JP5545819B2 - Sustained release pesticide granules - Google Patents
Sustained release pesticide granules Download PDFInfo
- Publication number
- JP5545819B2 JP5545819B2 JP2010020147A JP2010020147A JP5545819B2 JP 5545819 B2 JP5545819 B2 JP 5545819B2 JP 2010020147 A JP2010020147 A JP 2010020147A JP 2010020147 A JP2010020147 A JP 2010020147A JP 5545819 B2 JP5545819 B2 JP 5545819B2
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- JP
- Japan
- Prior art keywords
- agrochemical
- granule
- mass
- fatty acid
- active ingredient
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000008187 granular material Substances 0.000 title claims description 202
- 239000000575 pesticide Substances 0.000 title description 13
- 238000013268 sustained release Methods 0.000 title 1
- 239000012730 sustained-release form Substances 0.000 title 1
- 239000003905 agrochemical Substances 0.000 claims description 138
- 239000000203 mixture Substances 0.000 claims description 54
- 239000004480 active ingredient Substances 0.000 claims description 45
- 230000000361 pesticidal effect Effects 0.000 claims description 41
- 238000002844 melting Methods 0.000 claims description 30
- 230000008018 melting Effects 0.000 claims description 29
- 238000001125 extrusion Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 27
- 239000004094 surface-active agent Substances 0.000 claims description 25
- 239000004359 castor oil Substances 0.000 claims description 23
- 235000019438 castor oil Nutrition 0.000 claims description 23
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 23
- 238000005469 granulation Methods 0.000 claims description 20
- 230000003179 granulation Effects 0.000 claims description 20
- 235000021355 Stearic acid Nutrition 0.000 claims description 19
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 19
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 19
- 239000008117 stearic acid Substances 0.000 claims description 19
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- 238000004519 manufacturing process Methods 0.000 claims description 13
- 235000004443 Ricinus communis Nutrition 0.000 claims description 12
- 150000004676 glycans Chemical class 0.000 claims description 12
- 229920001282 polysaccharide Polymers 0.000 claims description 12
- 239000005017 polysaccharide Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
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- 229930195729 fatty acid Natural products 0.000 description 87
- 150000004665 fatty acids Chemical class 0.000 description 86
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- ICTQUFQQEYSGGJ-UHFFFAOYSA-N thiocyclam oxalate Chemical compound OC(=O)C(O)=O.CN(C)C1CSSSC1 ICTQUFQQEYSGGJ-UHFFFAOYSA-N 0.000 description 31
- 238000002360 preparation method Methods 0.000 description 24
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- DSOOGBGKEWZRIH-UHFFFAOYSA-N nereistoxin Chemical compound CN(C)C1CSSC1 DSOOGBGKEWZRIH-UHFFFAOYSA-N 0.000 description 10
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- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 9
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
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- 239000002736 nonionic surfactant Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- OTYZDIRNFDVXFG-UHFFFAOYSA-N (2-butylphenyl) n-methylcarbamate Chemical group CCCCC1=CC=CC=C1OC(=O)NC OTYZDIRNFDVXFG-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
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- WHHIPMZEDGBUCC-UHFFFAOYSA-N probenazole Chemical compound C1=CC=C2C(OCC=C)=NS(=O)(=O)C2=C1 WHHIPMZEDGBUCC-UHFFFAOYSA-N 0.000 description 3
- MSHXTAQSSIEBQS-UHFFFAOYSA-N s-[3-carbamoylsulfanyl-2-(dimethylamino)propyl] carbamothioate;hydron;chloride Chemical compound [Cl-].NC(=O)SCC([NH+](C)C)CSC(N)=O MSHXTAQSSIEBQS-UHFFFAOYSA-N 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 3
- CFRPSFYHXJZSBI-DHZHZOJOSA-N (E)-nitenpyram Chemical compound [O-][N+](=O)/C=C(\NC)N(CC)CC1=CC=C(Cl)N=C1 CFRPSFYHXJZSBI-DHZHZOJOSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- IZHVBANLECCAGF-UHFFFAOYSA-N 2-hydroxy-3-(octadecanoyloxy)propyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)COC(=O)CCCCCCCCCCCCCCCCC IZHVBANLECCAGF-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- CVQODEWAPZVVBU-UHFFFAOYSA-N XMC Chemical compound CNC(=O)OC1=CC(C)=CC(C)=C1 CVQODEWAPZVVBU-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- YFXPPSKYMBTNAV-UHFFFAOYSA-N bensultap Chemical compound C=1C=CC=CC=1S(=O)(=O)SCC(N(C)C)CSS(=O)(=O)C1=CC=CC=C1 YFXPPSKYMBTNAV-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
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- YKBZOVFACRVRJN-UHFFFAOYSA-N dinotefuran Chemical compound [O-][N+](=O)\N=C(/NC)NCC1CCOC1 YKBZOVFACRVRJN-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- YREQHYQNNWYQCJ-UHFFFAOYSA-N etofenprox Chemical compound C1=CC(OCC)=CC=C1C(C)(C)COCC1=CC=CC(OC=2C=CC=CC=2)=C1 YREQHYQNNWYQCJ-UHFFFAOYSA-N 0.000 description 2
- PTCGDEVVHUXTMP-UHFFFAOYSA-N flutolanil Chemical compound CC(C)OC1=CC=CC(NC(=O)C=2C(=CC=CC=2)C(F)(F)F)=C1 PTCGDEVVHUXTMP-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 2
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- PHTHKSNCQCCOHM-UHFFFAOYSA-N (4,6-dimethylpyrimidin-2-yl)hydrazine Chemical group CC1=CC(C)=NC(NN)=N1 PHTHKSNCQCCOHM-UHFFFAOYSA-N 0.000 description 1
- PGOOBECODWQEAB-UHFFFAOYSA-N (E)-clothianidin Chemical compound [O-][N+](=O)\N=C(/NC)NCC1=CN=C(Cl)S1 PGOOBECODWQEAB-UHFFFAOYSA-N 0.000 description 1
- HOKKPVIRMVDYPB-UVTDQMKNSA-N (Z)-thiacloprid Chemical compound C1=NC(Cl)=CC=C1CN1C(=N/C#N)/SCC1 HOKKPVIRMVDYPB-UVTDQMKNSA-N 0.000 description 1
- ODRMRGQYRJGWTH-UHFFFAOYSA-N 1,2,5,6-tetrahydro-4h-pyrrolo(3,2,1-ij)quinoline Chemical compound C1CCN2CCC3=CC=CC1=C32 ODRMRGQYRJGWTH-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- PRLVTUNWOQKEAI-UHFFFAOYSA-N 2-(tert-butylimino)-5-phenyl-3-(propan-2-yl)-1,3,5-thiadiazinan-4-one Chemical compound O=C1N(C(C)C)C(=NC(C)(C)C)SCN1C1=CC=CC=C1 PRLVTUNWOQKEAI-UHFFFAOYSA-N 0.000 description 1
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- NWWZPOKUUAIXIW-UHFFFAOYSA-N thiamethoxam Chemical compound O=N(=O)N=C1N(C)COCN1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-UHFFFAOYSA-N 0.000 description 1
- NWWZPOKUUAIXIW-FLIBITNWSA-N thiamethoxam Chemical compound [O-][N+](=O)\N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-FLIBITNWSA-N 0.000 description 1
- 125000004305 thiazinyl group Chemical group S1NC(=CC=C1)* 0.000 description 1
- VJQYLJSMBWXGDV-UHFFFAOYSA-N tiadinil Chemical compound N1=NSC(C(=O)NC=2C=C(Cl)C(C)=CC=2)=C1C VJQYLJSMBWXGDV-UHFFFAOYSA-N 0.000 description 1
- JARYYMUOCXVXNK-IMTORBKUSA-N validamycin Chemical compound N([C@H]1C[C@@H]([C@H]([C@H](O)[C@H]1O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)CO)[C@H]1C=C(CO)[C@H](O)[C@H](O)[C@H]1O JARYYMUOCXVXNK-IMTORBKUSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002492 water-soluble polymer binding agent Substances 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は農薬活性成分を担持した農薬粒剤に関し、農薬活性成分の溶出を制御し、溶出期間を長期化させることにより、所望の期間に亘り農薬効力を持続的に発現させることができる農薬粒剤の製剤技術に関する。また当該粒剤の粒硬度を向上させた農薬粒剤に関し、市場流通過程における保存中及び輸送中での粒の崩壊を抑制し、機械的強度が向上した長期保存安定性に優れた農薬粒剤技術に関する。さらには当該農薬粒剤の散布初期おける農薬活性成分溶出量を抑制し、散布初期から長期間に亘り一定の効力持続を可能にさせた農薬粒剤に関する。詳しくは、農薬活性成分、脂肪酸及び/又は脂肪酸誘導体、並びに無機物質を含む農薬組成物を押出造粒した後に、加熱処理して得られる農薬粒剤に関し、水溶解度の高い農薬活性成分の溶出を制御し溶出期間を長期化させ、散布回数を減らし省力化を可能にする農薬粒剤に関する。 TECHNICAL FIELD The present invention relates to an agrochemical granule carrying an agrochemical active ingredient, and relates to an agrochemical grain capable of continuously expressing the agrochemical efficacy over a desired period by controlling the elution of the agrochemical active ingredient and extending the elution period. The present invention relates to drug formulation technology. In addition, with respect to the agrochemical granules whose grain hardness has been improved, the agrochemical granules with excellent long-term storage stability with improved mechanical strength by suppressing the collapse of grains during storage and transportation in the market distribution process Regarding technology. Further, the present invention relates to an agrochemical granule that suppresses the elution amount of an agrochemical active ingredient in the initial stage of application of the agrochemical granule and allows a certain level of efficacy to be maintained over a long period from the initial stage of application. Specifically, for the pesticide granules obtained by extrusion granulation of agrochemical compositions containing agrochemical active ingredients, fatty acids and / or fatty acid derivatives, and inorganic substances, elution of pesticide active ingredients with high water solubility The present invention relates to an agrochemical granule that can be controlled to extend the elution period, reduce the number of sprays, and save labor.
近年、農業従事者の高齢化が益々深刻になり、農作業の省力化が求められている。それに伴い農薬も省力散布製剤やその省力的散布方法に関する技術が開発されてきている。さらに環境負荷低減という面から、農薬の使用量及び使用回数の減少と使用期間の早期化が望まれる。これらの要請を受け、農薬活性成分の溶出制御、溶出期間の長期化を目的とした農薬粒剤の開発が行われている。そこで、農薬活性成分の土壌中及び水中における溶出速度を制御する製剤技術の開発が必要となるが、農薬活性成分の溶出を制御する製剤としては、これまでにも様々な農薬基材を用いた製剤が開発されている。これらの中において脂肪酸及び/又は脂肪酸誘導体や、各種ワックスを用いた溶出制御製剤が知られている。例えば特許文献1には20℃における水溶解度が50ppm以上の殺虫活性成分、炭素数が10〜18の高級脂肪酸の炭素数1〜6のアルキルエステル、吸油性粒状担体からなる農薬粒剤が開示されている。また特許文献2にはアルコール型ワックスを含有することを特徴とする農薬粒剤が開示されている。さらに、特許文献3ではモンタンロウ誘導体混合物を含有することを特徴とする農薬粒剤が開示されている。 In recent years, the aging of farmers has become more and more serious, and labor saving of farm work has been demanded. Along with this, techniques relating to labor-saving spray formulations and their labor-saving spraying methods have been developed. Furthermore, from the viewpoint of reducing the environmental burden, it is desired to reduce the amount and number of use of agricultural chemicals and accelerate the period of use. In response to these requests, agrochemical granules have been developed for the purpose of controlling the elution of agrochemical active ingredients and extending the elution period. Therefore, it is necessary to develop a formulation technology that controls the dissolution rate of agricultural chemical active ingredients in soil and water, but various pharmaceutical base materials have been used as preparations to control the dissolution of agricultural chemical active ingredients. Formulations are being developed. Among these, dissolution controlled preparations using fatty acids and / or fatty acid derivatives and various waxes are known. For example, Patent Document 1 discloses an agrochemical granule comprising an insecticidal active ingredient having a water solubility at 20 ° C. of 50 ppm or more, a C 1-6 alkyl ester of a higher fatty acid having 10 to 18 carbon atoms, and an oil-absorbing granular carrier. ing. Patent Document 2 discloses an agrochemical granule characterized by containing an alcohol type wax. Furthermore, Patent Document 3 discloses an agrochemical granule characterized by containing a montan wax derivative mixture.
しかし、特許文献1に示した溶出制御粒剤は、数日から数週間といった長期の溶出制御はできず、十分な生物効果を得られない。特許文献2においては、農薬活性成分の溶出効率が十分でなく、農薬粒剤中に薬物が一部もしくは多くの含量が留まってしまい、一定の施用量において生物効果を得るための十分な溶出が得られないといった欠点があった。また、特許文献3の農薬粒剤の製造方法は、基材であるモンタンロウ誘導体と農薬活性成分を加熱溶融して混合した後に、冷却固化したものを破砕造粒することによって得られる。しかしながら、熱に不安定な農薬活性成分を用いた場合、上記のような加熱溶融工程を含む製造方法では製造することができない。また、モンタンロウ誘導体などの脂肪酸誘導体と農薬活性成分を固体のまま直接混合し、加熱工程を経ずに押出造粒を行うと、得られる粒の硬度が低く、保存や輸送時に粒が割れたり欠けたりすることで粒剤の総表面積が大きくなり望む溶出速度が得られなくなるおそれがある。
本発明の課題は、水溶性の高い農薬活性成分を含有する農薬粒剤において、散布初期における薬剤過剰溶出を抑制し、薬剤の溶出を長期間維持できる農薬製剤を提供することにある。加えて市場流通過程において、粒破砕等がなく粒剤形状が保たれる十分な粒硬度を有し、保存性が良好な粒剤を提供することにある。更には熱分解性農薬活性成分の製剤調製にも適用し得るような、高温または長時間の加熱処理を加える工程を経ることない農薬粒剤の製造方法を提供することにある。
However, the elution control granule shown in Patent Document 1 cannot perform elution control for a long time such as several days to several weeks, and a sufficient biological effect cannot be obtained. In Patent Document 2, the elution efficiency of the pesticidal active ingredient is not sufficient, and some or much of the drug remains in the pesticidal granule, and sufficient elution for obtaining a biological effect at a constant application rate is achieved. There was a disadvantage that it could not be obtained. Moreover, the manufacturing method of the agrochemical granule of patent document 3 is obtained by crushing and granulating what was solidified by cooling, after heat-melting and mixing the montan wax derivative which is a base material, and an agrochemical active ingredient. However, when a thermally unstable agricultural chemical active ingredient is used, it cannot be produced by a production method including the heating and melting step as described above. In addition, when a fatty acid derivative such as a montan wax derivative and an agrochemical active ingredient are directly mixed in a solid state and subjected to extrusion granulation without passing through a heating step, the resulting grains have low hardness, and the grains are cracked or chipped during storage and transportation. The total surface area of the granule may increase and the desired elution rate may not be obtained.
An object of the present invention is to provide an agrochemical formulation capable of suppressing excessive drug elution at the initial stage of application and maintaining elution of the drug for a long period of time in an agrochemical granule containing an agrochemical active ingredient having high water solubility. In addition, in the market distribution process, the present invention is to provide a granule having sufficient grain hardness that maintains the shape of the granule without grain crushing and has good storage stability. Furthermore, it is providing the manufacturing method of the agrochemical granule which does not go through the process of adding the heat processing for a high temperature or a long time which can be applied also to the formulation preparation of a thermally decomposable agrochemical active ingredient.
本発明者らは、農薬粒剤に使用され得る種々の製剤基材や添加剤を用い、様々な製剤調製処方及び条件について鋭意検討した結果、農薬活性成分、脂肪酸及び/又は脂肪酸誘導体、並びに無機物質を含有する農薬活性体組成物を造粒してなる農薬粒剤が、水溶解度の高い農薬活性成分の長期間に亘る薬剤溶出を制御できることを見出した。また、当該造粒してなる農薬粒状物を、用いた脂肪酸及び/又は脂肪酸誘導体の融点以下の温度で短時間加熱処理することによって、当該農薬粒剤の粒硬度を増強すると共に、製剤散布初期における薬剤の過剰溶出を制御し、散布当初から長期間に亘り薬効力を持続発揮させ得ることを見出した。
すなわち本発明は、
(1) 農薬活性成分(a)、脂肪酸及び/又は脂肪酸誘導体(b)、並びに無機物質(c)を含む混合物を造粒した後、前記脂肪酸及び/又は脂肪酸誘導体(b)の融点より低い温度で加熱処理して得られることを特徴とする農薬粒剤、
(2) 脂肪酸及び/又は脂肪酸誘導体(b)が、C8〜C40アルキル鎖カルボン酸及びその誘導体の中から選ばれる1種、または2種以上の混合物である(1)に記載の農薬粒剤、
(3) 脂肪酸及び/又は脂肪酸誘導体(b)として、ヒマシ硬化油、ヒマシ油、及びステアリン酸の混合物である(1)または(2)に記載の農薬粒剤、
(4) 農薬活性成分(a)として、ネライストキシン系農薬活性成分を含む(1)〜(3)のいずれか一項に記載の農薬粒剤、
(5) 無機物質(c)がクレー、タルク、白土、珪藻土、ゼオライト、硫酸バリウム、二酸化チタン、及び非晶質二酸化珪素(ホワイトカーボン)からなる群から選ばれる1種以上である(1)〜(4)のいずれか一項に記載の農薬粒剤、
(6) 農薬活性成分(a)を3〜25質量%、脂肪酸及び/又は脂肪酸誘導体(b)を10〜80質量%、並びに無機物質(c)を10〜60質量%を含有する(1)〜(5)のいずれか一項の農薬粒剤、
(7) 粒径が2〜10mmであることを特徴とする(1)〜(6)のいずれか一項に記載の農薬粒剤、
(8) 界面活性剤(d)を0.1〜10質量%含有する(1)〜(7)のいずれか一項に記載の農薬粒剤、
(9) 水難溶性多糖類(e)を0.5〜20質量%含有する(1)〜(8)のいずれか一項に記載の農薬粒剤、
(10) 加熱処理が50℃以上80℃より低い温度で、60分以内で行われることを特徴とする(1)〜(9)のいずれか一項に記載の農薬粒剤、
(11) (1)〜(10)のいずれか一項に記載の農薬粒剤に、界面活性剤(d)をコーティングして得られる農薬粒剤、
(12) 農薬活性成分(a)、脂肪酸及び/又は脂肪酸誘導体(b)、並びに無機物質(c)を含む農薬組成物を混合する工程、次いでこれを粒状に造粒する工程、その後この造粒物を前記脂肪酸及び/又は脂肪酸誘導体(b)の融点より低い温度で加熱処理する工程、を含むことを特徴とする農薬粒剤の製造方法、
(13) 造粒が縦型押出造粒機によって行われる(12)に記載の農薬粒剤の製造方法、
(14) 加熱処理が50℃以上80℃より低い温度で、60分以内で行われることを特徴とする(12)または(13)に記載の農薬粒剤の製造方法、に関する。
As a result of intensive investigations on various preparation preparations and conditions using various preparation bases and additives that can be used in agrochemical granules, the present inventors have found that agrochemical active ingredients, fatty acids and / or fatty acid derivatives, and inorganics It has been found that an agrochemical granule formed by granulating an agrochemical active composition containing a substance can control drug elution over a long period of an agrochemical active ingredient having high water solubility. In addition, the granulated agricultural chemical granules are heat-treated at a temperature below the melting point of the fatty acid and / or fatty acid derivative used for a short time, thereby enhancing the grain hardness of the agricultural chemical granules and at the initial stage of spraying the formulation. It was found that the drug elution can be controlled and the drug efficacy can be continuously exerted over a long period from the beginning of spraying.
That is, the present invention
(1) A temperature lower than the melting point of the fatty acid and / or fatty acid derivative (b) after granulating a mixture containing the agrochemical active ingredient (a), fatty acid and / or fatty acid derivative (b), and inorganic substance (c). Agrochemical granules characterized by being obtained by heat treatment with
(2) The agrochemical granule according to (1), wherein the fatty acid and / or fatty acid derivative (b) is one or a mixture of two or more C8-C40 alkyl chain carboxylic acids and derivatives thereof,
(3) The agrochemical granule according to (1) or (2), which is a mixture of castor oil, castor oil, and stearic acid as the fatty acid and / or fatty acid derivative (b),
(4) The agrochemical granule according to any one of (1) to (3), which contains a nereistoxin agrochemical active ingredient as the agrochemical active ingredient (a),
(5) The inorganic substance (c) is at least one selected from the group consisting of clay, talc, white clay, diatomaceous earth, zeolite, barium sulfate, titanium dioxide, and amorphous silicon dioxide (white carbon). The agrochemical granule according to any one of (4),
(6) 3 to 25% by mass of the agrochemical active ingredient (a), 10 to 80% by mass of the fatty acid and / or fatty acid derivative (b), and 10 to 60% by mass of the inorganic substance (c) (1) The agrochemical granule according to any one of to (5),
(7) The agrochemical granule according to any one of (1) to (6), wherein the particle size is 2 to 10 mm,
(8) The agrochemical granule according to any one of (1) to (7), which contains 0.1 to 10% by mass of the surfactant (d),
(9) The agricultural chemical granule according to any one of (1) to (8), which contains 0.5 to 20% by mass of the poorly water-soluble polysaccharide (e),
(10) The agrochemical granule according to any one of (1) to (9), wherein the heat treatment is performed at a temperature of 50 ° C. or higher and lower than 80 ° C. within 60 minutes.
(11) Agrochemical granules obtained by coating the agrochemical granules according to any one of (1) to (10) with a surfactant (d),
(12) A step of mixing an agrochemical composition containing an agrochemical active ingredient (a), a fatty acid and / or a fatty acid derivative (b), and an inorganic substance (c), then a step of granulating this, and then this granulation A process for heat treating the product at a temperature lower than the melting point of the fatty acid and / or fatty acid derivative (b), and a method for producing an agrochemical granule,
(13) The method for producing an agrochemical granule according to (12), wherein the granulation is performed by a vertical extrusion granulator,
(14) The method for producing an agrochemical granule according to (12) or (13), wherein the heat treatment is performed at a temperature of 50 ° C. or higher and lower than 80 ° C. within 60 minutes.
本発明の農薬粒剤は、製剤基材に用いる脂肪酸及び/又は脂肪酸誘導体の種類や組合せ組成、及び無機物質の種類や含有量の調整すること、さらにそれら組成物の造粒体を、用いた脂肪酸及び/又は脂肪酸誘導体の融点以下で加熱処理することによって、種々の農薬活性成分の溶出速度を制御した農薬粒剤を調製することができる。したがって用いる農薬活性成分の至適濃度、対象とする病害虫、散布時期、作用期間に応じた製剤をデザインすることができ、その結果、用いる農薬活性成分の効力が十分に発揮される農薬粒剤を提供できる。また、加熱処理を経ることにより当該粒剤の粒硬度が向上し、機械的強度安定性が高く、市場流通過程における長期保存性が良好な農薬粒剤を提供できる。加えて当該農薬散布初期における農薬活性成分の過剰溶出が抑制され、散布初期から長期間に亘り薬効力を持続発揮させ得る農薬粒剤を提供できる。 The agrochemical granule of the present invention uses the type and combination composition of fatty acids and / or fatty acid derivatives used for the preparation base, and the type and content of inorganic substances, and further uses the granule of these compositions. By carrying out heat treatment below the melting point of the fatty acid and / or fatty acid derivative, it is possible to prepare pesticidal granules with controlled elution rates of various pesticidal active ingredients. Therefore, it is possible to design a formulation according to the optimum concentration of the pesticidal active ingredient to be used, the target pest, the spraying time, and the duration of action. Can be provided. Moreover, the grain hardness of the said granule improves by passing through heat processing, the mechanical strength stability is high, and the agrochemical granule with long-term preservability in a market distribution process can be provided. In addition, excessive elution of the pesticidal active ingredient in the initial stage of spraying of the pesticide can be suppressed, and a pesticide granule that can continuously exert its drug efficacy for a long period from the initial stage of spraying can be provided.
以下に本発明の農薬粒剤及びその製造方法についてより詳しく説明する。
本発明の農薬粒剤に使用される農薬活性成分は、通常、農薬殺虫活性成分または農薬殺菌活性成分であればいずれでもよく、特に制限はない。これらの中でも水の溶解度が高い農薬活性成分が特に適している。具体的には、20℃における水溶解度が0.01〜50質量%程度の親水性物質であり、水中への溶出性が高い傾向にある農薬活性成分が好ましい。農薬活性成分としては、具体的には例えば次のようなものが挙げられるがこれに限定されるものではない。農薬殺虫活性成分としては、例えば1,3−ジカルバモイルチオ−2−(N、N−ジメチルアミノ)−プロパン塩酸塩(カルタップ塩酸塩)、5−ジメチルアミノ−1,2,3−トリチアンシュウ酸塩(チオシクラムシュウ酸塩)、S,S'‐2‐ジメチルアミノトリメチレン=ジ(ベンゼンチオスルホナート)(ベンスルタップ)等のネライストキシン系殺虫剤;1‐(6‐クロロ‐3‐ピリジルメチル)‐N‐ニトロイミダゾリジン‐2‐イリデンアミン(イミダクロプリド)、3‐(2‐クロロ‐1,3‐チアゾール‐5‐イルメチル)‐5‐メチル‐1,3,5‐オキサジアジナン‐4‐イリデン(ニトロ)アミン(チアメトキサム)、(E)‐1‐(2‐クロロ‐1,3‐チアゾール‐5‐イルメチル)‐3‐メチル‐2‐ニトログアニジン(クロチアニジン)、(RS)‐1‐メチル‐2‐ニトロ‐3‐(テトラヒドロ‐3‐フリルメチル)グアニジン(ジノテフラン)、3‐(6‐クロロ‐3‐ピリジルメチル)‐1,3‐チアゾリジン‐2‐イリデンシアナミド(チアクロプリド)、(E)‐N‐(6‐クロロ‐3‐ピリジルメチル)‐N‐エチル‐N'‐メチル‐2‐ニトロビニリデンジアミン(ニテンピラム)、(E)‐N‐[(6‐クロロ‐3‐ピリジル)メチル]‐N'‐シアノ‐N‐メチルアセトアニジン(アセタミプリド)等のネオニコチノイド系殺虫剤;S−メチル−N−[(メチルカルバモイル)オキシ]チオアセトイミデート(メソミル)、2−セコンダリーブチルフェニル−N−メチルカーバメート(BPMC)等のカーバメイト系殺虫剤が挙げられる。農薬殺菌活性成分としては、例えば、3−アリルオキシ−1,2−ベンゾイソチアゾール−1,1−ジオキシド(プロベナゾール)、1,2,5,6−テトラヒドロピロロ[3,2,1−ij]キノリン−4−オン(ピロキロン)、(E)−2−メトキシイミノ−N−メチル−2−(2−フェノキシフェニル)アセトアミド(メトミノストロピン)、5−メチル−1,2,4―トリアゾロ[3,4−b]ベンゾチアゾール(トリシクラゾール)、3'-クロロ−4,4'−ジメチル−1,2,3−チアジアゾール−5−カルボキサニリド(チアジニル)、[5−アミノ−2−メチル−6−(2,3,4,5,6−ペンタヒドロキシシクロヘキシロキシ)テトラヒドロピラン−3−イル]アミノ−α−イミノ酢酸(一般名:カスガマイシン)等が挙げられる。これらの中でも、ネライストキシン系殺虫剤、またはネオニコチノイド系殺虫剤の溶出制御型農薬粒剤を調製するために適用できる。農薬活性成分としてより好ましくはカルタップ塩酸塩、チオシクラムシュウ酸塩である。本発明の農薬粒剤にはこれらの農薬活性成分を単独又は2種以上を併用してもよい。
The agrochemical granule of the present invention and the production method thereof will be described in more detail below.
The pesticidal active ingredient used in the pesticidal granule of the present invention may be any pesticidal active ingredient or pesticidal active ingredient and is not particularly limited. Among these, agricultural chemical active ingredients having high water solubility are particularly suitable. Specifically, an agrochemical active ingredient which is a hydrophilic substance having a water solubility of about 0.01 to 50% by mass at 20 ° C. and tends to have high elution into water is preferable. Specific examples of the agrochemical active ingredient include, but are not limited to, the following. Examples of the agrochemical insecticidal active ingredient include 1,3-dicarbamoylthio-2- (N, N-dimethylamino) -propane hydrochloride (cartap hydrochloride), 5-dimethylamino-1,2,3-trithianshu Nereistoxin insecticides such as acid salts (thiocyclam oxalate), S, S′-2-dimethylaminotrimethylene di (benzenethiosulfonate) (bensultap); 1- (6-chloro-3 -Pyridylmethyl) -N-nitroimidazolidin-2-ylideneamine (imidacloprid), 3- (2-chloro-1,3-thiazol-5-ylmethyl) -5-methyl-1,3,5-oxadiazinan-4-ylidene ( Nitro) amine (thiamethoxam), (E) -1- (2-chloro-1,3-thiazol-5-ylmethyl) -3-methyl-2-nitrog Nidin (clothianidin), (RS) -1-methyl-2-nitro-3- (tetrahydro-3-furylmethyl) guanidine (dinotefuran), 3- (6-chloro-3-pyridylmethyl) -1,3-thiazolidine -2-Iridenecyanamide (thiacloprid), (E) -N- (6-Chloro-3-pyridylmethyl) -N-ethyl-N'-methyl-2-nitrovinylidenediamine (Nitenpyram), (E) -N -Neonicotinoid insecticides such as [(6-chloro-3-pyridyl) methyl] -N′-cyano-N-methylacetanidin (acetamipride); S-methyl-N-[(methylcarbamoyl) oxy] Carbamate insecticides such as thioacetimidate (mesomyl), 2-secondary butylphenyl-N-methyl carbamate (BPMC) That. Examples of agricultural chemical bactericidal active ingredients include 3-allyloxy-1,2-benzisothiazole-1,1-dioxide (provenazole), 1,2,5,6-tetrahydropyrrolo [3,2,1-ij] quinoline. -4-one (pyroxylone), (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide (methinostropine), 5-methyl-1,2,4-triazolo [3 4-b] benzothiazole (tricyclazole), 3′-chloro-4,4′-dimethyl-1,2,3-thiadiazole-5-carboxanilide (thiazinyl), [5-amino-2-methyl-6- (2 , 3,4,5,6-pentahydroxycyclohexyloxy) tetrahydropyran-3-yl] amino-α-iminoacetic acid (generic name: kasugamycin) It is. Among these, it can be applied to prepare an elution-controlled pesticide granule for nereistoxin insecticide or neonicotinoid insecticide. More preferred as an agrochemical active ingredient are cartap hydrochloride and thiocyclam oxalate. These agrochemical active ingredients may be used alone or in combination of two or more in the agrochemical granule of the present invention.
前記好ましい農薬活性成分であるネライストキシン系殺虫剤、ネオニコチノイド系殺虫剤を適用した場合、これらに対して化学的安定性の面で影響を与えない範囲であれば1種類以上併用することができる。ネライストキシン系殺虫剤、及びネオニコチノイド系殺虫剤と混用し得る好ましい併用薬剤とは、具体的には例えば次のようなものが挙げられる。例えば殺虫活性成分としては、BPMC(2‐sec‐ブチルフェニル‐N‐メチルカーバメート)、MIPC(2‐イソプロピルフェニル‐N‐メチルカーバメート)、NAC(1‐ナフチル‐N‐メチルカーバメート)、ピラクロホス((RS)‐〔O‐1‐(4‐クロロフェニル)ピラゾール‐4‐イル〕‐O‐エチル‐S‐プロピル‐ホスホロチオエート)、ブプロフェジン(2‐tert‐ブチルイミノ‐3‐イソプロピル‐5‐フェニル‐3,4,5,6‐テトラヒドロ‐2H‐1,3,5‐チアジアジン‐4‐オン)、フルシトリネート((RS)‐α‐シアノ‐3‐フェノキシベンジル‐(S)‐2‐(4‐ジフルオロメトキシフェニル)‐3‐メチルブチラート)、メソミル(S‐メチル‐N‐〔(メチルカルバモイル)オキシ〕チオアセトイミデート)、エトフェンプロックス(2‐(4‐エトキシフェニル)‐2‐メチルプロピル‐3‐フェノキシベンジル−エーテル)、XMC(3,5‐キシリル‐N‐メチルカーバメート)などが挙げられる。殺菌活性成分としては、IBP(O,O‐ジイソプロピル‐S‐ベンジルチオホスフェート)、トリシクラゾール(5‐メチル‐1,2,4−トリアゾロ〔3,4−b〕ベンゾチアゾール)、フサライド(4,5,6,7‐テトラクロロフタリド)、バリダマイシン、プロベナゾール(3‐アリルオキシ‐1,2‐ベンゾイソチアゾール‐1,1‐ジオキシド)、フェリムゾン((Z)‐2'‐メチルアセトフェノン=4,6‐ジメチルピリミジン‐2‐イルヒドラジン)、フルトラニル(α,α,α‐トリフルオロ‐3'‐イソプロポキシ‐O‐トルアニリド)、フラメトピル((RS)‐5‐クロロ‐N‐(1,3‐ジヒドロ‐1,1,3‐トリメチルイソベンゾフラン‐4‐イル)‐1,3‐ジメチルピラゾール‐4‐カルボキサミド、ペンシクロン(1‐(4‐クロロベンジル)‐1‐シクロペンチル‐3‐フェニル尿素、ジクロメジン(6‐(3,5‐ジクロロ‐4‐メチルフェニル)‐3(2H)‐ピリダジノン)、カスガマイシン一塩酸塩などが挙げられる。また、2種以上の農薬活性成分を本発明の農薬粒剤に含有させる場合には、農薬活性成分の種類によっては農薬活性成分が脂肪酸及び/又は脂肪酸誘導体の内部構造を粗くする作用が生じる場合があり、この場合、農薬活性成分が水中溶出を調整する効果を発揮する。そのため所望の溶出制御を発現させるためには、用いる農薬活性成分の種類及びその含有量を調整することが好ましい。 When nereistoxin-based insecticides and neonicotinoid-based insecticides, which are the preferred pesticidal active ingredients, are applied, one or more of them should be used in combination as long as they do not affect the chemical stability. Can do. Specific examples of preferable concomitant drugs that can be used in combination with nereistoxin insecticides and neonicotinoid insecticides include the following. For example, pesticidal active ingredients include BPMC (2-sec-butylphenyl-N-methylcarbamate), MIPC (2-isopropylphenyl-N-methylcarbamate), NAC (1-naphthyl-N-methylcarbamate), pyraclophos (( RS)-[O-1- (4-chlorophenyl) pyrazol-4-yl] -O-ethyl-S-propyl-phosphorothioate), buprofezin (2-tert-butylimino-3-isopropyl-5-phenyl-3,4 , 5,6-tetrahydro-2H-1,3,5-thiadiazin-4-one), flucitrinate ((RS) -α-cyano-3-phenoxybenzyl- (S) -2- (4-difluoromethoxy) Phenyl) -3-methylbutyrate), mesomil (S-methyl-N-[(methylcarbamoyl)) Xy] thioacetimidate), etofenprox (2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl-ether), XMC (3,5-xylyl-N-methylcarbamate), etc. It is done. Bactericidal active ingredients include IBP (O, O-diisopropyl-S-benzylthiophosphate), tricyclazole (5-methyl-1,2,4-triazolo [3,4-b] benzothiazole), and fusalide (4,5 , 6,7-tetrachlorophthalide), validamycin, probenazole (3-allyloxy-1,2-benzisothiazole-1,1-dioxide), ferimzone ((Z) -2′-methylacetophenone = 4,6- Dimethylpyrimidin-2-ylhydrazine), flutolanil (α, α, α-trifluoro-3'-isopropoxy-O-toluanilide), furametopyl ((RS) -5-chloro-N- (1,3-dihydro-) 1,1,3-trimethylisobenzofuran-4-yl) -1,3-dimethylpyrazole-4-carboxamide, pe Cyclone (1- (4-chlorobenzyl) -1-cyclopentyl-3-phenylurea, dichromedin (6- (3,5-dichloro-4-methylphenyl) -3 (2H) -pyridazinone), kasugamycin monohydrochloride, etc. In addition, when two or more kinds of pesticidal active ingredients are contained in the pesticidal granules of the present invention, the pesticidal active ingredient roughens the internal structure of the fatty acid and / or fatty acid derivative depending on the type of the pesticidal active ingredient. In this case, the pesticidal active ingredient exerts the effect of adjusting the elution in water, so in order to express the desired elution control, the type and content of the pesticidal active ingredient to be used should be adjusted. Is preferred.
本発明の農薬粒剤中の農薬活性成分の含有割合は、通常3.0〜25.0質量%、好ましくは4.0〜15.0質量%である。粒剤中の含有量が3.0質量%に満たない場合は農薬活性成分の十分な効力発現が期待できず、25質量%を超えると農薬活性成分の水中への溶出を十分に制御し得ないために、長期の残効を期待できない。 The content ratio of the pesticidal active ingredient in the pesticidal granules of the present invention is usually 3.0 to 25.0% by mass, preferably 4.0 to 15.0% by mass. If the content in the granule is less than 3.0% by mass, sufficient efficacy of the agrochemical active ingredient cannot be expected, and if it exceeds 25% by mass, the elution of the agrochemical active ingredient into water can be controlled sufficiently. Therefore, long-term aftereffects cannot be expected.
本発明の農薬粒剤は、脂肪酸及び/又は脂肪酸誘導体が製剤基材の一つとして適用される。当該脂肪酸及び脂肪酸誘導体は加工性に優れており、溶融等の加熱工程を経なくても混合及び押出造粒によって均一で所望の粒径及び粒長の粒剤に調製することができる。そのため脂肪酸及び/又は脂肪酸誘導体と農薬活性成分、無機物質、及びその他任意の原材料を均一に混合する場合、加熱溶融し混合する工程を経ることなく農薬粒剤を製造することができ、熱に不安定な農薬活性成分にも適用できる。
本発明に使用できる脂肪酸及び脂肪酸誘導体は、農薬活性成分に対して不活性であれば特に限定されずに使用することができる。本発明に好適な脂肪酸及び脂肪酸誘導体は、C8〜C40アルキル鎖カルボン酸及びその誘導体である。より好ましくはC10〜C30アルキル鎖カルボン酸及びその誘導体である。これらの脂肪酸及び脂肪酸誘導体は、総じて常温固体のものであり、農薬活性成分を含浸保持する粒剤基材として適用できるものである。粒剤調製における加工性及びその後の加熱処理工程条件を勘案すると、当該脂肪酸及び脂肪酸誘導体の融点が45〜100℃の範囲の物性のものが特に好適に使用され得る。より好ましくは、融点が50〜90℃の範囲の脂肪酸及び脂肪酸誘導体が優れた物性の粒剤を調製し得る。
In the agrochemical granule of the present invention, fatty acids and / or fatty acid derivatives are applied as one of the preparation bases. The fatty acid and the fatty acid derivative are excellent in processability, and can be prepared into granules having a desired particle size and length by mixing and extrusion granulation without passing through a heating step such as melting. Therefore, when the fatty acid and / or fatty acid derivative and the agrochemical active ingredient, inorganic substance, and other arbitrary raw materials are mixed uniformly, the agrochemical granule can be produced without going through the process of heating, melting and mixing, and it is insensitive to heat. It can also be applied to stable agrochemical active ingredients.
The fatty acid and fatty acid derivative that can be used in the present invention can be used without particular limitation as long as they are inactive with respect to the pesticidal active ingredient. Fatty acids and fatty acid derivatives suitable for the present invention are C8-C40 alkyl chain carboxylic acids and derivatives thereof. More preferred are C10 to C30 alkyl chain carboxylic acids and derivatives thereof. These fatty acids and fatty acid derivatives are generally solid at room temperature and can be applied as a granule base material impregnated and held with an agrochemical active ingredient. Considering the processability in granule preparation and subsequent heat treatment process conditions, those having physical properties in which the melting point of the fatty acid and fatty acid derivative is in the range of 45 to 100 ° C. can be used particularly suitably. More preferably, it is possible to prepare granules having excellent physical properties of fatty acids and fatty acid derivatives having a melting point in the range of 50 to 90 ° C.
脂肪酸の具体例としては、ステアリン酸(融点約70℃)、ミリスチン酸(融点約54℃)、ベヘン酸(融点約80℃)、パルミチン酸(融点約63℃)、ラウリン酸(融点約45℃)、等が挙げられる。脂肪酸誘導体の具体例としては、12‐ヒドロキシステアリン酸(融点約75℃)が挙げられる。更には、牛硬化油(融点40〜50℃)、ヒマシ硬化油(融点75〜90℃)、大豆硬化油(融点50〜65℃)、パーム硬化油(融点40〜45℃)、菜種硬化油(融点60〜65℃)といった動物性油脂若しくは植物性油脂等の脂肪酸エステルを水素添加して得られた硬化油なども含まれる。前記例示した脂肪酸及び脂肪酸誘導体の単独使用や、これらの中から選ばれる2種以上の混合物を任意に組み合わせて使用することもできる。2種類以上の脂肪酸及び脂肪酸誘導体を混合物として使用することにより、加工性が向上し、尚且つ好ましい融点範囲に調整することが可能となる。またこれら脂肪酸及び脂肪酸誘導体の選択が、当該農薬粒剤の農薬活性成分の溶出特性に大きく影響を及ぼすものであり、農薬活性成分の至適有効濃度及び時間に応じ、適宜選択し使用することが好ましい。
本発明に係る脂肪酸及び/又は脂肪酸誘導として、ヒマシ硬化油単独、ヒマシ硬化油とステアリン酸の組合せ、または牛硬化油とステアリン酸の組合せが農薬活性成分の良好な溶出性を示すことから好ましい。これら好適な脂肪酸及び/又は脂肪酸誘導体は、加工性や農薬活性成分との相溶性に優れ、優れた粒剤性能を発揮させる製剤基材である。特にヒマシ硬化油は、融点が最も高く熱化学的安定性に優れる点で、本発明に係る農薬粒剤の好適な主基材として選択される脂肪酸及び脂肪酸誘導体として挙げることができる。
また前記の脂肪酸及び/又は脂肪酸誘導体と共に、ヒマシ油、菜種油、パーム油、大豆油、綿実油、亜麻仁油等の常温液体性の植物性脂肪酸誘導体を適宜添加することは、本願に係る農薬粒剤の造粒性が向上する事から好ましい。しかしながら当該植物性脂肪酸誘導体の混用は、当該粒剤硬度を低下させる懸念もあることから、その添加は粒剤中に0.05〜10質量%の範囲において用いられるものである。当該粒剤の造粒性向上と粒硬度の両立の観点から、当該農薬粒剤中で0.1〜5質量%の適用がより好ましい。
脂肪酸及び/又は脂肪酸誘導体は、本発明の農薬粒剤中に10〜80質量%の割合で含有させることができる。好ましくは20〜70質量%である。10質量%未満では脂肪酸及び脂肪酸誘導体による溶出制御効果が期待できず、また農薬粒剤の形状に成形することが困難となる。また80質量%を超えると、農薬活性成分が十分に水中に溶出されず、粒剤中に農薬活性成分が残留するため、十分な効果が発揮できない可能性がある。本発明に係る農薬粒剤において、脂肪酸及び/又は脂肪酸誘導体の含量を多くすると薬剤溶出速度が遅く制御された粒剤を調製できる。逆に脂肪酸及び/又は脂肪酸誘導体の含量を少なくすると、早い薬剤溶出パターンを示す粒剤を調製できる。
Specific examples of fatty acids include stearic acid (melting point: about 70 ° C.), myristic acid (melting point: about 54 ° C.), behenic acid (melting point: about 80 ° C.), palmitic acid (melting point: about 63 ° C.), lauric acid (melting point: about 45 ° C.) ), And the like. Specific examples of the fatty acid derivative include 12-hydroxystearic acid (melting point: about 75 ° C.). Furthermore, beef hydrogenated oil (melting point 40-50 ° C), castor oil (melting point 75-90 ° C), soybean hardened oil (melting point 50-65 ° C), palm hardened oil (melting point 40-45 ° C), rapeseed hydrogenated oil Also included are hardened oils obtained by hydrogenating fatty acid esters such as animal oils or vegetable oils (melting point 60-65 ° C.). The fatty acids and fatty acid derivatives exemplified above can be used alone, or a mixture of two or more selected from these can be used in any combination. By using two or more kinds of fatty acids and fatty acid derivatives as a mixture, processability is improved and it is possible to adjust to a preferable melting point range. In addition, the selection of these fatty acids and fatty acid derivatives greatly affects the elution characteristics of the pesticidal active ingredient of the pesticidal granule, and can be appropriately selected and used according to the optimum effective concentration and time of the pesticidal active ingredient. preferable.
As the fatty acid and / or fatty acid derivative according to the present invention, castor oil hardened alone, a combination of castor oil hardened and stearic acid, or a combination of cow hardened oil and stearic acid is preferable because it shows good dissolution properties of the agrochemical active ingredient. These suitable fatty acids and / or fatty acid derivatives are preparation bases that are excellent in processability and compatibility with agrochemical active ingredients and exhibit excellent granule performance. Especially castor hydrogenated oil can be mentioned as a fatty acid and a fatty acid derivative selected as a suitable main base material of the agrochemical granule according to the present invention in that it has the highest melting point and excellent thermochemical stability.
In addition to the above fatty acids and / or fatty acid derivatives, the addition of room temperature liquid vegetable fatty acid derivatives such as castor oil, rapeseed oil, palm oil, soybean oil, cottonseed oil, linseed oil, etc. It is preferable because the granulation property is improved. However, since the mixed use of the vegetable fatty acid derivative may cause a decrease in the granule hardness, the addition thereof is used in the range of 0.05 to 10% by mass in the granule. Application of 0.1 to 5% by mass in the agrochemical granule is more preferable from the standpoint of improving the granulation property and the particle hardness of the granule.
Fatty acids and / or fatty acid derivatives can be contained in the agrochemical granule of the present invention in a proportion of 10 to 80% by mass. Preferably it is 20-70 mass%. If it is less than 10 mass%, the elution control effect by a fatty acid and a fatty acid derivative cannot be expected, and it becomes difficult to form the shape of an agrochemical granule. If it exceeds 80% by mass, the pesticidal active ingredient is not sufficiently dissolved in water, and the pesticidal active ingredient remains in the granule, so that a sufficient effect may not be exhibited. In the agrochemical granule according to the present invention, when the content of fatty acid and / or fatty acid derivative is increased, a granule in which the drug elution rate is controlled slowly can be prepared. On the contrary, if the content of fatty acid and / or fatty acid derivative is decreased, a granule showing a fast drug elution pattern can be prepared.
本発明の農薬粒剤は無機物質を含有する。当該無機物質は、本発明に係る農薬粒剤の内部の構造を粗くする作用を有し、粒剤内部に分散存在する農薬活性成分の水中への溶出を促進するとともに、その溶出速度を適宜調整する機能を担うものである。更に、当該農薬粒剤の比重を調整し、当該農薬粒剤の水中沈降性を付与させるものである。脂肪酸及び/又は脂肪酸誘導体を製剤基材として適用した農薬粒剤は、基材の比重が1に近く、その比重軽さと基材由来の撥水性によって、水田等の湛水圃場に散布した場合、該粒剤が水面に浮遊する。水面に浮遊した該粒剤は、風の影響を受けて圃場の一部に局在化して効力が不均一になるだけでなく、水流の影響を受けて圃場から流亡し、期待される効力を発揮できないおそれがある。当該無機物質は、比重の軽さによる効力不均一及び効力低下を防ぐために機能するものであり、水田等の湛水圃場に散布した場合に速やかに水中に沈降させる作用を付与させるものである。
本発明に用いられる無機物質はクレー、珪石、タルク、白土、珪藻土、アッシュメント、非晶質二酸化珪素(通称:ホワイトカーボン)、硫酸バリウム、二酸化チタン、塩化ナトリウム、塩化カリウムなどから選ばれる1種または2種以上の組合せで用いられるが、農薬活性成分の安定性を損なうものでなければこれに限るものではない。無機物質の粒径は様々なものが使用できるが、その中でも20μm〜200μmのものが製造上及び/又は農薬活性成分の溶出を促す作用を導き出すのに好ましい。
当該無機物質は本発明の農薬粒剤中に10〜60質量%の割合で含有させることができる。好ましくは20〜50質量%である。10質量%未満では比重調整の効果が期待できず、60質量%を超えると農薬活性成分の溶出制御が困難となるばかりでなく、農薬粒剤としての形状に成形することが難しくなる。
The agrochemical granule of the present invention contains an inorganic substance. The inorganic substance has the effect of roughening the internal structure of the agrochemical granule according to the present invention, promotes the elution of agrochemical active ingredients dispersed in the granule into water, and appropriately adjusts the elution rate. It bears the function to perform. Furthermore, the specific gravity of the pesticide granule is adjusted, and the sedimentation property of the pesticide granule is imparted. Agrochemical granules in which fatty acids and / or fatty acid derivatives are applied as formulation bases, the specific gravity of the base material is close to 1, and due to the lightness of the specific gravity and water repellency derived from the base material, when sprayed on flooded fields such as paddy fields, The granules float on the water surface. The granules floating on the surface of the water are not only localized in a part of the field under the influence of the wind and become non-uniform in efficacy, but also run away from the field under the influence of the water flow and have the expected efficacy. There is a possibility that it cannot be demonstrated. The said inorganic substance functions in order to prevent the non-uniformity of effect and the effect fall by the lightness of specific gravity, and when it sprays on the flooded fields, such as a paddy field, it gives the effect | action to settle in water rapidly.
The inorganic substance used in the present invention is one selected from clay, silica, talc, white clay, diatomaceous earth, ashment, amorphous silicon dioxide (common name: white carbon), barium sulfate, titanium dioxide, sodium chloride, potassium chloride, and the like. Or it is used in combination of 2 or more types, but is not limited to this as long as it does not impair the stability of the agrochemical active ingredient. Various inorganic particle diameters can be used. Among them, those having a particle size of 20 μm to 200 μm are preferable for deriving the effect of promoting the elution of the agrochemical active ingredient in production and / or agricultural chemicals.
The said inorganic substance can be contained in the ratio of 10-60 mass% in the agrochemical granule of this invention. Preferably it is 20-50 mass%. If it is less than 10% by mass, the effect of adjusting the specific gravity cannot be expected. If it exceeds 60% by mass, it becomes difficult not only to control the elution of the pesticidal active ingredient but also to form it into a shape as an agrochemical granule.
本発明の農薬粒剤は任意成分として界面活性剤を含有し得るものである。当該界面活性剤は、ノニオン性及び/又はアニオン性界面活性剤が適用される。アニオン性界面活性剤及び/又はノニオン性界面活性剤は、湛水圃場に本発明に係る農薬粒剤を散布した際、その水親和性によって本発明の農薬粒剤の撥水性を抑えて水中沈降性を改善し、速やかに水中に沈降する機能を付与させるものである。また、本発明に用いられる界面活性剤は、当該農薬粒剤の親水性を高めて、粒内部に存在する農薬活性成分の水中への溶出を適宜調整する役割をも有する。本発明に用いられるノニオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンアルキルエステル、ポリオキシエチレンフェニルエーテルポリマー、ポリオキシエチレンアルキレンアリールフェニルエーテル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ポリオキシエチレン化ヒマシ油、ポリオキシエチレン化硬化ヒマシ油、ポリオキシエチレンソルビタンモノオレート、グリセリルモノステアレート、グリセリルジステアレートなどが挙げられる。アニオン性界面活性剤としては、ポリオキシエチレンスチリルフェニルエーテルサルフェート、リグニンスルホン酸塩、アルキルアリールスルホン酸塩、アルキルナフタレンスルホン酸塩等が挙げられる。農薬活性成分の安定性を損なうものでなければこれら例示物質に限るものではない。これらノニオン性及びアニオン性界面活性剤の群より選ばれる1種又は2種以上の組合せによって水中沈降性効果を発揮することができる。
当該界面活性剤がその効果を発揮する使用の形態は、農薬活性成分やその他原材料と共に混合して押出造粒して農薬粒剤に形成してもよいし、農薬活性成分やその他原材料を混合、押出造粒してできた農薬粒剤の粒表面に界面活性剤を均一にコーティングすることも可能である。また、その両方を併用することも可能である。
当該界面活性剤は本発明の農薬粒剤中に0.1〜10質量%の割合で含有させることができる。より好ましくは0.3%〜10質量%である。0.1質量%未満では当該農薬粒剤を水中に沈降させるには足りず、10質量%を超えると良好な水中沈降性は得られるものの、界面活性剤によって農薬活性成分の水中溶出速度が大幅に促進されるため、溶出制御が困難になる。
The agrochemical granule of the present invention can contain a surfactant as an optional component. As the surfactant, a nonionic and / or anionic surfactant is applied. When an anionic surfactant and / or a nonionic surfactant is sprayed with a pesticide granule according to the present invention in a flooded field, its water affinity suppresses the water repellency of the pesticide granule according to the present invention and settles in water. It improves the property and imparts a function to quickly settle in water. The surfactant used in the present invention also has a role of increasing the hydrophilicity of the agrochemical granule and appropriately adjusting the elution of the agrochemical active ingredient present in the grain into water. Nonionic surfactants used in the present invention include polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene phenyl ether polymer, polyoxyethylene alkylene aryl phenyl ether, polyoxyethylene Examples include polyoxypropylene block polymer, polyoxyethylenated castor oil, polyoxyethylenated hydrogenated castor oil, polyoxyethylene sorbitan monooleate, glyceryl monostearate, glyceryl distearate and the like. Examples of the anionic surfactant include polyoxyethylene styryl phenyl ether sulfate, lignin sulfonate, alkyl aryl sulfonate, and alkyl naphthalene sulfonate. Unless it impairs the stability of the agrochemical active ingredient, it is not limited to these exemplified substances. An underwater sedimentation effect can be exhibited by one or a combination of two or more selected from the group of these nonionic and anionic surfactants.
The form of use in which the surfactant exerts its effect may be formed by mixing with an agrochemical active ingredient and other raw materials and extrusion granulation to form an agrochemical granule, or mixing an agrochemical active ingredient and other raw materials, It is also possible to uniformly coat the surface of the particles of the agrochemical granules produced by extrusion granulation with a surfactant. Moreover, it is also possible to use both together.
The said surfactant can be contained in the ratio of 0.1-10 mass% in the agrochemical granule of this invention. More preferably, it is 0.3% to 10% by mass. If the amount is less than 0.1% by mass, the pesticidal granule is not sufficient to settle in water. If the amount exceeds 10% by mass, good water sedimentation can be obtained, but the surfactant can significantly increase the rate of dissolution of the pesticidal active ingredient in water. Therefore, elution control becomes difficult.
本発明の無機物質及び/又は界面活性剤は、当該農薬粒剤に良好な水中沈降性を付与すると共に、農薬活性成分の水中溶出速度を調整する役割を果たしている。無機物質及び/又は界面活性剤の含有量を適宜調整することにより、粒剤への成形を困難にすることなく良好な水中沈降性を保ちつつ所望の水中溶出速度を有する農薬粒剤を得ることができる。通常、本発明の農薬粒剤は農薬活性成分を3〜25質量%、脂肪酸及び/又は脂肪酸誘導体を10〜80質量%、無機物質を10〜60質量%を含有し、この範囲内で適宜調整することで所望の水中溶出速度を得ることができる。加えて、当該農薬粒剤には界面活性剤を0.1〜10質量%の割合で含有することができ、当該農薬粒剤の水中沈降性ならびに農薬活性成分の水中溶出速度を適宜調整することができる。界面活性剤は、農薬活性成分、脂肪酸及び/又は脂肪酸誘導体、無機物質で構成される農薬粒剤の、粒表面にコーティングして適用される。また、界面活性剤を農薬組成物中に合わせて混合し、これを造粒する形態も挙げられる。若しくは、界面活性剤を含んだ農薬組成物造粒体に、更に粒表面に界面活性剤をコーティングして適用される。 The inorganic substance and / or surfactant of the present invention plays a role of adjusting the dissolution rate of agrochemical active ingredients in water as well as imparting good subsidence in water to the agrochemical granule. By appropriately adjusting the content of the inorganic substance and / or surfactant, it is possible to obtain an agrochemical granule having a desired dissolution rate in water while maintaining good sedimentation without making it difficult to form into a granule. Can do. Usually, the agrochemical granule of the present invention contains 3 to 25% by mass of an agrochemical active ingredient, 10 to 80% by mass of a fatty acid and / or a fatty acid derivative, and 10 to 60% by mass of an inorganic substance, and is appropriately adjusted within this range. By doing so, a desired dissolution rate in water can be obtained. In addition, the pesticide granule may contain a surfactant in a proportion of 0.1 to 10% by mass, and the water sedimentation rate of the pesticide granule and the elution rate of the pesticide active ingredient in water should be adjusted as appropriate. Can do. The surfactant is applied by coating on the grain surface of an agrochemical granule composed of an agrochemical active ingredient, a fatty acid and / or a fatty acid derivative, and an inorganic substance. Moreover, the form which mix | blends surfactant and mixes in an agrochemical composition, and granulates this is also mentioned. Alternatively, it is applied to a granulation body of an agrochemical composition containing a surfactant and further coated with a surfactant on the particle surface.
本発明の農薬粒剤は、前記農薬組成物(農薬活性成分、脂肪酸及び/又は脂肪酸誘導体、無機物質、必要により界面活性剤、及び水難溶性多糖類)を混合し、粒状に造粒する事により成形されるものである。粒状に造粒する方法は特に限定されるものではないが、前記農薬組成物の混合物を調製し、これを押出成形する方法が、粒剤成形方法及び製造操作上において好ましい。当該農薬粒剤は、前記農薬組成物の混合物を押出造粒機によって圧縮形成することにより得られるものであり、水や結合剤といった形成助剤の使用、若しくは製剤基材溶融工程を必要としない。したがって、水や熱による分解が懸念される比較的化学的安定性が低い農薬活性成分の、造粒成形にも適用できるものである。
本発明の農薬粒剤の成形体調製工程に用いられる押出造粒機は、縦型押出造粒機が好ましく、原材料をよく混合した後に当該造粒機に投入して造粒する。このとき、ダイスの厚さが10mm以上、粒剤粒径が2〜10mmであることが粒剤を製造する上で重要になる。ダイスの厚さが10mmに満たない場合、原材料にかかる圧力が足りず粒剤としての形に成形することが困難となる。また、粒径が2〜10mmの範囲外の場合、やはり原材料にかかる圧力が足りず粒剤として成形することが難しくなる。縦型押出造粒機は、一般に被造粒組成物に圧力をかけて水平に設置されたダイスから押出して造粒する機器の一般名称で、ディスクペレッター(不二パウダル社製)等が挙げられる。
The agrochemical granule of the present invention is prepared by mixing the agrochemical composition (pesticidal active ingredient, fatty acid and / or fatty acid derivative, inorganic substance, surfactant if necessary, and poorly water-soluble polysaccharide) and granulating it into granules. It is to be molded. The method of granulating into granules is not particularly limited, but a method of preparing a mixture of the agrochemical composition and extruding the mixture is preferable in terms of the granule molding method and manufacturing operation. The agrochemical granule is obtained by compression-forming the mixture of the agrochemical composition with an extrusion granulator, and does not require the use of a forming aid such as water or a binder, or a preparation base material melting step. . Therefore, it can be applied to granulation molding of an agrochemical active ingredient with relatively low chemical stability, which is feared to be decomposed by water or heat.
The extrusion granulator used in the molded product preparation step of the agrochemical granule according to the present invention is preferably a vertical extrusion granulator, and after mixing raw materials well, it is put into the granulator and granulated. At this time, it is important to manufacture the granule that the thickness of the die is 10 mm or more and the particle size of the granule is 2 to 10 mm. When the thickness of the die is less than 10 mm, the pressure applied to the raw material is insufficient, and it becomes difficult to form into a shape as a granule. Moreover, when the particle size is outside the range of 2 to 10 mm, the pressure applied to the raw materials is still insufficient, and it becomes difficult to form the granules. A vertical extrusion granulator is a general name for a device that is generally granulated by extruding from a horizontally installed die by applying pressure to the composition to be granulated, and includes a disk pelleter (manufactured by Fuji Powder Co., Ltd.). It is done.
農薬組成物を造粒する際、その粒剤粒径は好ましくは2〜10mmが適用される。2mm未満では造粒の際に当該農薬組成物にかかる圧力が足りず、粒剤としての形に成形することが困難となる。また、水田に散布する際に風などの影響を受けて当該農薬粒剤が狙う水田以外の畦畔等に落下するおそれがある。10mmを超える場合も造粒が難しくなるばかりか、単位面積当たりの散布粒数が少なくなり散布ムラや効力が不均一化する等の問題が起きるおそれがある。 When granulating the agricultural chemical composition, the particle size of the granule is preferably 2 to 10 mm. If it is less than 2 mm, the pressure applied to the agrochemical composition is insufficient at the time of granulation, and it becomes difficult to form it into a form as a granule. Moreover, when spraying on a paddy field, there exists a possibility that it may fall to the shore etc. other than the paddy field which the said agrochemical granule aims at under the influence of a wind. When it exceeds 10 mm, not only granulation becomes difficult, but the number of sprayed particles per unit area decreases, and there may be problems such as uneven spraying and non-uniform effects.
本発明の農薬粒剤は、前記農薬組成物を混合し、押出成形方法により粒状に造粒する事により成形されるものである。しかしながら、造粒工程においてできた造粒物の粒硬度が一定せず、硬度の低い粒が少量ながら混在する場合がある。本発明に係る脂肪酸及び/又は脂肪酸誘導体は、加工性において良好な物性である半面、得られる粒剤成形体の粒硬度不足が生じる場合がある。このような現象を改善し、溶融工程を経ずに十分な硬度を持った均質な粒剤を得る方法として、脂肪酸及び/又は脂肪酸誘導体と農薬活性成分、並びに無機物質を良く混合したものを押出造粒機で造粒した後、得られた造粒物を、用いた脂肪酸及び/又は脂肪酸誘導体の融点以下の温度で加熱処理する工程を採用することで、得られる粒剤硬度が向上することを見出した。加熱処理工程を経ることにより、当該農薬粒剤成形体中で分断されていた脂肪酸及び/又は脂肪酸誘導体が、効果的なネットワークを構築することにより粒硬度が向上するものと考えられる。
粒状成形体の加熱処理は、恒温槽や流動層乾燥機により施されれるものであるが、当該粒状成形体が一様に加熱される機器であればこれに限るものではない。なお、本明細書で言う加熱温度は、粒を包囲する雰囲気の温度を指すものとする。従って、恒温槽の場合は、目的の温度になったことを確認した後、当該農薬組成物の造粒物を槽内に所望の時間だけ静置する。流動層乾燥機の場合は流動層内に当該農薬組成物の造粒物を投入し、運転開始後、流動槽内が目的とする温度で一定となってから適切な時間、流動層内で加熱処理を行う。加熱温度は室温以上であり、より好ましくは35℃以上、更に好ましくは40℃以上であり、粒剤を構成する脂肪酸及び/又は脂肪酸誘導体の融点以下である必要がある。製剤基材として採用する脂肪酸及び/又は脂肪酸誘導体がC8〜C40アルキル鎖カルボン酸である場合、加熱処理温度は40〜90℃にて行なわれる。
より具体的な例として、脂肪酸及び/又は脂肪酸誘導体がヒマシ硬化油、ヒマシ油、及びステアリン酸の混合物である場合、加熱処理温度は50℃以上で80℃より低い温度であり、好ましくは75℃以下である。より好ましくは50〜75℃であり、更に好ましくは55〜70℃である。80℃以上では当該農薬粒剤成形体の表面が融解し、粒剤同士付着してブロッキング現象を起こしてしまい農薬粒剤として不具合をもたらす。また50℃未満では、加熱による当該農薬粒剤の構造改良の効果は期待できない。粒の加熱時間は、少なくとも当該粒表面が改質されるごく短時間で良い。加熱時間は加熱処理機器の性能容量にも依存するものであるが、60分以内が適切である。好ましくは15秒以上で45分以内であり、より好ましくは30秒以上で30分以内である。
The agrochemical granule of the present invention is formed by mixing the agrochemical composition and granulating it into granules by an extrusion method. However, the particle hardness of the granulated product formed in the granulation step is not constant, and a small amount of low hardness particles may be mixed. The fatty acid and / or fatty acid derivative according to the present invention, which has good physical properties in processability, may result in insufficient grain hardness of the obtained granule molded product. As a method of improving such a phenomenon and obtaining a homogeneous granule having sufficient hardness without going through a melting step, a mixture of a fatty acid and / or fatty acid derivative, an agrochemical active ingredient, and an inorganic substance is mixed. After granulating with a granulator, the granule hardness obtained is improved by adopting a step of heat-treating the obtained granulated product at a temperature below the melting point of the fatty acid and / or fatty acid derivative used. I found. By passing through the heat treatment step, it is considered that the fatty acid and / or the fatty acid derivative that has been divided in the agrochemical granule molded body improves the particle hardness by constructing an effective network.
The heat treatment of the granular formed body is performed by a thermostatic bath or a fluidized bed dryer, but is not limited to this as long as the granular formed body is uniformly heated. In addition, the heating temperature said by this specification shall point out the temperature of the atmosphere which surrounds a grain. Therefore, in the case of a thermostatic bath, after confirming that the target temperature is reached, the granulated product of the agricultural chemical composition is allowed to stand in the bath for a desired time. In the case of a fluidized bed dryer, the granulated product of the agrochemical composition is charged into the fluidized bed, and after the start of operation, the fluidized tank is heated to the desired temperature and heated in the fluidized bed for an appropriate time. Process. The heating temperature is room temperature or higher, more preferably 35 ° C. or higher, still more preferably 40 ° C. or higher, and needs to be lower than the melting point of the fatty acid and / or fatty acid derivative constituting the granule. When the fatty acid and / or fatty acid derivative employed as the preparation base is a C8 to C40 alkyl chain carboxylic acid, the heat treatment temperature is 40 to 90 ° C.
As a more specific example, when the fatty acid and / or fatty acid derivative is a mixture of castor oil, castor oil, and stearic acid, the heat treatment temperature is 50 ° C. or higher and lower than 80 ° C., preferably 75 ° C. It is as follows. More preferably, it is 50-75 degreeC, More preferably, it is 55-70 degreeC. Above 80 ° C., the surface of the agrochemical granule molded body melts and adheres to each other to cause a blocking phenomenon, resulting in a defect as an agrochemical granule. Moreover, if it is less than 50 degreeC, the effect of the structure improvement of the said agrochemical granule by heating cannot be expected. The heating time for the grains may be at least a very short time during which the grain surface is modified. The heating time depends on the performance capacity of the heat treatment apparatus, but is preferably within 60 minutes. Preferably, it is 15 seconds or longer and within 45 minutes, more preferably 30 seconds or longer and within 30 minutes.
上記の加熱処理工程は粒硬度増強作用だけでなく、農薬製剤散布直後における、初期の農薬有効成分の過剰溶出を抑制する働きがある。縦型押出造粒機による造粒で得られた粒の底面は切断面で形成されており、表面が粗く当該農薬粒剤表面積が大きい。更には粒剤の粗表面は粒剤内部への水の侵入を許し、溶出速度、特に散布直後の溶出速度を速める傾向がある。当該農薬粒剤を、用いた脂肪酸及び/又は脂肪酸誘導体の融点以下の温度で加熱処理することにより、農薬粒剤基材の表面が融解し表面改質され、粒をあたかも継ぎ目のないカプセルのようにすることができる。この結果、当該農薬粒剤の散布直後における薬剤過剰溶出を抑制できる。必要以上の農薬活性成分を散布直後の一時に溶出させず、長期間効力を持続させることができる効果を発揮する。 The above heat treatment process not only has an effect of enhancing grain hardness, but also functions to suppress excessive elution of the initial agricultural chemical active ingredient immediately after the application of the agricultural chemical formulation. The bottom surface of the granule obtained by granulation by a vertical extrusion granulator is formed by a cut surface, and the surface is rough and the surface area of the agricultural chemical granule is large. Furthermore, the rough surface of the granule allows water to enter the granule and tends to increase the elution rate, particularly the elution rate immediately after spraying. By heat-treating the agrochemical granule at a temperature below the melting point of the fatty acid and / or fatty acid derivative used, the surface of the agrochemical granule base material is melted and surface-modified, so that the grains look like seamless capsules. Can be. As a result, it is possible to suppress excessive drug elution immediately after application of the agrochemical granule. Exhibits more than necessary pesticidal active ingredients at a time immediately after spraying and exerts the effect of maintaining efficacy for a long time.
本発明に係る農薬粒剤は、更に粒硬度を向上させることを目的として製剤中に水難溶性多糖類を加えることができる。水難溶性多糖類は、脂肪酸及び/又は脂肪酸誘導体を基材とする当該農薬粒剤中でネットワークを形成して、粒の硬度を高める機能を有する。更に圧縮成形性を付与して、押出造粒による圧縮で硬度を持った粒剤が得られる。粒剤の加熱処理により当該農薬粒剤の粒硬度は向上するが、水難溶性多糖類を更に添加することにより、当該農薬粒剤の粒硬度は十分に担保されたものとなる。
本発明の農薬粒剤に用いられる水難溶性多糖類としては結晶セルロース、水不溶性ペクチン、キチン・キトサン等が挙げられるが、押出造粒による造粒性を向上し得るもので、当該農薬粒剤中の農薬活性成分の安定性を損なうものでなければこれに限るものではない。水難溶性多糖類の平均粒子径は1〜45μmのものを用いることができる。好ましくは平均粒径5〜20μmである。当該農薬粒剤には水難溶性多糖類を0.5〜20質量%用いることで十分な硬度を与えることができる。0.5質量%未満では水難溶性多糖類による圧縮形成性と硬度を与えることができない。また、20質量%を超えると農薬粒剤としての形状に成形することが難しくなる。
In the agrochemical granule according to the present invention, a poorly water-soluble polysaccharide can be added to the preparation for the purpose of further improving the grain hardness. The poorly water-soluble polysaccharide has a function of forming a network in the agrochemical granule based on a fatty acid and / or a fatty acid derivative to increase the hardness of the grain. Furthermore, a granule having hardness is obtained by imparting compression moldability and compression by extrusion granulation. Although the grain hardness of the agrochemical granule is improved by the heat treatment of the granule, the grain hardness of the agrochemical granule is sufficiently secured by further adding a poorly water-soluble polysaccharide.
Examples of poorly water-soluble polysaccharides used in the agricultural chemical granules of the present invention include crystalline cellulose, water-insoluble pectin, chitin / chitosan, etc., which can improve the granulation properties by extrusion granulation. If it does not impair the stability of the pesticidal active ingredient, it is not limited to this. A poorly water-soluble polysaccharide having an average particle size of 1 to 45 μm can be used. The average particle size is preferably 5 to 20 μm. Sufficient hardness can be given to the said agrochemical granule by using 0.5-20 mass% of poorly water-soluble polysaccharides. If it is less than 0.5% by mass, the compression-forming property and hardness due to the poorly water-soluble polysaccharide cannot be provided. Moreover, when it exceeds 20 mass%, it will become difficult to shape | mold into the shape as an agrochemical granule.
当該農薬粒剤の硬度は、全農が制定した「農薬製剤の製品規格および規格試験法」(昭和62年12月改定)により定められた試験方法により規定される。具体的な試験方法は以下の通りである。当該農薬粒剤100gをボールミル用磁製ポット(内径100×内深100mm)に入れる。次に磁製玉(直径30±2mm、質量35g±3g)を任意に3個取り、3個分の全質量が105gとし、ポットに入れる。ふたをし、予め回転を調整(75rpm)しておいた可変ローラーの上にポットを置き、正しく15分間回転させる。回転が終了したら中身を取り出し、標準篩500μmで篩い、通過した微粉を上皿天秤で量る。硬度は次の式で表され、値の小さいものほど硬度が高いということができる。
硬度(%)=500μm通過微粉量(g)/100(g)×100
前記農薬粒剤硬度試験方法において硬度が不十分である場合、市場流通における製剤保管及び輸送中において、粒が割れたり欠けたりすることが懸念される。その場合、粒剤の総表面積が大きくなり、所望の溶出速度や水沈降性が得られなくなるおそれがある。本発明に係る農薬粒剤は、前記の粒剤硬度試験方法において、粒剤硬度が7.0%以下の物性を示すことを特徴とする。更に過酷な市場流通を考慮すると、粒剤硬度が5.0%以下の物性であることがより好ましい。本発明に係る農薬粒剤は十分な機械強度を示すものであり、輸送及び保管を含めた一般市場流通条件に耐えうる安定性に優れた物性を有する。
The hardness of the agrochemical granule is defined by a test method defined by “Product Standard and Standard Test Method for Agrochemical Formulation” (revised in December 1987) established by Zen-no-no. The specific test method is as follows. 100 g of the agrochemical granule is placed in a magnetic pot for ball mill (inner diameter 100 × inner depth 100 mm). Next, three pieces of porcelain balls (diameter: 30 ± 2 mm, mass: 35 g ± 3 g) are arbitrarily taken, and the total mass of the three pieces is set to 105 g, which is put in a pot. Close the lid, place the pot on the variable roller whose rotation is adjusted in advance (75 rpm), and rotate it correctly for 15 minutes. When the rotation is completed, the contents are taken out, sieved with a standard sieve of 500 μm, and the fine powder that has passed is weighed with an upper pan balance. The hardness is expressed by the following formula, and the smaller the value, the higher the hardness.
Hardness (%) = Amount of fine powder passing through 500 μm (g) / 100 (g) × 100
When the hardness is insufficient in the agrochemical granule hardness test method, there is a concern that the grains may break or chip during storage and transportation of the preparation in the market distribution. In that case, the total surface area of the granule becomes large, and there is a possibility that a desired elution rate and water sedimentation property cannot be obtained. The agrochemical granule according to the present invention is characterized in that, in the above-mentioned granule hardness test method, the granule hardness shows a physical property of 7.0% or less. Further, considering severe market distribution, it is more preferable that the particle hardness is 5.0% or less. The agrochemical granule according to the present invention exhibits sufficient mechanical strength, and has excellent physical properties that can withstand general market distribution conditions including transportation and storage.
本発明の農薬粒剤の好ましい製造方法は以下の2通りがある。
1) 農薬活性成分、脂肪酸及び/又は脂肪酸誘導体、無機物質、及び場合によっては水難溶性多糖類を混合し農薬組成混合物を調製する工程、次いで前記農薬組成混合物を造粒機に投入して粒状成形体に造粒する工程、その後得られた粒状成形体を加熱処理する工程、を含むものである。更にこの加熱処理した農薬粒剤の表面に、界面活性剤をコーティングする工程が任意に加えられる。
2) 農薬活性成分、脂肪酸及び/又は脂肪酸誘導体、無機物質、界面活性剤、及び場合によっては水難溶性多糖類を混合し農薬組成混合物を調製する工程、次いで前記農薬組成混合物を造粒機に投入し粒状成形体に造粒する工程、その後得られた粒状成形体を加熱処理する工程、を含むものである。更にこの加熱処理した農薬粒剤の表面に、界面活性剤をコーティングする工程が任意に加えられる。
There are the following two preferred methods for producing the agrochemical granule of the present invention.
1) A step of preparing an agrochemical composition mixture by mixing agrochemical active ingredients, fatty acids and / or fatty acid derivatives, inorganic substances, and, in some cases, poorly water-soluble polysaccharides, and then introducing the agrochemical composition mixture into a granulator to form granules A step of granulating the body, and a step of heat-treating the granular molded body obtained thereafter. Further, a step of coating a surfactant on the surface of the heat-treated agrochemical granule is optionally added.
2) A step of preparing an agrochemical composition mixture by mixing agrochemical active ingredients, fatty acids and / or fatty acid derivatives, inorganic substances, surfactants and, in some cases, poorly water-soluble polysaccharides, and then introducing the agrochemical composition mixture into the granulator And a step of granulating the granular molded body, and a step of heat-treating the granular molded body obtained thereafter. Further, a step of coating a surfactant on the surface of the heat-treated agrochemical granule is optionally added.
農薬組成混合物を調製する工程において、その混合方法は各農薬組成成分が十分混合できる方法であれば特に限定されない。具体的にはニーダーやスパルタンリューザー、リボンミキサーなどが使用できる。一般的に、押出成形法による農薬粒剤の調製において、農薬活性成分や製剤基材、添加物等の農薬組成物を混合する場合、混練性を高め、各成分を結着させる目的で、水や水溶性高分子バインダー水溶液を加えて混合する。しかしながら、本発明に係る農薬粒剤は、用いる基材が加工性に優れる脂肪酸及び/又は脂肪酸誘導体であり、水を加えることなく十分に混合することができるものである。特に水溶性の農薬活性成分を用いる場合、製剤調製過程において水を添加することは、得られる製剤物性に好ましくない影響を及ぼすことが懸念される。すなわち造粒時の加圧状態で農薬活性成分の少なくとも一部を溶解した水が農薬組成混合物内に均一に分散せず、特に粒剤の表面に薬剤の局在化をもたらし、農薬組成混合物内に農薬活性成分が均一に分散しない現象をもたらす。このため均質な農薬組成混合物が得られず、所望の製剤特性が発揮されないものとなる。したがって本願に係る農薬粒剤の調製の混合工程において水を添加しないことは、製剤特性を発揮させる上で重要である。
農薬組成混合物を造粒する工程は、前記縦型押出造粒機による方法が好ましい。具体的にはディスクペレッターの使用が挙げられる。粒状成形体を加熱処理する工程は、当該粒状成形体雰囲気を所定の温度で維持できる方法であれば特に問題はなく、縦型押出造粒機によって得られた粒状形成体を均一に広げた状態で恒温槽に静置または流動層乾燥機で処理する方法が挙げられる。
上記の方法で得られた粒剤の表面に界面活性剤をコーティングする方法としては、コンクリートミキサーやコーティングパンなどが用いられる。ミキサーに、上記の方法で得られた粒剤、界面活性剤の順に投入し、内部を撹拌することで粒剤表面に均一に界面活性剤をコーティングすることができる。
In the step of preparing the agrochemical composition mixture, the mixing method is not particularly limited as long as each agrochemical composition component can be sufficiently mixed. Specifically, a kneader, a Spartan luzer, a ribbon mixer, etc. can be used. Generally, in the preparation of agrochemical granules by extrusion molding, when mixing agrochemical compositions such as agrochemical active ingredients, formulation bases, and additives, water is added for the purpose of enhancing kneadability and binding each component. Or water-soluble polymer binder aqueous solution is added and mixed. However, the agrochemical granule according to the present invention is a fatty acid and / or fatty acid derivative in which the substrate used is excellent in processability, and can be sufficiently mixed without adding water. In particular, when a water-soluble pesticidal active ingredient is used, there is a concern that adding water in the preparation process may adversely affect the properties of the resulting preparation. That is, water in which at least a part of the pesticidal active ingredient is dissolved in the pressurized state at the time of granulation does not uniformly disperse in the pesticidal composition mixture, and particularly causes localization of the drug on the surface of the granule. This causes a phenomenon that the pesticidal active ingredient is not uniformly dispersed. For this reason, a homogeneous agricultural chemical composition mixture cannot be obtained, and the desired formulation characteristics cannot be exhibited. Therefore, it is important to not add water in the mixing step of preparing the agrochemical granule according to the present application in order to exert formulation characteristics.
The step of granulating the agrochemical composition mixture is preferably a method using the vertical extrusion granulator. Specifically, the use of a disk pelleter can be mentioned. The step of heat-treating the granular molded body is not particularly problematic as long as the granular molded body atmosphere can be maintained at a predetermined temperature, and the granular molded body obtained by the vertical extrusion granulator is uniformly spread. And a method of standing in a thermostat or treating with a fluidized bed dryer.
As a method of coating the surface of the granule obtained by the above method with a surfactant, a concrete mixer, a coating pan, or the like is used. The surfactant can be uniformly coated on the surface of the granule by adding the granule and the surfactant obtained by the above method in this order to the mixer and stirring the inside.
以下に実施例により本発明を更に詳細に説明するが、本発明はこれにより何ら限定されるものではない。また農薬活性成分として供試したチオシクラムシュウ酸塩の純度は約89.9%であった。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The purity of thiocyclam oxalate used as an agrochemical active ingredient was about 89.9%.
実施例1
チオシクラムシュウ酸塩9.2質量部及びステアリン酸13.1質量部、ヒマシ硬化油24.8質量部、シルト#500(商品名、丸中白土社製、白土、平均粒子径:約40μm)50.0質量部、ヒマシ油0.35質量部、NPファイバー(商品名、日本製紙ケミカル社製、微粉結晶セルロース、平均粒子径:10μm)2.5質量部をよく混合したものをディスクペレッター(商品名、不二パウダル社製、縦型押出造粒機、ダイス厚さ15mm、粒径4.0mm)に投入して造粒し、3mm(7メッシュ)の篩で篩別したものを流動層乾燥機(ミゼットドライヤー、MDD−400N型、不二パウダル社製)にて55℃、5分間処理した。これをコンクリートミキサーに投入し、レオドールTW−O120V(商品名、花王社製、POEソルビタンモノオレート)0.3質量部をコーティングし、チオシクラムシュウ酸塩8.3%粒剤を得た。
Example 1
9.2 parts by weight of thiocyclam oxalate and 13.1 parts by weight of stearic acid, 24.8 parts by weight of castor hydrogenated oil, silt # 500 (trade name, manufactured by Marunaka Shiratosha, white clay, average particle size: about 40 μm ) 50.0 parts by mass, castor oil 0.35 parts by mass, NP fiber (trade name, manufactured by Nippon Paper Chemical Co., Ltd., finely divided crystalline cellulose, average particle size: 10 μm) (Product name, manufactured by Fuji Powder Co., Ltd., vertical extrusion granulator, die thickness 15 mm, particle size 4.0 mm), granulated and sieved with a 3 mm (7 mesh) sieve It processed at 55 degreeC for 5 minute (s) with the fluidized bed dryer (Midget dryer, MDD-400N type, Fuji Paudal company make). This was put into a concrete mixer and coated with 0.3 part by mass of Rheodor TW-O120V (trade name, manufactured by Kao Corporation, POE sorbitan monooleate) to obtain 8.3% thiocyclam oxalate granules.
実施例2
チオシクラムシュウ酸塩9.2質量部及びステアリン酸13.1質量部、ヒマシ硬化油24.8質量部、シルト#500(商品名、丸中白土社製、白土、平均粒子径:約40μm)50.0質量部、ヒマシ油0.35質量部、NPファイバー(商品名、日本製紙ケミカル社製、微粉結晶セルロース、平均粒子径:10μm)2.5質量部をよく混合したものをディスクペレッター(商品名、不二パウダル社製、縦型押出造粒機、ダイス厚さ15mm、粒径4.0mm)に投入して造粒し、3mm(7メッシュ)の篩で篩別したものを流動層乾燥機(ミゼットドライヤー、MDD−400N型、不二パウダル社製)にて60℃、5分間処理した。これをコンクリートミキサーに投入し、レオドールTW−O120V(商品名、花王社製、POEソルビタンモノオレート)0.3質量部をコーティングし、チオシクラムシュウ酸塩8.3%粒剤を得た。
Example 2
9.2 parts by weight of thiocyclam oxalate and 13.1 parts by weight of stearic acid, 24.8 parts by weight of castor hydrogenated oil, silt # 500 (trade name, manufactured by Marunaka Shiratosha, white clay, average particle size: about 40 μm ) 50.0 parts by mass, castor oil 0.35 parts by mass, NP fiber (trade name, manufactured by Nippon Paper Chemical Co., Ltd., finely divided crystalline cellulose, average particle size: 10 μm) (Product name, manufactured by Fuji Powder Co., Ltd., vertical extrusion granulator, die thickness 15 mm, particle size 4.0 mm), granulated and sieved with a 3 mm (7 mesh) sieve It processed at 60 degreeC for 5 minute (s) with the fluidized bed dryer (Midget dryer, MDD-400N type, Fuji Paudal company make). This was put into a concrete mixer and coated with 0.3 part by mass of Rheodor TW-O120V (trade name, manufactured by Kao Corporation, POE sorbitan monooleate) to obtain 8.3% thiocyclam oxalate granules.
実施例3
チオシクラムシュウ酸塩9.2質量部及びステアリン酸13.1質量部、ヒマシ硬化油24.8質量部、シルト#500(商品名、丸中白土社製、白土、平均粒子径:約40μm)50.0質量部、ヒマシ油0.35質量部、NPファイバー(商品名、日本製紙ケミカル社製、微粉結晶セルロース、平均粒子径:10μm)2.5質量部をよく混合したものをディスクペレッター(商品名、不二パウダル社製、縦型押出造粒機、ダイス厚さ15mm、粒径4.0mm)に投入して造粒し、3mm(7メッシュ)の篩で篩別したものを流動層乾燥機(ミゼットドライヤー、MDD−400N型、不二パウダル社製)にて60℃、10分間処理した。これをコンクリートミキサーに投入し、レオドールTW−O120V(商品名、花王社製、POEソルビタンモノオレート)0.3質量部をコーティングし、チオシクラムシュウ酸塩8.3%粒剤を得た。
Example 3
9.2 parts by weight of thiocyclam oxalate and 13.1 parts by weight of stearic acid, 24.8 parts by weight of castor hydrogenated oil, silt # 500 (trade name, manufactured by Marunaka Shiratosha, white clay, average particle size: about 40 μm ) 50.0 parts by mass, castor oil 0.35 parts by mass, NP fiber (trade name, manufactured by Nippon Paper Chemical Co., Ltd., finely divided crystalline cellulose, average particle size: 10 μm) (Product name, manufactured by Fuji Powder Co., Ltd., vertical extrusion granulator, die thickness 15 mm, particle size 4.0 mm), granulated and sieved with a 3 mm (7 mesh) sieve It processed at 60 degreeC for 10 minute (s) with the fluidized bed dryer (Midget dryer, MDD-400N type | mold, the product made from Fuji powder). This was put into a concrete mixer and coated with 0.3 part by mass of Rheodor TW-O120V (trade name, manufactured by Kao Corporation, POE sorbitan monooleate) to obtain 8.3% thiocyclam oxalate granules.
実施例4
チオシクラムシュウ酸塩9.2質量部及びステアリン酸13.1質量部、ヒマシ硬化油24.8質量部、シルト#500(商品名、丸中白土社製、白土、平均粒子径:約40μm)50.0質量部、ヒマシ油0.35質量部、NPファイバー(商品名、日本製紙ケミカル社製、微粉結晶セルロース、平均粒子径:10μm)2.5質量部をよく混合したものをディスクペレッター(商品名、不二パウダル社製、縦型押出造粒機、ダイス厚さ15mm、粒径4.0mm)に投入して造粒し、3mm(7メッシュ)の篩で篩別したものを流動層乾燥機(ミゼットドライヤー、MDD−400N型、不二パウダル社製)にて65℃、1分間処理した。これをコンクリートミキサーに投入し、レオドールTW−O120V(商品名、花王社製、POEソルビタンモノオレート)0.3質量部をコーティングし、チオシクラムシュウ酸塩8.3%粒剤を得た。
Example 4
9.2 parts by weight of thiocyclam oxalate and 13.1 parts by weight of stearic acid, 24.8 parts by weight of castor hydrogenated oil, silt # 500 (trade name, manufactured by Marunaka Shiratosha, white clay, average particle size: about 40 μm ) 50.0 parts by mass, castor oil 0.35 parts by mass, NP fiber (trade name, manufactured by Nippon Paper Chemical Co., Ltd., finely divided crystalline cellulose, average particle size: 10 μm) (Product name, manufactured by Fuji Powder Co., Ltd., vertical extrusion granulator, die thickness 15 mm, particle size 4.0 mm), granulated and sieved with a 3 mm (7 mesh) sieve It processed at 65 degreeC for 1 minute with the fluidized bed dryer (Midget dryer, MDD-400N type | mold, the product made from Fuji powder). This was put into a concrete mixer and coated with 0.3 part by mass of Rheodor TW-O120V (trade name, manufactured by Kao Corporation, POE sorbitan monooleate) to obtain 8.3% thiocyclam oxalate granules.
実施例5
チオシクラムシュウ酸塩9.2質量部及びステアリン酸13.1質量部、ヒマシ硬化油24.8質量部、シルト#500(商品名、丸中白土社製、白土、平均粒子径:約40μm)50.0質量部、ヒマシ油0.35質量部、NPファイバー(商品名、日本製紙ケミカル社製、微粉結晶セルロース、平均粒子径:10μm)2.5質量部をよく混合したものをディスクペレッター(商品名、不二パウダル社製、縦型押出造粒機、ダイス厚さ15mm、粒径4.0mm)に投入して造粒し、3mm(7メッシュ)の篩で篩別したものを流動層乾燥機(ミゼットドライヤー、MDD−400N型、不二パウダル社製)にて65℃、5分間処理した。これをコンクリートミキサーに投入し、レオドールTW−O120V(商品名、花王社製、POEソルビタンモノオレート)0.3質量部をコーティングし、チオシクラムシュウ酸塩8.3%粒剤を得た。
Example 5
9.2 parts by weight of thiocyclam oxalate and 13.1 parts by weight of stearic acid, 24.8 parts by weight of castor hydrogenated oil, silt # 500 (trade name, manufactured by Marunaka Shiratosha, white clay, average particle size: about 40 μm ) 50.0 parts by mass, castor oil 0.35 parts by mass, NP fiber (trade name, manufactured by Nippon Paper Chemical Co., Ltd., finely divided crystalline cellulose, average particle size: 10 μm) (Product name, manufactured by Fuji Powder Co., Ltd., vertical extrusion granulator, die thickness 15 mm, particle size 4.0 mm), granulated and sieved with a 3 mm (7 mesh) sieve It processed at 65 degreeC for 5 minute (s) with the fluidized bed dryer (Midget dryer, MDD-400N type, Fuji Paudal company make). This was put into a concrete mixer and coated with 0.3 part by mass of Rheodor TW-O120V (trade name, manufactured by Kao Corporation, POE sorbitan monooleate) to obtain 8.3% thiocyclam oxalate granules.
実施例6
チオシクラムシュウ酸塩9.2質量部及びステアリン酸13.1質量部、ヒマシ硬化油24.8質量部、シルト#500(商品名、丸中白土社製、白土、平均粒子径:約40μm)50.0質量部、ヒマシ油0.35質量部、NPファイバー(商品名、日本製紙ケミカル社製、微粉結晶セルロース、平均粒子径:10μm)2.5質量部をよく混合したものをディスクペレッター(商品名、不二パウダル社製、縦型押出造粒機、ダイス厚さ15mm、粒径4.0mm)に投入して造粒し、3mm(7メッシュ)の篩で篩別したものを流動層乾燥機(ミゼットドライヤー、MDD−400N型、不二パウダル社製)にて70℃、5分間処理した。これをコンクリートミキサーに投入し、レオドールTW−O120V(商品名、花王社製、POEソルビタンモノオレート)0.3質量部をコーティングし、チオシクラムシュウ酸塩8.3%粒剤を得た。
Example 6
9.2 parts by weight of thiocyclam oxalate and 13.1 parts by weight of stearic acid, 24.8 parts by weight of castor hydrogenated oil, silt # 500 (trade name, manufactured by Marunaka Shiratosha, white clay, average particle size: about 40 μm ) 50.0 parts by mass, castor oil 0.35 parts by mass, NP fiber (trade name, manufactured by Nippon Paper Chemical Co., Ltd., finely divided crystalline cellulose, average particle size: 10 μm) (Product name, manufactured by Fuji Powder Co., Ltd., vertical extrusion granulator, die thickness 15 mm, particle size 4.0 mm), granulated and sieved with a 3 mm (7 mesh) sieve It processed at 70 degreeC for 5 minute (s) with the fluidized bed dryer (Midget dryer, MDD-400N type, Fuji Paudal company make). This was put into a concrete mixer and coated with 0.3 part by mass of Rheodor TW-O120V (trade name, manufactured by Kao Corporation, POE sorbitan monooleate) to obtain 8.3% thiocyclam oxalate granules.
実施例7
チオシクラムシュウ酸塩9.2質量部及びステアリン酸13.1質量部、ヒマシ硬化油24.8質量部、シルト#500(商品名、丸中白土社製、白土、平均粒子径:約40μm)50.0質量部、ヒマシ油0.35質量部、NPファイバー(商品名、日本製紙ケミカル社製、微粉結晶セルロース、平均粒子径:10μm)2.5質量部をよく混合したものをディスクペレッター(商品名、不二パウダル社製、縦型押出造粒機、ダイス厚さ15mm、粒径4.0mm)に投入して造粒し、3mm(7メッシュ)の篩で篩別したものを流動層乾燥機(ミゼットドライヤー、MDD−400N型、不二パウダル社製)にて75℃、5分間処理した。これをコンクリートミキサーに投入し、レオドールTW−O120V(商品名、花王社製、POEソルビタンモノオレート)0.3質量部をコーティングし、チオシクラムシュウ酸塩8.3%粒剤を得た。
Example 7
9.2 parts by weight of thiocyclam oxalate and 13.1 parts by weight of stearic acid, 24.8 parts by weight of castor hydrogenated oil, silt # 500 (trade name, manufactured by Marunaka Shiratosha, white clay, average particle size: about 40 μm ) 50.0 parts by mass, castor oil 0.35 parts by mass, NP fiber (trade name, manufactured by Nippon Paper Chemical Co., Ltd., finely divided crystalline cellulose, average particle size: 10 μm) (Product name, manufactured by Fuji Powder Co., Ltd., vertical extrusion granulator, die thickness 15 mm, particle size 4.0 mm), granulated and sieved with a 3 mm (7 mesh) sieve It processed at 75 degreeC for 5 minute (s) with the fluidized bed dryer (Midget dryer, MDD-400N type, Fuji Paudal company make). This was put into a concrete mixer and coated with 0.3 part by mass of Rheodor TW-O120V (trade name, manufactured by Kao Corporation, POE sorbitan monooleate) to obtain 8.3% thiocyclam oxalate granules.
実施例8
チオシクラムシュウ酸塩9.2質量部及びステアリン酸13.1質量部、ヒマシ硬化油24.8質量部、シルト#500(商品名、丸中白土社製、白土、平均粒子径:約40μm)50.0質量部、ヒマシ油0.35質量部、NPファイバー(商品名、日本製紙ケミカル社製、微粉結晶セルロース、平均粒子径:10μm)2.5質量部をよく混合したものをディスクペレッター(商品名、不二パウダル社製、縦型押出造粒機、ダイス厚さ15mm、粒径4.0mm)に投入して造粒し、3mm(7メッシュ)の篩で篩別したものを流動層乾燥機(ミゼットドライヤー、MDD−400N型、不二パウダル社製)にて50℃、10分間処理した。これをコンクリートミキサーに投入し、レオドールTW−O120V(商品名、花王社製、POEソルビタンモノオレート)0.3質量部をコーティングし、チオシクラムシュウ酸塩8.3%粒剤を得た。
Example 8
9.2 parts by weight of thiocyclam oxalate and 13.1 parts by weight of stearic acid, 24.8 parts by weight of castor hydrogenated oil, silt # 500 (trade name, manufactured by Marunaka Shiratosha, white clay, average particle size: about 40 μm ) 50.0 parts by mass, castor oil 0.35 parts by mass, NP fiber (trade name, manufactured by Nippon Paper Chemical Co., Ltd., finely divided crystalline cellulose, average particle size: 10 μm) (Product name, manufactured by Fuji Powder Co., Ltd., vertical extrusion granulator, die thickness 15 mm, particle size 4.0 mm), granulated and sieved with a 3 mm (7 mesh) sieve It processed at 50 degreeC for 10 minute (s) with the fluidized bed dryer (Midget dryer, MDD-400N type | mold, the product made from Fuji powder). This was put into a concrete mixer and coated with 0.3 part by mass of Rheodor TW-O120V (trade name, manufactured by Kao Corporation, POE sorbitan monooleate) to obtain 8.3% thiocyclam oxalate granules.
比較例1
チオシクラムシュウ酸塩9.2質量部及びステアリン酸13.1質量部、ヒマシ硬化油24.8質量部、シルト#500(商品名、丸中白土社製、白土、平均粒子径:約40μm)50.0質量部、ヒマシ油0.35質量部、NPファイバー(商品名、日本製紙ケミカル社製、微粉結晶セルロース、平均粒子径:10μm)2.5質量部をよく混合したものをディスクペレッター(商品名、不二パウダル社製、縦型押出造粒機、ダイス厚さ15mm、粒径4.0mm)に投入して造粒し、3mm(7メッシュ)の篩で篩別したものをコンクリートミキサーに投入し、レオドールTW−O120V(商品名、花王社製、POEソルビタンモノオレート)0.3質量部をコーティングし、チオシクラムシュウ酸塩8.3%粒剤を得た。
Comparative Example 1
9.2 parts by weight of thiocyclam oxalate and 13.1 parts by weight of stearic acid, 24.8 parts by weight of castor hydrogenated oil, silt # 500 (trade name, manufactured by Marunaka Shiratosha, white clay, average particle size: about 40 μm ) 50.0 parts by mass, castor oil 0.35 parts by mass, NP fiber (trade name, manufactured by Nippon Paper Chemical Co., Ltd., finely divided crystalline cellulose, average particle size: 10 μm) (Product name, manufactured by Fuji Powder Co., Ltd., vertical extrusion granulator, die thickness 15 mm, particle size 4.0 mm), granulated and sieved with a 3 mm (7 mesh) sieve The mixture was put into a concrete mixer and coated with 0.3 parts by mass of Rheodor TW-O120V (trade name, manufactured by Kao Corporation, POE sorbitan monooleate) to obtain 8.3% thiocyclam oxalate granules.
比較例2
チオシクラムシュウ酸塩9.2質量部及びステアリン酸13.1質量部、ヒマシ硬化油24.8質量部、シルト#500(商品名、丸中白土社製、白土、平均粒子径:約40μm)50.0質量部、ヒマシ油0.35質量部、NPファイバー(商品名、日本製紙ケミカル社製、微粉結晶セルロース、平均粒子径:10μm)2.5質量部をよく混合したものをディスクペレッター(商品名、不二パウダル社製、縦型押出造粒機、ダイス厚さ15mm、粒径4.0mm)に投入して造粒し、3mm(7メッシュ)の篩で篩別したものを流動層乾燥機(ミゼットドライヤー、MDD−400N型、不二パウダル社製)にて80℃、1分間処理したところ、粒同士が付着するブロッキング現象が起き、農薬粒剤として不適格であった。
Comparative Example 2
9.2 parts by weight of thiocyclam oxalate and 13.1 parts by weight of stearic acid, 24.8 parts by weight of castor hydrogenated oil, silt # 500 (trade name, manufactured by Marunaka Shiratosha, white clay, average particle size: about 40 μm ) 50.0 parts by mass, castor oil 0.35 parts by mass, NP fiber (trade name, manufactured by Nippon Paper Chemical Co., Ltd., finely divided crystalline cellulose, average particle size: 10 μm) (Product name, manufactured by Fuji Powder Co., Ltd., vertical extrusion granulator, die thickness 15 mm, particle size 4.0 mm), granulated and sieved with a 3 mm (7 mesh) sieve When treated with a fluidized bed dryer (midget dryer, MDD-400N type, manufactured by Fuji Powder Co., Ltd.) at 80 ° C. for 1 minute, a blocking phenomenon occurs in which particles adhere to each other, which is not suitable as an agrochemical granule.
試験例1 硬度試験
農薬粒剤100gをボールミル用磁製ポット(内径100×内深100mm)に入れる。次に磁製玉(直径30±2mm、質量35g±3g)を任意に3個取り、3個分の全質量が105gとし、ポットに入れる。ふたをし、予め回転を調整(75rpm)しておいた可変ローラーの上にポットを置き、正しく15分間回転させる。回転が終了したら中身を取り出し、標準篩500μmで篩い、通過した微粉を上皿天秤で量る。硬度は次の式で表され、値の小さいものほど硬度が高いということができる。
硬度(%)=500μm通過微粉量(g)/100(g)×100
Test Example 1 Hardness Test 100 g of agrochemical granule is placed in a magnetic pot for ball mill (inner diameter 100 × inner depth 100 mm). Next, three pieces of porcelain balls (diameter: 30 ± 2 mm, mass: 35 g ± 3 g) are arbitrarily taken, and the total mass of the three pieces is set to 105 g, which is put in a pot. Close the lid, place the pot on the variable roller whose rotation is adjusted in advance (75 rpm), and rotate it correctly for 15 minutes. When the rotation is completed, the contents are taken out, sieved with a standard sieve of 500 μm, and the fine powder that has passed is weighed with an upper pan balance. The hardness is expressed by the following formula, and the smaller the value, the higher the hardness.
Hardness (%) = Amount of fine powder passing through 500 μm (g) / 100 (g) × 100
試験例1の結果を表1に示した。
表1 各農薬粒剤の硬度
硬度(%)
実施例1 4.7
実施例2 2.9
実施例3 2.8
実施例4 2.9
実施例5 2.8
実施例6 4.9
実施例7 4.0
実施例8 6.2
比較例1 8.7
The results of Test Example 1 are shown in Table 1.
Table 1 Hardness of each agricultural chemical granule
hardness(%)
Example 1 4.7
Example 2 2.9
Example 3 2.8
Example 4 2.9
Example 5 2.8
Example 6 4.9
Example 7 4.0
Example 8 6.2
Comparative Example 1 8.7
試験例2 初期薬剤溶出試験
本発明の粒剤0.5gを100mL共栓付き三角フラスコに入れ、100mLの蒸留水を静かに注ぐ(粒剤中の全てのチオシクラムシュウ酸塩が水中に溶出した場合500ppmとなる)。これを25℃恒温槽に2時間静置後、水中に溶出したチオシクラムシュウ酸塩の量をHPLCにより測定した。
Test Example 2 Initial Drug Dissolution Test Put 0.5 g of the granule of the present invention into a 100 mL conical flask and gently pour 100 mL of distilled water (all thiocyclam oxalate in the granule is dissolved in water) In this case, it becomes 500 ppm). This was allowed to stand in a thermostatic bath at 25 ° C. for 2 hours, and then the amount of thiocyclam oxalate eluted in water was measured by HPLC.
試験例2の結果を表2にまとめた。
表2 粒剤からのチオシクラムシュウ酸塩の初期水中溶出量
チオシクラムシュウ酸塩濃度(ppm)
実施例1 40
実施例2 25
実施例3 18
実施例4 25
実施例5 24
実施例6 35
実施例7 36
実施例8 32
比較例1 53
The results of Test Example 2 are summarized in Table 2.
Table 2 Elution amount of thiocyclam oxalate from the granules in the initial water
Thiocyclam oxalate concentration (ppm)
Example 1 40
Example 2 25
Example 3 18
Example 4 25
Example 5 24
Example 6 35
Example 7 36
Example 8 32
Comparative Example 1 53
試験例3 経時的薬剤溶出量試験
本発明の粒剤0.5gを100mL共栓付き三角フラスコに入れ、100mLの蒸留水を静かに注ぐ(粒剤中の全てのチオシクラムシュウ酸塩が水中に溶出した場合500ppmとなる)。これを25℃恒温槽に一昼夜静置後、水中に溶出したチオシクラムシュウ酸塩の量をHPLCにより測定した。その後、フラスコ内の全ての水を除き、改めて100mLの蒸留水を静かに注ぎ、25℃恒温槽に一昼夜静置した。この操作を繰り返し、チオシクラムシュウ酸塩の24時間毎の溶出量を経時的に測定した。
Test Example 3 Elution test of drug over time Place 0.5 g of the granule of the present invention into a 100 mL Erlenmeyer flask with a stopper, and gently pour 100 mL of distilled water (all thiocyclam oxalate in the granule is in water When it elutes, it becomes 500 ppm). This was allowed to stand in a thermostatic bath at 25 ° C. all day and night, and the amount of thiocyclam oxalate eluted in water was measured by HPLC. Then, all the water in the flask was removed, and 100 mL of distilled water was gently poured again, and left still in a 25 ° C. constant temperature bath for a whole day and night. This operation was repeated, and the elution amount of thiocyclam oxalate every 24 hours was measured over time.
試験例3の結果を表3にまとめた。
表3
粒剤からのチオシクラムシュウ酸塩の24時間水中溶出量
チオシクラムシュウ酸塩濃度(ppm)
実施例6 比較例1
1日後 95 132
3日後 23 29
5日後 21 22
7日後 20 16
10日後 14 11
14日後 12 7
The results of Test Example 3 are summarized in Table 3.
Table 3
Elution amount of thiocyclam oxalate from granule in water for 24 hours
Thiocyclam oxalate concentration (ppm)
Example 6 Comparative Example 1
1 day later 95 132
3 days later 23 29
5 days later 21 22
7 days later 20 16
10 days later 14 11
14 days later 12 7
表1に示すように、実施例の何れの製剤例においても粒剤硬度が6.5%以下の硬度を示した。したがって保存及び輸送中に粒が割れたり欠けたりする懸念が少ないものであった。この結果から当該農薬粒剤は市場流通過程における粒破砕が少なく、農薬活性成分の溶出性能等の粒剤品質低下の懸念が少ない事が示された。
また表2に示すように、本発明の農薬粒剤は散布後2時間の農薬活性成分の溶出量が40ppm以下であった。すなわち、農薬粒剤散布初期の農薬放出率が8%以下に抑えられた製剤であった。一方、加熱処理工程を行なわない比較例1では、初期薬剤溶出量が53ppmと認められた。初期薬剤溶出量が多い場合、農薬活性成分による農作物への薬害が懸念される。加えて、粒剤内に滞留する農薬活性成分量が少なくなり、効力の長期持続が期待できなくなる。本願に係る農薬粒剤は初期薬剤溶出量が抑制されており、これら課題を解決できることが示された。
さらに表3に示した経時的な薬剤溶出量分析では、実施例6の1日目の農薬放出量が比較例1よりも低く抑えられていた。更に実施例6の14日後の農薬放出量は、比較例1より高い結果であった。実施例6は粒剤内に農薬活性成分が確実に保持されていることを示しており、初期の薬剤溶出が抑え、尚且つ散布後長時間経過後も粒剤からの薬物放出の持続が達成されていた。
試験例1〜3の結果を総合すると、本願に係る農薬粒剤は、粒剤硬度と初期溶出抑制効果に相関があり、農薬組成物の造粒体の加熱処理によりこれら粒剤物性を規定できるものであった。すなわち加熱処理により当該粒剤の表面改質がなされ、粒硬度が向上すると共に、薬剤溶出制御作用に寄与する効果が得られた。加熱処理の温度及び時間条件を変えることで、所望の溶出制御特性を持った農薬粒剤が得られる事が示唆された。
As shown in Table 1, the granule hardness was 6.5% or less in any formulation example. Therefore, there was little concern that the grains would break or chip during storage and transportation. From these results, it was shown that the agrochemical granule has little particle crushing in the market distribution process, and that there is little concern about degradation of granule quality such as elution performance of the agrochemical active ingredient.
As shown in Table 2, the agrochemical granule of the present invention had an elution amount of an agrochemical active ingredient of 2 hours after spraying of 40 ppm or less. That is, it was a preparation in which the agricultural chemical release rate at the initial stage of spraying the agricultural chemical granules was suppressed to 8% or less. On the other hand, in Comparative Example 1 where the heat treatment step was not performed, the initial drug elution amount was found to be 53 ppm. When the initial drug elution amount is large, there is a concern about phytotoxicity to agricultural crops due to agricultural chemical active ingredients. In addition, the amount of the pesticidal active ingredient staying in the granule is reduced, and long-lasting efficacy cannot be expected. The agrochemical granule according to the present application has a suppressed initial drug elution amount, which indicates that these problems can be solved.
Furthermore, in the drug elution amount analysis with time shown in Table 3, the amount of the agricultural chemical released on the first day of Example 6 was suppressed to be lower than that of Comparative Example 1. Furthermore, the amount of agricultural chemicals released after 14 days of Example 6 was higher than that of Comparative Example 1. Example 6 shows that the pesticidal active ingredient is reliably retained in the granules, suppressing the initial drug elution, and achieving sustained drug release from the granules even after a long time after spraying. It had been.
Combining the results of Test Examples 1 to 3, the agrochemical granule according to the present application has a correlation between the granule hardness and the initial elution suppression effect, and these granule physical properties can be defined by heat treatment of the granule of the agrochemical composition. It was a thing. That is, the surface of the granule was modified by the heat treatment, and the hardness of the granule was improved and the effect of contributing to the drug elution control action was obtained. It was suggested that by changing the temperature and time conditions of the heat treatment, agrochemical granules having desired elution control characteristics can be obtained.
本発明に係る農薬粒剤は、農薬有効成分の溶出を制御した機能性農薬製剤であり、農園芸産業において、農薬の溶出期間を長期化させることにより散布回数を減らし省力化を可能とする農薬製剤として適用されるものである。当該農薬粒剤は粒硬度が高く、機械的強度が保たれ、輸送環境下及び長期保存条件下において粒の粉砕現象が抑えられる。したがって所定の製剤特性が担保された薬剤溶出制御型農薬粒剤として適用されるものであり、農園芸用殺虫製剤、殺菌製剤、殺ダニ製剤、除草性製剤として適用され得るものである。
The agrochemical granule according to the present invention is a functional agrochemical formulation in which elution of active ingredients of agrochemicals is controlled, and in the agricultural and horticultural industries, agrochemicals that can save labor by reducing the number of spraying by extending the elution period of agrochemicals. It is applied as a preparation. The agrochemical granule has high grain hardness, maintains mechanical strength, and suppresses the phenomenon of grain crushing under transportation conditions and long-term storage conditions. Therefore, it is applied as a drug elution control type agricultural chemical granule in which a predetermined formulation characteristic is secured, and can be applied as an agricultural and horticultural insecticidal preparation, a bactericidal preparation, an acaricide preparation, and a herbicidal preparation.
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