-〇'〇·-mercaptothiobenzoic acid (common name: methyl stand) , 3,··Isopropoxy-2-methylbenzoquinone-stupidamine (common name: chlorpheniramine), α,α,α-trifluoroisopropoxy- 0-indole phenylamine (common name: Fudonine) ), 1-(4-carbobenzyl)-cyclopentyl-100690.doc 1343239 3-phenylurea (common name: Binclones), N_tris-methylthiotetrahydroindenine (common name: Gapden , 3-(3,5-dioxaphenyliso-2,4.dioxoimidazolidin-1-carboxamide (common name: Yiputong), ethyl bisdithiocarbamic acid Zinc (common name: Zinc Naipu), bis(dimethylthiocarbamic acid) disulfide (common name: thiram), four gas phthalonitrile (common name: ΤΝΡ), 4,5,6,7 _Four gas o-phthalamide (common name: Pyrbis), 3,4,5,6_ four gas _ Ν · (2,3 · di-phenyl) phthalic acid (common name:枯 烂), 〇-ethyl-S, S-diphenyldithiocyanate (common name: EDDP), ν·(3,5-dichlorophenyl)-l,2-dimethylcyclopropane -1,2-dicarboxyl Indoleamine (common name: chlorpyrifos), • trifluoro·v_ (1-imidazol-1-yl-2-propoxyethyl) 〇-toluidine (common name: Saifu), 6· (3,5 - 二气_4_methylphenyl)-3(2Η)_pyridazinone (common name: sputum sputum), 3·allyloxy·1,2· stupid isothiazole _;!, 〗 _ In the case of the pesticide preparation of the present invention, hydrazine, 3_dimethyl-2-imidazolidinone (hereinafter referred to as DMI) is used. The use of DMI, considering the bathing property of the active ingredient of the IGR-based pesticide, requires at least 2.5 times the weight of the active ingredient, and the amount of the effect of the emulsification, potency, container, etc., must be 4 times or less the active ingredient. Further, in the pesticide preparation of the present invention, in addition to DMI, the IGR-based pesticide active ingredient can be efficiently dissolved, and a solvent capable of suppressing moisture absorption which is a cause of crystal precipitation and phase separation can be used in combination, but generally the solubility is still An aprotic polar solvent is preferred. Specific examples thereof include a group of methyl formamide, N-methylpyrrolidone, and the like. In the present invention, castor oil, because it can effectively act to inhibit the water of the preparation 100690.doc •10- €) 1343239 is a moisture-absorbing and IGR-based resistant pest, and is a suitable component. The content thereof is preferably from 30 to 80% by weight, more preferably from 60 to 78% by weight/s. Above 80% by weight, due to the lack of enthalpy of the end of the interface activity sword that keeps the emulsification, the emulsion of the preparation is poor, and the oil layer is separated into the upper layer when diluted, which is not conducive to the uniform distribution. Further, 30% by weight or less is not preferable because the effect of suppressing moisture absorption and the effect of the coffee-based medicine against the pests are insufficient. The castor oil used in the present invention is not particularly rated, but it is preferable to exclude the float which is the cause of crystallization. The emulsifying and dispersing surfactant used in the present invention may be emulsified and dispersed in a degree that the oil droplet which is a problem at the time of dilution does not float, and as a specific example thereof, for example, polyoxyethylene reinforced gluten oil, polyoxyethylene Sorbitan fatty acid ester, polyoxyethylene styryl phenyl ether, polycarboxylate, dialkyl sulfosuccinate, alkyl sulfonate, alkyl benzene sulfonate, lignosulfonic acid Salt, polyoxyethylene glycol alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, polyoxypropylene fatty acid φ ester, alkyl two Glycol ether sulfate, polyoxyethylene hardened t sesame oil, glycerin fatty acid ester 'sorbitan monooleate, polyoxyethylene sorbitan monolaurate vinegar' fatty acid alcohol polyglycol ether polyoxyethylene alkyl An aryl ether sulfate, a polyoxyethylene alkyl aryl phosphate salt, a mixture of these. Among them, a nonionic surfactant is preferred, and polyoxyethylene castor oil ether is particularly preferred. The proportion of the surfactant for emulsifying and dispersing contained in the agricultural chemical emulsion can be suitably 6 weeks. However, since the effect of the ultrafine emulsified particles on the Igr-based drug-resistant pest is insufficient, it is preferably 4-5 to 15.5% by weight. In the present invention, the imidazoline-based surfactant is particularly important because it is combined with castor oil to impart the effect of the active ingredient of the strong IGR system. It is found that it is effective as an IGR-based agent-resistant pest, which is considered to be a dispersing agent for inhibiting particle binding in oil. . As a carbazole-based surfactant, Pionine C-I59-ES (trade name: Takemoto, manufactured by Fat Co., Ltd.), and Homogenol L-95 (trade name, A system) are not limited to this. . In the pesticide preparation of the present invention, the content of the imidazoline-based surfactant is preferably 2 to 8% by weight. • The preferred form of the pesticide preparation of the present invention comprises: IGR-based pesticide effective knives 1.25 12% by weight; 13-dimethyl-2-imidazolidinone 3 〜 weight/〇, emulsification dispersion surfactant 4 .H 5 5 wt%; Jidong. Sitting on the interface is 2~8 wt% of active agent; and castor oil 3 0~80 wt%. The pesticide preparation of the present invention 'substantially does not require m or the like; the east agent. In addition, a stabilizer such as BTH which prevents oxidation of castor oil (such as an oxidation preventive agent), a synergistic agent such as piperonyl butoxide, an antifungal agent such as 1,2-benzisothiazolin-3-one, or a coloring agent may be added. Agents, fragrances, etc. φ ~ The agricultural chemical preparation of the present invention 'In order to maintain the safety of the active ingredient of the IGR-based agricultural chemical, the aprotic polar solvent DMI is used, so that the deterioration of the material of the container such as a bottle is likely to occur. JP-A-2003-89603 discloses dimethyl sulfoxide (dms〇) and/or 1,3-dimethyl-2-imidazoline (DMI) as a liquid pesticide composition superior to storage stability. And a mixture of antifreeze agents, and it is recommended to use a polyethylene container. However, as a container made of polyethylene, a sealed bottle made of high-density polyethylene, high-density polyethylene and a sealant (denatured nylon) is kneaded or made of southern density polyethylene (added calcium carbonate) / Ebral. The multi-layer Ebra bottle 100690.doc 1343239 (both manufactured by the North Acid Co., Ltd.), etc., is considered to be damaged or leaked in the bottle test. The agricultural emulsion of the present invention does not have to be damaged after a long period of time

Or a leaky storage container preferably uses a multi-layer nylon bottle. In particular, a nylon bottle composed of an outer layer composed of high-density polyethylene containing potassium carbonate and an inner layer composed of nylon is advantageously provided for long-term preservation of the durability of the agricultural chemical emulsion of the present invention, and advantageously It is used as a storage container for the agricultural chemical emulsion of the present invention.

The agrochemical emulsion of the present invention stored in such a container does not precipitate out of the precipitate during storage (4), and as a result, it can be stored safely and for a long period of time. Further, the agricultural chemical emulsion of the present invention did not cause problems such as consolidation and crystallization under the conditions of a low temperature storage test of rcx for 72 hours. This long-term storage stability is considered to be because the moisture absorption property of the active ingredient of the bottle-based pesticide can be suppressed by the balance between the components of the present invention. As for the method for producing the pesticide preparation of the present invention, for example,

f The active ingredient of the drug, if necessary, the solid stabilizer can be dissolved in Cong, and then the method of adding the sesame oil and the surfactant to obtain the pesticide preparation may be based on the preparation process. (4) These are based on the patent document (1 or Patent Document 2 or other general pesticide preparations. The sweating is carried out. [Examples] The following describes the examples of the present invention, but the present invention is not limited to the above. I00690.doc •13·1343239. (Example 1) (1) Circumstance (purity: 95%) .. 5.5 parts by weight (2) Castor oil · · · · · · · · · · · · · -212 (trade name, manufactured by Takemoto Oil Co., Ltd., polyoxyethylene castor oil ether) · · 7.0 parts by weight (4) Homogenol L-95 (trade name, manufactured by Kao Corporation, imidazoline surfactant) · · 3 · 0 parts by weight (5) 1,3-dimethyl-2-°m turmeric] (DMI) ... 15.0 parts by weight (6) SL-BHT-P (trade name 'common drug, oxidation inhibitor · 重量 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份Cyclosporin (purity: 95%) · · 5.5 parts by weight (2) 蓖 rattan, · . 6 1. 〇 by weight (3) New Calgen D-212 (trade name, manufactured by Takemoto Oil Co., Ltd., polyoxyethylene Castor oil ether)...1 5, Parts by weight (4) H〇m〇gen〇l L-95 (trade name, manufactured by Kao Corporation, imidazoline-based surfactant)..·3.0 parts by weight.”-Dimercapto^-imidazolidinone (1) River "...'^川重量份(6)SL-BHT-P (trade name, common drug, oxidation inhibitor) · 〇5 parts by weight (1) and (6) are placed in (5) to 4〇 The warm water bath of 〇c was dissolved, and then the remaining components were added to 100690.doc -14·M) 1343239 to obtain an emulsion of the present invention. (Example 3) (1) Ringworm simmering (purity: 95%) ... 10,0 parts by weight (2) 蓖蔚油·· .46.5 parts by weight (3) New Calgen D-212 (product name, bamboo Manufactured by the company of fats and oils, polyoxyethylene castor oil ether)...1 〇.〇 parts by weight (4) Homogenol L-95 (trade name, 'imidazoline surfactant prepared by Kao Corporation')...3 · 0 parts by weight (5) 1,3-Dimethyl-2-imidone (DMI) . · .30.0 parts by weight (6) SL-BHT-P (trade name, common drug, oxidation inhibitor) · · 5 parts by weight of (1) and (6) were placed in (5), and the emulsion of the present invention was obtained by 4 (temperature residual component of TC). (Example 4) The water tank was dissolved, and then added.

(1) Circumstance (purity: 95%) ... 1.3 weight ^ (2) Castor oil. · .77.8 parts by weight (3) New Calgen D-212 (trade name, bamboo, olefinic sesame oil ether) ... 5.0 parts by weight (4) Burning benzoic acid... 5.0 parts by weight of the company, polyoxyethylene (5) Homogen 〇l L-95 (trade name, Kaowanggong active agent). 7.0 parts by weight, imidazoline-based (6) 1,3-dimethyl-2-imidazolidinone (DMI) . q Λ J · 9 heavy (1) placed in (6) '4 〇 The warm water tank of °c dissolves the component 'to obtain the emulsion of the present invention. Add the remaining 100690.doc •15· 1343239

(Example 5) (1) Cyclosporin (purity: 95°/.) . . .2.6 parts by weight (2) Dry oil...77.6 parts by weight (3) New CalgenD_212 (trade name, Zhuben Oil Company) System

Ethyl castor oil 趟)..·9. 〇 parts by weight (4) Homogenol L-95 (trade name, Kao company; imidazoline-based surfactant)..·3·〇 parts by weight

(5) 1,3-Dimethyl-2-imidazolidinone (DMI) . · ·7.8 parts by weight (1) was placed in (5), dissolved in a warm water bath at 40 ° C, and then the remaining components were added. The emulsion of the invention is obtained. (Example 6) The emulsion prepared in Example 1 was packed in a high-density polyethylene (including carbonated) (outer layer) / nylon (inner layer) multi-layer nylon bottle (manufactured by Kitakatsu Co., Ltd.) (The main body is made of polypropylene, and the middle plug is made of low-density polyethylene), and the product of the present invention is obtained.

(Example 7) (1) Defenol (Synthetic product: Purity: 95%) . . . 5.5 parts by weight (2) Castor oil... 69.0 parts by weight (3) New Calgen D_212 (trade name, manufactured by Takemoto Oil Co., Ltd., Polyoxyethylene castor oil ether)········································································· Dimethyl-2-imidazolidinone (DMI).. (6) SL-BHT-P (trade name, common drug, _ΐ5·〇 part by weight oxidation inhibitor). ..0.5 I00690.doc -16· 1343239 Weight Parts (1) and (6) were placed in (5), dissolved in 4 (rc warm water tank, and then added to be added to the emulsion of the present invention. (Example 8)

(1) Methotrexate (Synthetic product: Purity: 95%) ·. .5 5 parts by weight (2) Storage oil, .61.0 parts by weight (3) NeW CalgenD_2l2 (trade name, manufactured by Takemoto Oil Co., Ltd., Polyoxyethylene sesame oil shouts ··· · 1 5. 〇 Parts by weight (4) H〇m〇geno丨u95 (trade name, manufactured by Kao Corporation, imidazoline-based surfactant)...3·0 parts by weight (5) 1,3-Dimethyl-2-imyl linone (dmi) ... 1 5. 〇 by weight (6) SL-BHT-P (trade name, co-drug, oxidation inhibitor weight part • 0.5

(1) and (6) were placed in (5), dissolved in a warm water bath at 40 ° C, and then the remaining components were added to obtain an emulsion of the present invention. (Example 9) (1) Lufenlong (medicinal extract; purity: 95%) . . . ί & JU parts by weight (2) Castor oil · · · 77,8 parts by weight (3) New Ca丨genD_212 (trade name, manufactured by Takemoto Oil Co., Ltd., polyoxyethylene castor oil ether)...5.0 parts by weight (4) calcium alkyl sulfonate. 5.0 parts by weight (5) Homogenol L-95 (trade name, Kao company noodles) Active agent) ... 7.0 parts by weight of taste ° sitting on the line (6) 1,3-dimethyl-2-flavor. Sitting with the same weight (DMI). · 3.9 weight 100690.doc p 1343239 Put (1) into (6), dissolve in 4 (rc in the warm water tank, then add the remaining ingredients 'to get the emulsion of the invention. Example 10) The emulsion prepared in Example 7 was packed in a multilayer nylon bottle (manufactured by Kitacic Acid Co., Ltd.) composed of high-density polyethylene (including calcium carbonate) (outer layer) / nylon (inner layer), and sealed with a seal. (The main body is polypropylene (PP), medium plug (low density polyethylene)) sealed to obtain the product of the present invention. (Comparative Example 1 (Patent Document 1 Example) (1) Cyclic cockroach (purity: 95%). .5.5 parts by weight (2) Castor oil..·8〇.5 parts by weight (3) New CalgenD-212 (trade name 'made by Takemoto Oil Co., Ltd., polyoxyethylene onion oil test>·.5.0 parts by weight ( 4) Homogenol L-95 (trade name, Kao company, taste π sitin surfactant) ·. 3.0 parts by weight (5) 1,3-dimethyl-2-mi. linalone (DMI) .6.0 parts by weight, (1) was placed in (5), dissolved in a warm water bath at 40 ° C, and then the remaining components were added to obtain a comparative emulsion. (Comparative Example 2 (Patent Document 1; 11)) (1) Circumstance (purity: 95%) · . · 5. 5 parts by weight (2) Castor oil · · · 35.5 parts by weight (3) Soybean oil · 40.0 parts by weight (4) New CalgenD-2l2 (trade name: manufactured by Takemoto Oil Co., Ltd., polyoxyethylene castor oil ether) ♦ · · 1 〇. 〇 by weight (5) Pi〇nine C-159-ES (trade name 'Bamboo Oil Co., Ltd., Mi. Sitting

100690.doc -18- (D 1343239 is a surfactant) 3.0 parts by weight of (6) 1,3-dimethyl-2-imidazolidinone (DMI) · ·6·〇 by weight () It was placed in (6), dissolved in a 40 C warm water bath, and then the remaining component was added to obtain a comparative emulsion.

(Comparative Example 3) (1) Circumstance (purity: 95%) . . . 5.5 parts by weight (2) 11 sesame oil... 76.5 parts by weight

(3) New Calgen D-212 (trade name, manufactured by Takemoto Oil Co., Ltd., polyoxyethylene castor oil scale)...5.0 parts by weight (4) H〇m〇genol L-95 (trade name, manufactured by Kao Corporation) Departmental surfactant)..·3·〇 parts by weight (5) 1,3-monomethyl·2-flavored 嗣 (DMI) ... 1 〇〇 by weight (1) into (5) In the middle, 4 (the molten water bath of TC was dissolved, and then the remaining components were added to obtain a comparative emulsion) (Comparative Example 4)

(1) Cyclosporin (purity: 95%) .. 5.5 parts by weight (2) Castor oil. · .66.5 parts by weight (3) New CalgenDJl2 (product name 'Bamboo Oil Co., Ltd., Polyethylene 稀·Oil mystery)...5.0 parts by weight (4) Homogenol L-95 (trade name, manufactured by Kao Corporation, imidazoline surfactant)..····0 parts by weight (5) Diterpenoid sulfoxide... 20.0 parts by weight (1) was placed in (5) and dissolved in a 40 ° C hot water bath, and then the remaining components were added to obtain a comparative emulsion. 100690.doc -19· 1343239 (Comparative Example 5) (1) Circumstance (purity: 95%) . . . 5.5 parts by weight (2) dry sesame oil... 56.5 parts by weight (3) New CalgenD_2i2 (trade name , manufactured by Takemoto Oil Co., Ltd., polyoxyethylene 蓖 vegetable oil mystery)...5 〇 by weight (4) Homogen〇l L-95 (trade name, manufactured by Kao Corporation, imidazoline surfactant). 3.0 parts by weight of (5) - 甲亚硬··30.0 parts by weight (1) was placed in (5), dissolved in a warm water bath at 40 ° C, and then the remaining components were added to obtain a comparative emulsion. (Comparative Example 6) (1) Cyclosporin (purity: 95%) . . . 5.5 parts by weight (2) Castor oil · · 41·0 parts by weight (3) 03074 ΤΧ (trade name, manufactured by Takemoto Oil Co., Ltd.; Polyoxyethylene pen oil ether, yard-based benzene continued acid)) * · 3 0,0 parts by weight (4) Japanese stone Haizorl SAS-296 (trade name, manufactured by Sakamoto Oil Co., Ltd., solvent). · · 14.0 weight (5) Homogenol L-95 (trade name, Kao company, spider spit surfactant). · · 3.0 parts by weight (6) 1,3-dimethyl-2-imidazolidinone (DMI) .6.0 parts by weight (7) SL-BHT-P (trade name, common drug; oxidation inhibitor).· .5 parts by weight (1) and (7) are placed in (6) '4°° The warm water tank of C was dissolved, and then the remaining components were added to obtain a comparative emulsion. The average particle diameter is 1 to 2 μm η ^ 100690.doc -20 - 1343239 (Comparative Example 7) (1) Cyclosporin (purity: 95%) ♦ · · 15.0 parts by weight (2) Castor oil ♦ · · 26 · 5 parts by weight of polyoxyethylene ramie (3) 03075 ΤΧ (trade name, manufactured by Takemoto Oil Co., Ltd., oil test, burnt base benzene acid) about 20.0 parts by weight (4) Homogenol L-95 (trade name surface activity) Agent) ♦· *3.0 parts by weight of the company, imidazoline system

(5) 1,3-Dimethyl-2-imidazolidinone (DMI) ·. .35 〇 Weight production (6) SL-BHT-P (trade name, common drug; oxygen non-chemical inhibitor)... (1) and (6) are placed in (5), and the temperature is 40 °C, and the remaining ingredients are added to obtain the comparative emulsion. (Comparative Example 8) (1)醯肼 (purity: 95%), .20.0 parts by weight (2) castor oil 16.5 parts by weight

Polyoxyethylene ramie (3) 03〇75TX (trade name, oil ether of Zhuben Oil Co., Ltd., calcium benzoate sulfonate)... 20.0 parts by weight (4) Homogenol L-95 (trade name surfactant) ♦ · 3 · 0 parts by weight of the company, imidazoline system • 0.5 ◦ ^ mouth - dimethyl ^ - imidazolinone (1) PCT" ... - village ❹ weight (6) SL-BHT-P (trade name, After adding the weight of the common drug and the oxidation inhibitor, (1) and (6) were placed in (5), and the remaining component was dissolved in a warm water bath of 4 Torr: to obtain a comparative emulsion. 100690.doc 21 (Comparative Example 9 (1) Circumstance (purity: 95%) . . . 5. 5 parts by weight (2) dimethyl sulfoxide... 20.0 parts by weight (7) S〇LVESSO #2〇〇 (trade name, manufactured by Exxon Corporation; High-boiling aromatic solvent)...64.5 parts by weight (4) New Calgen. 155LL (trade name, 'polyoxyethylene alkylphenyl _, alkyl benzene sulfonate metal salt, manufactured by Takemoto Oil Co., Ltd.) ·. The weight fractions (1) to (4) were uniformly mixed and dissolved to obtain a comparative emulsion. Comparative Example 1 0 (1) Cyclosporin (purity: 95%) . . . 5.5 parts by weight (2) New Ca丨gen PS_P (trade name, manufactured by Takemoto Oil Co., Ltd.; naphthalene shrinkage Combined anionic surfactant)._. 7. 〇 by weight (3) KF-96-l〇〇cp (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.05 parts by weight (4) tap water ···86.85 parts by weight (5) Xanthan gum.·,〇.〇5 parts by weight (6) Kimipia F (trade name, Guofeng Industrial, organic bentonite). . . . 5 parts by weight (7) PROXEL GXL (trade name , made by ZENEGA, preservative) · 0.05 parts by weight (1) ~ (7) uniformly mixed, wet pulverized with a sand mill at 1 800 rpm for 50 minutes 'to obtain an average particle size 丨.〇μηι (Comparative Example 11) The emulsion prepared in Example 1 was filled in a high-density polyethylene bottle (manufactured by Kitacic Acid Co., Ltd., 100690.doc -22·8 1343239, Ltd.), with a seal cover (body & Ethylene) Sealed to make a comparative sample (Comparative Example 12)

The emulsion prepared in Example U is filled in a sealed bottle formed by mixing high-density polyethylene and sealant (denatured nylon) with a seal cover (body: polypropylene); medium plug: low-density polyethylene Sealed and made a comparative sample. (Comparative Example 13)

(1) Defenol (synthetic product; purity: 95%) . . . 5 5 heavy parts (2) castor oil... 76.5 parts by weight (3) New Calgen D-212 (trade name, manufactured by Takemoto Oil Co., Ltd., Polyoxyethylene castor oil ether)· . . . 5 parts by weight (4) Homogenol L-95 (trade name, manufactured by Kao Corporation; imidazoline-based surfactant)..·3·〇 parts by weight

(5) 1,3-Dimethyl-2-imidazolidinone (〇河1)...1〇0 parts by weight (1) is placed in (5) to 40. (: The warm water tank was dissolved, and then the remaining components were added to obtain a comparative emulsion. (Comparative Example 14) (1) Definol (synthetic product; purity: 95%)... 55 parts by weight (2) Castor oil, , 66.5 parts by weight (3) New Calgen D-212 (trade name, manufactured by Takemoto Oil Co., Ltd.; polyoxyethylene castor oil shouting) ... 5.0 parts by weight (4) Homogenol L-95 (trade name, Kao company; Imidazoline-based surfactant] 3.0 parts by weight of (5) dimethyl sulfoxide (DMSO) · · 20·0 parts by weight 100690.doc . 23 - 1343239 (υ) into (5), to 40 The warm water tank of °c was dissolved, and then the remaining components were added to obtain a comparative emulsion. (Comparative Example 1 5) (1) Definol (synthetic product; purity: 95%) · 1.5 parts by weight (2) Castor oil. ..41.0 parts by weight (3) 03 075ΤΧ (trade name, manufactured by Takemoto Oil Co., Ltd.; polyoxyethylene n-sodium oleate, calcium alkylbenzenesulfonate)...30.0 parts by weight (4) Vermiculite Haizorl SAS-296 (trade name, manufactured by Sakamoto Oil Co., Ltd.; solvent) · · · ·················································································· (6) l,3-dimethyl-2 -^I m β-hostile ketone (DMI) ♦..6.0 parts by weight (7) SL-BHT-P (trade name 'common drug; oxidation inhibitor)., 〇5 parts by weight (1) and (7) It was placed in (6) and dissolved in a 40 ° warm water bath, and then the remaining components were added to obtain a comparative emulsion. (Comparative Example 16) (1) Defen (synthesis; purity: 95%)...15.0 by weight \ (2) Castor oil · · · 26.5 parts by weight (3) 03075 ΤΧ (trade name, manufactured by Takemoto Oil Co., Ltd.; polyoxyethylene castor oil test 'burning basic (four) acid about)... 20.0 parts by weight (4) Homogenol L- 95 (trade name, manufactured by Kao Corporation. A j I, imidazoline-based surfactant) · · ♦ 3.0 parts by weight 100690.doc •24·1 1,3-dimethyl-2-imidazolidinone (dmi). .. 35 〇重旦, 1343239 (6) SL-BHT-P (trade name, common drug; oxidation inhibitor).·〇5 parts by weight

Put (1) and (6) in (5) to 40. (: The warm water tank is dissolved), and the remaining components are added to obtain a comparative emulsion β (Comparative Example 17) (1) Fu Nuo (synthetic product; purity: 95%) * .. 20.0 parts by weight (2) castor oil. ·· 16.5 parts by weight

(3) 〇3〇75TX (trade name, manufactured by Takemoto Oil Co., Ltd.; polyoxyethylene castor oil ether, calcium alkylbenzene sulfonate).··20·0 parts by weight (4) H〇m〇gen〇] L- 95 (trade name, manufactured by Kao Corporation; imidazoline surfactant) ···························· *0.5 (6) SL-BHT-P (trade name, common drug; oxidation inhibitor) Part by weight (1) and (6) into (5), with 40DC of warm water. 々μ not groove Dissolved, and then added the remaining components to obtain a comparative emulsion" (Comparative Example 18) (1) Defenol (synthetic product; purity: 95%) . · s θ 0 J菫 Placement (2) New CalgenPS-P (trade name, manufactured by Takemoto Oil Co., Ltd.; naphthalene polymerized anionic surfactant)...7.0 parts by weight "" (3) KF-96-100 cP (trade name, Shin-Etsu Chemical Industry Co., Ltd.) ..·0.05 parts by weight (4) tap water..·86·85 parts by weight (5) xanthan gum...0.05 parts by weight 100690.doc •25· 1343239 (6) Kunipia F (trade name, Guofeng Industrial Co., Ltd.; Organic bentonite). .〇5 parts by weight (7) PROXEL GXL (trade name, ZENEK) A company made; preservative) 0.05 parts by weight (1) to (7) were uniformly mixed, and wet-pulverized by a sand mill under the conditions of 1 800 rpm, 50 minutes; a flowable agent for comparison was obtained. (Comparative Example 19) (1) Methotrexate (synthesis product: purity: 950/〇) · · .5.5 parts by weight (2) New Calgen PS-P (trade name, manufactured by Takemoto Oil Co., Ltd.; naphthalene condensation type anion interface Active agent)._.7.0 parts by weight (3) KF-96-100 cp (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.; methyl stone net)..*0.05 parts by weight (4) tap water · · ·86,85 weight (5) Xanthan gum · · · 0.05 parts by weight (6) Kunipia F (trade name, Guofeng Industrial; organic bentonite). · .〇5 parts by weight (7) PR〇XEL GXL (trade name, ZENEKA company Preparation, preservative) (0.05 parts by weight (1) to (7) uniformly mixed 'fishing and pulverizing at 1 800 rpm for 50 minutes using a sand mill to obtain a comparative flowable agent. (Test Example 1 (long-term room temperature storage stability test)) The test drug was placed in a JIS glass bottle, sealed with an inner lid and an outer lid, and stored at room temperature for 3 years. After the end of the storage, the naked eye was observed to investigate the crystal precipitation and phase separation. The results are shown in Table 1. '00690.doc 1343239 [Table 1] Table 1 : State observation after long-term storage Example 1 Example 2 was not confirmed. Comparative Example 1 was not confirmed. Crystal precipitation Comparative Example 2 Crystal precipitation Comparative Example 3 Crystal precipitation Comparative Example 4 Crystal precipitation Comparative Example 5 Crystal precipitation The results of Table 1 show that the present invention has good emulsion properties and long-term storage stability (Test Example 2 (open test)). The test agent is placed in a JIS glass bottle, and the inner lid and the outer lid are not used to open. In the state, an incubator having a temperature of 25 ° C and a humidity of 65% was placed for 3 weeks, and then observed with the naked eye to investigate crystal precipitation and phase separation of the test agent. The water content was measured by Karl Fischer moisture measurement. The results are shown in Table 2.

[Table 2] Moisture content 1.2% 1-2% 3.5% Unmeasured 4.0% !4.〇〇/0 !7.0% ^.0% Table 2: State observation of open experiment and state after 3 weeks of water content Example (1) No crystal precipitation and phase separation were observed. No crystal precipitation and phase separation were observed. Comparative Example 1 Crystal precipitation Comparative Example 2 Crystal precipitation Comparative Example 3 Crystal deposition Comparative Example 4 Crystal deposition Comparative Example 5 Crystal precipitation Comparative Example 9 12 hours After 3 days of phase separation, crystallization occurred, σ 100690.doc -27. From Table 2, the initial moisture content was ο 5% or less of any comparative preparation: in the open experiment of 3 weeks, moisture absorption occurred, Crystal precipitation, phase separation, etc. 'But the agrochemical emulsion of the present invention does not cause such problems, and the crystallization is excellently suppressed. (Test Example 3 (field test for the drug resistant leaf roller moth)) The test agent was diluted with water until the concentration of the active ingredient ringworm was 5 〇 ppm ocean 25 ppm, and the dilution of the water was doubled in the dilution.

Gramin (trade name, exhibition liquid), scattered in the tea garden (5 5吣6 plus 1 zone: 2 serial system). The insecticide rate of the leaf roller moth was investigated after 2 weeks of dissemination. The tea field leaf curler, the result of the sensitivity test, is an IGR-resistant drug-resistant leaf roller moth. The results are shown in Table 3. [Table 3] Table 3 - Field test results for the drug-resistant leaf roller moth The leafworm moth mortality rate (circumferential worm concentration) Example Comparative Example 6 Comparative Example 1 0 50 PPm 25 ppm 67.6% 47.1% 52.9 〇 / 〇 17.6% ^.7% 3% or less of the results of the field coating, it can be seen that the pesticide emulsion of the present invention shows a stable price control in comparison with the comparative example. (Test Example 4 (Emulsification Test)) The test agent 1 〇〇 μΐ was added to a jis glass bottle which was steamed with water, and the emulsified state was visually observed. The state immediately after emulsification and after 2 hours was investigated. The results of shai are shown in Table 4. 100690.doc -28- 1343239 [Table 4] Table 4: Observation of emulsified state Observation of emulsified state Immediately after emulsification Example 1 Dispersion emulsification Good Example 3 Dispersion emulsification Good Example 4 Dispersion emulsification Good Example 5 Dispersion emulsification Good Comparative Example 7 dispersion Poor Comparative Example 8 Dispersion was poor after 2 hours. Dispersion and emulsification. Good dispersion. Emulsification. Good dispersion, emulsification, good dispersion, emulsification, good precipitation at the bottom, emulsification, collapse, precipitation at the bottom, emulsification collapse.

From the results shown in Table 4, the product of the present invention was well emulsified. (Test Example 5 (bottle test)) This test was carried out in accordance with the Agricultural Plastic Bottle Test Method (June, June, 1993: Joint Research and Development Conference for Agricultural Plastic Containers). For the test article (n=3), a 3-cycle abusive test was performed with a cycle of -15 ° C, 3 days; room temperature, 1 day; 40 ° C, 30 days. From the height of 1.2 m, the test article was dropped vertically on the horizontal plane of the concrete bottom, and the number of times of destruction was measured at room temperature. The results are shown in Table 5.

[Table 5] Table 5: Drop test results Example 6 nl Example 6 n2 Example 6 n3 Comparative Example 11 nl Comparative Example 11 n2 Comparative Example 11 n3 Comparative Example 12 nl Comparative Example 12 n2 Comparative Example 12 n3 Until rupture The number of times of 30 times or more has not broken 30 times or more, has not broken 30 times or more, and has not broken 14 times. When the bottom cracks, the bottom cracks when it leaks 10 times, the bottom cracks when it leaks 12 times, and the bottom cracks when it leaks 3 times. When the bottom is leaked 6 times, the bottom cracks, the bottom cracks when it leaks 12 times, and the bottom cracks 100690.doc •29· From the results of Table 5, it is understood that the present invention uses a multilayer of high-density polyethylene (carbonated mother)/nylon. The nylon bottle is the best. (Test Example 6 (open test)) The test agent was placed in a JIS glass bottle. The inner lid and the outer lid were not used, and an open temperature L was placed in an incubator having a temperature of 2 5 C '6 6 %. After 3 weeks, observation with the naked eye was carried out to investigate the crystal precipitation and phase separation of the test agent. The water was measured by the Calfie Moisture Test. The results are shown in Table 6. [Table 6] Table 6: State observation after opening test and moisture content of water content: 1.5% 1.6% 3.5% Unmeasured 4.0% 14.0% _ After 3 weeks, Example 7 No crystal precipitation and phase separation were confirmed. No crystal precipitation and phase separation were observed. Comparative Example 1 Crystal precipitation Comparative Example 2 Crystal precipitation Comparative Example 13 Crystal precipitation Comparative Example 14 Crystal precipitation From the sixth table, it was found that the initial moisture content was 5% or less, and after 3 weeks. The open experiment 'has caused problems such as moisture absorption, crystallization precipitation, or phase separation: etc., but the embodiment of the present invention does not cause such a problem, and the crystallization is excellently suppressed. (Test Example 7) (Basic activity test for IG R-based drug-resistant leaf roller) The test agent was diluted with water until the concentration of the active ingredient of the pesticide was 2〇〇, 100, 50, 25, 12·5 ppm ' Into each dilution. The tea leaves were immersed in the diluted solution, and the drug-resistance leaf roller moth (the third generation leaf roller moth of Shizuoka prefecture cultivation; hereinafter referred to as R leafhopper) was examined, and the number of dead insects was investigated 5 days later. 100690.doc 1343239 [Table 7] Table 7: Test results for the drug-resistant leaf roller moth The test insecticide rate of the leaf roller moth (ppm) 200 100 50 25 12.5 Example 7 100% 100% 100% 100% 90% Example 8 100% 100% 100% 100% 95% Comparative Example 15 100% 80% 60% 30% 10% Comparative Example 16 100% 80% 45% 25% 10% Comparative Example 17 100% 75% 50% 30% 5% Comparison Example 18 80% 55% 10% 0% 0% Comparative Example 19 100% 100% 90% 75% 45% From the results of Table 7, it is understood that the agricultural emulsion of the present invention is diluted to a low concentration compared to the comparative example. Still showing the stability of the price. (Test Example 8 (Emulsification Test)) 100 μM of the test agent was added to a JIS glass bottle containing 100 ml of distilled water, and the emulsified state was visually observed. The state immediately after emulsification and after 2 hours was investigated. The results are shown in Table 8.

[Table 8] Table 8: Observation of emulsified state Observation of emulsified state 2 hours after emulsification Example 7 Dispersion emulsification Good Example 8 Dispersion emulsification Good Example 9 Dispersion emulsification was good Comparative Example 1 6 Dispersion poor Comparative Example 1 7 Dispersion failure The results of 8 show that the use of the industry is dispersed, the emulsion is well dispersed, the emulsion is well dispersed, the emulsion is well precipitated at the bottom, the emulsion collapses and precipitates at the bottom, and the emulsified collapsed product can be well emulsified. 100690.doc -31 · 1343239 The present invention provides a pesticide emulsion which has excellent long-term room temperature storage stability, low temperature stability, enhanced efficacy against phytotoxicity, emulsifying property, and 'enhanced resistance to active ingredients of IGR pesticides The effectiveness of sexual pests. The agricultural chemical emulsion of the present invention is used for a general pest-tolerant, and is particularly effective for obtaining a pest resistant to an active ingredient of an IGR-based pesticide. In general, a drug-resistant pest is obtained, and since the concentration of the median lethal dose of the drug is about 10 to 100 times or more, it is necessary to spread the previous one-fold amount, or it is not possible to disperse the amount or more depending on the case, but the effect is not obtained. When the agricultural chemical emulsion of the present invention is used, it can be sufficiently removed by a usual dispersion concentration. 100690.doc 32

Claims (1)

1343239 r Production Patent Application No. 094110880 (Related Patent Application No. 094110880) (Applicant's Patent Scope) X. Patent Application Range: A pesticide emulsion comprising: insect growth control (hereinafter referred to as IGR) is an active ingredient of pesticides, 1, 3· Dimethyl-2-mi. The acetonone's interface for emulsifying and dispersing is 〗 〖Live agent, imi η sitin-based surfactant and hydrazine oil. Among them, IGr-based pesticide active ingredient and 1,3·dimethyl-2-flavor»»坐琳嗣The weight ratio is 1: 2·5~1: 4, and contains IGR-based pesticide active ingredient 1 25~12 weight 0/〇; i,3·dimethyl-2-imidazolidinone 3.125~48% by weight; emulsified dispersion Use a surfactant of 4.5 to 15.5 weight. /〇; imidazoline surfactant 2~8 weight ° / 〇; and castor oil 30 ~ 80% by weight. 2. The agricultural chemical emulsion according to claim 1, wherein the surfactant for emulsification dispersion is a nonionic surfactant. 3. Agrochemical emulsion according to claim 1 or 2 which is used for insect growth control agent resistant pests. Agrochemical emulsion according to claim 1 or 2 wherein the igr-based pesticide active ingredient is a ring-growth. 5. The agricultural emulsion of claim 1 or 2, which is filled in a multi-layer nylon bottle comprising an outer layer and an inner layer, the outer layer comprising a high density polyethylene comprising calcium carbonate, the inner layer comprising nylon. 100690-1000308.doc