JPS6332044B2 - - Google Patents
Info
- Publication number
- JPS6332044B2 JPS6332044B2 JP54155238A JP15523879A JPS6332044B2 JP S6332044 B2 JPS6332044 B2 JP S6332044B2 JP 54155238 A JP54155238 A JP 54155238A JP 15523879 A JP15523879 A JP 15523879A JP S6332044 B2 JPS6332044 B2 JP S6332044B2
- Authority
- JP
- Japan
- Prior art keywords
- manufactured
- mep
- bentonite
- powder
- clay
- 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.)
- Expired
Links
- 239000004927 clay Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000440 bentonite Substances 0.000 claims description 19
- 229910000278 bentonite Inorganic materials 0.000 claims description 19
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 230000000749 insecticidal effect Effects 0.000 claims description 12
- -1 phosphoric acid compound Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- 230000001954 sterilising effect Effects 0.000 claims description 4
- 239000003905 agrochemical Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- ZNOLGFHPUIJIMJ-UHFFFAOYSA-N fenitrothion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(C)=C1 ZNOLGFHPUIJIMJ-UHFFFAOYSA-N 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 23
- 235000012216 bentonite Nutrition 0.000 description 19
- 239000000843 powder Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000008187 granular material Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000887 hydrating effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004563 wettable powder Substances 0.000 description 4
- 241001124134 Chrysomelidae Species 0.000 description 3
- 241001414720 Cicadellidae Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241001124076 Aphididae Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 241000254173 Coleoptera Species 0.000 description 2
- 241001466042 Fulgoromorpha Species 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 241000320508 Pentatomidae Species 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XUGISPSHIFXEHZ-UHFFFAOYSA-N 3beta-acetoxy-cholest-5-ene Natural products C1C=C2CC(OC(C)=O)CCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 XUGISPSHIFXEHZ-UHFFFAOYSA-N 0.000 description 1
- 241000254032 Acrididae Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 239000005947 Dimethoate Substances 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- 241000992277 Fleutiauxia armata Species 0.000 description 1
- 241001477931 Mythimna unipuncta Species 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 241000669298 Pseudaulacaspis pentagona Species 0.000 description 1
- 235000001630 Pyrus pyrifolia var culta Nutrition 0.000 description 1
- 244000079529 Pyrus serotina Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- YASYVMFAVPKPKE-UHFFFAOYSA-N acephate Chemical compound COP(=O)(SC)NC(C)=O YASYVMFAVPKPKE-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- XUGISPSHIFXEHZ-VEVYEIKRSA-N cholesteryl acetate Chemical compound C1C=C2C[C@@H](OC(C)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 XUGISPSHIFXEHZ-VEVYEIKRSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- XAMUDJHXFNRLCY-UHFFFAOYSA-N phenthoate Chemical compound CCOC(=O)C(SP(=S)(OC)OC)C1=CC=CC=C1 XAMUDJHXFNRLCY-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007909 solid dosage form Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明はＰに直結するCH3O−またはCH3S−
を少なくとも１個有する殺虫性有機リン酸化合物
とベントナイトまたは／および酸性白土に担持せ
しめた５―メチル―ｓ―トリアゾロ（３，４―
ｂ）ベンゾチアゾールとを含有する安定化された
殺虫殺菌用固状農薬組成物に関する。
従来、殺虫性有機リン酸化合物は、いわゆる有
機リン剤として、たとえば稲のウンカ、ニカメイ
チユウ、ヨコバイ類、カメムシ類、野菜のアオム
シ、ヨトウムシ、アブラムシ、果樹のアブラムシ
類、ハマキムシ類、モモヒメシンクイガ、ナシグ
ンバイ、クワコナカイガラムシ、桑のシントメタ
マバエ、茶のハマキムシ、チヤノホソガ等の害虫
に対して強い殺虫効果を有することから広く用い
られている。また、５―メチル―ｓ―トリアゾロ
（３，４−ｂ）ベンゾチアゾール（以下、TCと略
称する）は特開昭48―61499号公報に記載の新規
な殺菌剤であり、いもち病などに強い殺菌効果を
示すことが知られている。ところが稲いもち病の
発生はイネの全生育期間にわたるため、稲のウン
カ、ヨコバイ、メイチユウ類、カメムシ類の同時
防除を目的として、また農薬使用者の省力化のた
め、有機リン剤とTCの２種の有効成分を含有す
る製剤を稲用薬剤として用いることが考えられ
る。
しかしながら、特にＰに直結するCH3O−また
はCH3S−を少なくとも１個有する殺虫性有機リ
ン酸化合物（以下、“OP”と略称する）とTCを
担体で希釈して製造した混合固状製剤はOPとTC
との相互作用により、OPのみならずTCも速やか
に分解することがわかつた。例えば、TCとＯ，
Ｏ―ジメチル―Ｏ―（３―メチル―４―ニトロフ
エニル）チオホスフエート（以下MEPと略称す
る）の混合粉剤の場合、40℃で20日保存したとき
の残存率はそれぞれTCは40.5％、MEPは20.4％
であつた。TC、MEPが共存しないTC粉剤、
MEP粉剤では同様の苛酷条件下で残存率は、そ
れぞれTCは100％、MEPは99％であることから、
TCとMEPの相互作用により分解するものと考え
られる。
本発明者はTCとOPとの混合製剤が有する上記
の如き欠点を改良すべく鋭意研究を行なつた結
果、TCを水あるいはアルコール溶媒中で、ベン
トナイトまたは／および酸性白土に担持せしめ、
ついでこれを減圧下濃縮乾固したものとOPとの
混合製剤は、そうでないものに比較して著しく安
定化されることを見い出し本発明を完成した。
すなわち、本発明はＰに直結するCH3O−また
はCH3S−を少なくとも１個有する殺虫性有機リ
ン酸化合物とベントナイトまたは／および酸性白
土に担持せしめた５―メチル―ｓ―トリアゾロ
（３，４−ｂ）ベンゾチアゾールとを含有するこ
とを特徴とする安定化された殺虫殺菌用固状農薬
組成物である。
本発明にいうＰに直結するCH3O−または
CH3S−を少なくとも１個有する殺虫性有機リン
酸化合物（OP）とは、
The present invention relates to CH 3 O- or CH 3 S- directly connected to P.
5-methyl-s-triazolo(3,4-
b) A stabilized insecticidal and sterilizing solid pesticide composition containing benzothiazole. Conventionally, insecticidal organophosphate compounds have been used as so-called organic phosphorus agents, such as planthoppers on rice, leafhoppers, leafhoppers, stink bugs, green caterpillars on vegetables, armyworms, aphids, aphids on fruit trees, leaf beetles, peach beetles, It is widely used because it has a strong insecticidal effect against pests such as the Japanese pear beetle, the mulberry scale insect, the mulberry leaf beetle, the tea leaf beetle, and the tea leaf beetle. In addition, 5-methyl-s-triazolo(3,4-b)benzothiazole (hereinafter abbreviated as TC) is a new fungicide described in JP-A No. 48-61499, and is resistant to rice blast. It is known to exhibit bactericidal effects. However, since the outbreak of rice blast disease occurs throughout the entire growing period of rice, organic phosphorus agents and TC are used to simultaneously control rice planthoppers, leafhoppers, grasshoppers, and stink bugs, and to save labor for pesticide users. It is conceivable to use a preparation containing the active ingredient of the seeds as a rice drug. However, in particular, a mixed solid prepared by diluting an insecticidal organophosphoric acid compound (hereinafter abbreviated as "OP") with a carrier with at least one CH 3 O- or CH 3 S- directly linked to P and TC. The formulations are OP and TC
It was found that not only OP but also TC was rapidly decomposed by interaction with TC. For example, TC and O,
In the case of a mixed powder of O-dimethyl-O-(3-methyl-4-nitrophenyl) thiophosphate (hereinafter abbreviated as MEP), the residual rate when stored at 40°C for 20 days was 40.5% for TC and 20.4% for MEP. %
It was hot. TC powder where TC and MEP do not coexist;
The survival rate of MEP powder under similar harsh conditions is 100% for TC and 99% for MEP, respectively.
It is thought that the decomposition occurs due to the interaction between TC and MEP. The present inventor conducted extensive research to improve the above-mentioned drawbacks of mixed preparations of TC and OP, and as a result, TC was supported on bentonite or/and acid clay in water or alcohol solvent,
They then found that a mixed preparation of OP and a product obtained by concentrating this product to dryness under reduced pressure is significantly more stable than one without the same, and completed the present invention. That is, the present invention provides an insecticidal organophosphoric acid compound having at least one CH 3 O- or CH 3 S- directly linked to P, and 5-methyl-s-triazolo(3, 4-b) A stabilized insecticidal and sterilizing solid agricultural chemical composition characterized by containing benzothiazole. CH 3 O- or directly connected to P in the present invention
An insecticidal organophosphate compound (OP) having at least one CH 3 S- is
【式】（または −SCH3）あるいは[Formula] (or −SCH 3 ) or
【式】（または−
SCH3）なる分子構造を有し、Ｐに結合する他方
の置換基としては直鎖あるいは分枝状低級アルコ
キシ基（たとえばメトキシ、エトキシ、ｎ―また
はｉ―プロポキシ、ｎ−、sec−またはtert−ブ
トキシ基など）あるいは直鎖あるいは分枝状低級
アルキルチオ基（たとえばメチルチオ、エチルチ
オ、ｎ−またはｉ−プロピルチオ、ｎ−、sec−、
tert−ブチルチオなど）などがあり、またＰに直
結する残る１つの置換基はＯ、Ｓを介して種々の
有機残基が結合し、または、Ｎを介して有機残基
と直結するものである。かかる化合物としては、
たとえば(1)Ｏ，Ｏ―ジメチル―Ｏ―（３―メチル
―４―ニトロフエニル）チオホスフエート
（MEP）、(2)Ｓ―１，２―ビス（エトキシカーボ
ニル）エチルＯ，Ｏ―ジメチルホスホロチオロチ
オネート（マラソン）、(3)２，２―ジクロロビニ
ルＯ，Ｏ―ジメチルホスフエート（DDVP）、(4)
Ｏ，Ｏ―ジメチル２，２，２―トリクロロ―１―
ハイドロオキシ―エチルフオスフエネート
（DEP）、(5)Ｏ，Ｓ―ジメチル―Ｎ―アセチルホ
スホロアミドチオレート（アセフエート）、(6)１
―メチル―２―メチルカルバモイルビニルＯ，Ｏ
―ジメチルホスフエート（アルフエート）、(7)Ｓ
―〔α―（エトキシカルボニル）ベンジル〕Ｏ，
Ｏ―ジメチルホスホロチオロチオネート（エルサ
ン）、(8)Ｓ―（Ｎ―メチルカルバモイルメチル）
Ｏ，Ｏ―ジメチルホスホロチオロチオネート（ジ
メトエート）などが挙げられるが、何もこれらに
限定されるものでなく、Ｐに直結するCH3O−ま
たはCH3S−を少なくとも１個有する有機リン酸
化合物はすべて含まれる。これら殺虫性有機リン
酸化合物のうち、特に好ましい化合物としては、
たとえばＰに直結する２個のCH3O−を有する有
機リン酸化合物あるいはＰに直結するそれぞれ１
個のCH3O−およびCH3S−を有する有機リン酸
化合物が挙げられる。
また、本発明に用いられるベントナイト、酸性
白土はモンモリロナイトを主成分とする天然産コ
ロイド性含水ケイ酸アルミニウムであり、農薬、
医薬、化粧品等の賦形剤、結合剤として用いられ
ているいずれの品質のものも使用できる。
TCをベントナイト、酸性白土に担持せしめる
には、いわゆる含浸法、噴霧法など周知の方法を
有利に用いることができる。すなわち、一般には
溶媒を用いて担持せしめることができる。たとえ
ば、予め水あるいは有機溶媒（メタノール、エタ
ノールなどのアルコール類、アセトン、クロロホ
ルムなど）にTCを溶解し、この溶液をベントナ
イトなどの担体に噴霧、乾燥せしめる方法、ある
いはTC溶液にベントナイトなどの担体を投入し、
しばらく撹拌を続けたのち、蒸留、噴霧乾燥（ス
プレードライ）、凍結乾燥など常法により溶媒を
留去する方法、さらにはベントナイトなどの担体
を水または有機溶媒に懸濁させておき、これに
TC粉末あるいはその溶液を加え、しばらく撹拌
してのち溶媒を留去する方法などが挙げられる。
これらベントナイト等に対するTCの担持量は特
に限定されるものではなく１％（重量）以下ある
いは30％（重量）以上でも殺虫、殺菌両成分の安
定効果は認められるが、２〜20％（重量）の範囲
で著しい安定化効果を示す。また安定化効果が認
められる製剤中のベントナイト等の含量の範囲は
５〜80％であり、更に好ましくは10％（重量）〜
50％（重量）の範囲である。
本発明の安定化された殺虫殺菌用固状農薬組成
物は前記各有効成分を、例えばクレー、ジークラ
イト、タルク、カオリン、石膏、炭酸カルシウム
などの担体で希釈するなど周知の方法を用いて製
造することができ、通常、粉剤、水和剤、粒剤な
どの固状の剤型とする。もちろん、このような使
用形態において共力剤、酸化防止剤、分散剤、界
面活性剤、結合剤、流動助剤等を適宜使用するこ
とができ、その散布形態も従来汎用されている粉
剤、粒剤、水和剤などと同様である。
以下、実施例、製造例を挙げて本発明を説明す
る。
なおTCの分解の程度の測定は、所定の条件で
保存した試料の一定量を１／10N―苛性ソーダ液
とクロロホルム混合液で残存するTCを抽出し、
酢酸コレステロールを内部標準とするガスクロマ
トグラフイーにより測定した。OPの代表として
MEPを用いたが、MEPの分解の程度の測定は所
定の条件で保存した試料の一定量をガスクロマト
グラフイーにより測定した。
製造例 １
TCのベントナイト担持物の製造
TCの24g、12g、6g、2.4gをそれぞれとり、メ
タノール200mlおよび水200mlを加え、ベントナイ
ト（豊順鉱業製）100gを各々に加え１時間加熱
還流する。減圧下濃縮乾固して、粉末とし、TC
含量19.4％、10.7％、5.7％、2.3％のベントナイ
ト担持物を得る。
製造例 ２
TCの酸性白土担持物の製造
TCの24g、12g、6g、2.4gをそれぞれとり、メ
タノール200mlおよび水200mlを加え、酸性白土
（水沢化学製）100gを各々に加え以下実施例１と
同様に操作し、TC含量19.4％、10.7％、5.7％、
2.3％の酸性白土担持物を得る。
実施例 １
TC・MEP混合粉剤の製造
製造例１で製造したTC含量19.4％、10.7％、
5.7％、2.3％のベントナイト担持物をそれぞれ
5.5g、11g、22g、55gとり、MEP2.4g、PAP（イ
ソプロピルアシドホスフエート、日本化学製）
0.5g、クレーを加えて全100gとなるように乳鉢で
混合して粉剤とする。その結果、それぞれ4.4％、
9.8％、20.7％、53.7％のベントナイトを含有する
粉剤を得る。
実施例 ２
TC・MEP混合粉剤の製造
製造例２で製造したTC含量19.4％、10.7％、
5.7％、2.3％の酸性白土担持物をそれぞれ5.5g、
11g、22g、55gとり、MEP2.4g、PAP（イソプロ
ピルアシドホスフエート、日本化学製）0.5g、ク
レーを加えて全100gとなるようにし、混合して
粉剤とする。その結果、それぞれ4.4％、9.8％、
20.7％、53.7％の酸性白土を含有する粉剤を得
る。
実施例 ３
TC・MEP混合粉剤の製造
TCの6gにメタノール200ml、および水200mlを
加え更に酸性白土50g、ベントナイト50gを加え
たのち１時間加熱還流する。減圧下濃縮乾固して
粉末としTC含量5.7％のベントナイト、酸性白土
担持物を得る。この担持物22gにMEP2.4g、PAP
（イソプロピルアシドホスフエート、日本化学製）
0.5g、クレーを加えて全100gとなるようにし乳鉢
で混合して粉剤とする。
実施例 ４
TC・MEP混合粒剤の製造
製造例１で製造したTC含量10.7％のベントナ
イト担持物11gをとり、MEP2.4g、PAP（イソプ
ロピルアシドホスフエート、日本化学製）0.5g、
アルフアデンプン（日澱化学製）5g、クレーを
加えて全100gとし、ニーダー（菊水製作所製）
で混合したのち、注水しよく練合する。これを造
粒機（菊水製作所製RD―Ｓ型）を用い１mmφの
スクリーンで造粒し、その後流動層乾燥機（不二
電機製MD―Ｂ―400型）70℃の温風で乾燥し、
粒剤を得る。
実施例 ５
TC・MEP混合粒剤の製造
製造例１で製造したTC含量10％のベントナイ
ト担持物11gの代りに、製造例２で製造したTC
含量5.7％の酸性白土担持物22gをとり以下実施例
４と同様にして、20％の酸性白土を含有する混合
粒剤を得る。
実施例 ６
TC・MEP混合水和剤の製造
ホワイトカーボン（トクシールGU―Ｎ、徳山
ソーダ製）10gに、MEP10gを加えて乳鉢でよく
混合する。更にラウリル硫酸ナトリウム（アルソ
ープME、東邦化学製）5g、リグニンスルホン酸
ナトリウム（山陽パルプ製）2g、クレー23gを加
えてよく混合したのちTC含量20％のベントナイ
ト担持物50gを加えて乳鉢でよく混合する。フラ
ツシユミキサー（宝工機製）で再混合して水和剤
を得る。
実施例 ７
TC・MEP混合水和剤の製造
ホワイトカーボン（トクシールGU―Ｎ、徳山
ソーダ製）10gにMEP10gを加えて乳鉢でよく混
合する。更にラウリル硫酸ナトリウム（アルソー
プME、東邦化学製）5g、リグニンスルホン酸ナ
トリウム（山陽パルプ製）2g、クレー23gを加え
てよく混合したのち、TC含量20％のベントナイ
ト担持物50gを加えてよく混合する。フラツシユ
ミキサー（宝工機製）で再混合して水和剤を得
る。
なお、実施例１〜７に記載中の百分率は重量百
分率である。
製造例 ３
比較粉剤の製造
微粉砕したTC3.3gとクレー288.5gを混和し、
PAP（イソプロピルアシドホスフエート、日本化
学製）1.3g、MEP6.9gを加えて擂潰機で十分に混
和して粉剤とする。
製造例 ４
比較粒剤の製造
微粉砕したTC3.3gにクレー274.8gを加えPAP
（イソプロピルアシドホスフエート、日本化学製）
1.3g、MEP6.9g及びアルフアデンプン（日澱化学
製）15gを加えてニーダー（菊水製作所製）で混
合後、注水し良く練合する。これを造粒機（菊水
製作所RG―Ｓ型）を用いて１mmφのスクリーン
で造粒し、その後流動層乾燥機（不二電機製、
MD―Ｂ―400型）70℃の温風で乾燥し粒剤を得
る。
製造例 ５
比較水和剤の製造
ホワイトカーボン（トクシールGU―Ｎ、徳山
ソーダ製）10gにMEP5gを加えて乳鉢でよく混合
する。更にラウリル硫酸ナトリウム（アルスコー
プME、東邦化学製）5g、リグニンスルホン酸ナ
トリウム（山陽パルプ）2g、クレー73gを加えて
よく混合したのち、微粉砕したTC5gを加えて混
合する。フラツシユミキサー（宝工機製）で再混
合して水和剤を得る。
安定性試験
各混合固状製剤の40℃で苛酷試験の結果を示す
と次の通りである。
１ 粉剤It has the molecular structure [Formula] (or - SCH 3 ), and the other substituent bonded to P is a straight chain or branched lower alkoxy group (e.g. methoxy, ethoxy, n- or i-propoxy, n- , sec- or tert-butoxy groups) or straight-chain or branched lower alkylthio groups (such as methylthio, ethylthio, n- or i-propylthio, n-, sec-,
tert-butylthio, etc.), and the remaining substituent that is directly connected to P is one that is directly connected to various organic residues through O or S, or directly connected to an organic residue through N. . Such compounds include:
For example, (1) O,O-dimethyl-O-(3-methyl-4-nitrophenyl) thiophosphate (MEP), (2) S-1,2-bis(ethoxycarbonyl)ethyl O,O-dimethylphosphorothiolothio nate (marathon), (3) 2,2-dichlorovinyl O,O-dimethyl phosphate (DDVP), (4)
O,O-dimethyl 2,2,2-trichloro-1-
Hydroxy-ethyl phosphenate (DEP), (5) O,S-dimethyl-N-acetyl phosphoramidothiolate (acephate), (6)1
-Methyl-2-methylcarbamoylvinyl O,O
-Dimethyl phosphate (alphaate), (7)S
―[α-(ethoxycarbonyl)benzyl]O,
O-dimethylphosphorothiolothionate (elsan), (8)S-(N-methylcarbamoylmethyl)
Examples include, but are not limited to, O,O-dimethylphosphorothiolothionate (dimethoate), and organic phosphorus having at least one CH 3 O- or CH 3 S- directly connected to P. All acid compounds are included. Among these insecticidal organophosphoric acid compounds, particularly preferred compounds include:
For example, an organic phosphoric acid compound having two CH 3 O- directly connected to P or one each directly connected to P.
Examples include organic phosphoric acid compounds having CH 3 O- and CH 3 S-. In addition, the bentonite and acid clay used in the present invention are naturally produced colloidal hydrated aluminum silicate whose main component is montmorillonite, and the bentonite and acid clay used in the present invention are
Any quality used as an excipient or binder for medicines, cosmetics, etc. can be used. In order to support TC on bentonite or acid clay, well-known methods such as the so-called impregnation method and spraying method can be advantageously used. That is, it can generally be supported using a solvent. For example, TC is dissolved in water or an organic solvent (alcohols such as methanol, ethanol, acetone, chloroform, etc.) in advance, and this solution is sprayed onto a carrier such as bentonite and dried, or a carrier such as bentonite is added to the TC solution. put it in,
After stirring for a while, the solvent is removed by a conventional method such as distillation, spray drying, or freeze drying, or by suspending a carrier such as bentonite in water or an organic solvent.
Examples include adding TC powder or a solution thereof, stirring for a while, and then distilling off the solvent.
The amount of TC supported on these bentonites, etc. is not particularly limited, and the stabilizing effect of both insecticidal and bactericidal components is recognized even if it is less than 1% (weight) or more than 30% (weight), but it is 2 to 20% (weight) It shows a significant stabilizing effect in the range of . In addition, the content range of bentonite etc. in the formulation in which a stabilizing effect is observed is 5 to 80%, more preferably 10% to 80% (by weight).
50% (by weight) range. The stabilized insecticidal and sterilizing solid agricultural chemical composition of the present invention is produced using a well-known method such as diluting each of the above-mentioned active ingredients with a carrier such as clay, giclite, talc, kaolin, gypsum, calcium carbonate, etc. It is usually in a solid dosage form such as a powder, a wettable powder, or a granule. Of course, synergists, antioxidants, dispersants, surfactants, binders, flow aids, etc. can be used as appropriate in such usage forms, and the dispersion forms can also be the conventionally widely used powders and granules. The same applies to powders, hydrating agents, etc. The present invention will be explained below with reference to Examples and Production Examples. To measure the degree of TC decomposition, extract the remaining TC from a certain amount of a sample stored under specified conditions with a 1/10N caustic soda solution and chloroform mixture.
It was measured by gas chromatography using cholesterol acetate as an internal standard. As a representative of OP
Although MEP was used, the degree of decomposition of MEP was measured by gas chromatography on a certain amount of a sample stored under predetermined conditions. Production Example 1 Production of bentonite-supported TC 24 g, 12 g, 6 g, and 2.4 g of TC are each taken, 200 ml of methanol and 200 ml of water are added to each, 100 g of bentonite (manufactured by Hosun Mining Co., Ltd.) is added to each, and the mixture is heated under reflux for 1 hour. Concentrate to dryness under reduced pressure to form a powder, and TC
Bentonite supports with contents of 19.4%, 10.7%, 5.7%, and 2.3% are obtained. Production Example 2 Production of TC supported on acidic clay Take 24g, 12g, 6g, and 2.4g of TC, add 200ml of methanol and 200ml of water, add 100g of acidic clay (manufactured by Mizusawa Chemical) to each, and proceed as in Example 1 below. Similarly operated, TC content 19.4%, 10.7%, 5.7%,
Obtain 2.3% acid clay support. Example 1 Production of TC/MEP mixed powder The TC content produced in Production Example 1 was 19.4%, 10.7%,
5.7% and 2.3% bentonite loading, respectively.
5.5g, 11g, 22g, 55g, MEP2.4g, PAP (isopropyl acid phosphate, Nippon Chemical)
Add 0.5g and clay to make a powder by mixing in a mortar to make a total of 100g. The results were 4.4% and 4.4%, respectively.
A powder containing 9.8%, 20.7% and 53.7% bentonite is obtained. Example 2 Production of TC/MEP mixed powder The TC content produced in Production Example 2 was 19.4%, 10.7%,
5.5g each of 5.7% and 2.3% acid clay supports,
Take 11 g, 22 g, and 55 g, add 2.4 g of MEP, 0.5 g of PAP (isopropyl acid phosphate, manufactured by Nippon Chemical), and clay to make a total of 100 g, and mix to make a powder. The results were 4.4%, 9.8%, respectively.
A powder containing 20.7% and 53.7% acid clay is obtained. Example 3 Production of TC/MEP mixed powder To 6 g of TC, 200 ml of methanol and 200 ml of water were added, followed by 50 g of acid clay and 50 g of bentonite, and the mixture was heated under reflux for 1 hour. Concentrate to dryness under reduced pressure to obtain a powder containing bentonite and acid clay with a TC content of 5.7%. 22g of this carrier, 2.4g of MEP, PAP
(Isopropyl acid phosphate, manufactured by Nippon Kagaku)
Add 0.5g and clay to make a total of 100g and mix in a mortar to make a powder. Example 4 Manufacture of TC/MEP mixed granules 11 g of the bentonite support with a TC content of 10.7% manufactured in Production Example 1 was taken, and 2.4 g of MEP, 0.5 g of PAP (isopropyl acid phosphate, manufactured by Nippon Chemical),
Add 5g of alpha starch (manufactured by Nippon Chemistry) and clay to make a total of 100g, and use a kneader (manufactured by Kikusui Seisakusho).
After mixing, add water and mix well. This was granulated using a 1 mm diameter screen using a granulator (RD-S model manufactured by Kikusui Seisakusho), and then dried with hot air at 70°C using a fluidized bed dryer (MD-B-400 model manufactured by Fuji Electric).
Obtain granules. Example 5 Production of TC/MEP mixed granules Instead of 11 g of bentonite support with a TC content of 10% produced in Production Example 1, TC produced in Production Example 2 was used.
22 g of the acid clay supported material having a content of 5.7% is taken and the same procedure as in Example 4 is carried out to obtain a mixed granule containing 20% acid clay. Example 6 Production of TC/MEP mixed hydrating powder Add 10 g of MEP to 10 g of white carbon (Tokuseal GU-N, manufactured by Tokuyama Soda) and mix well in a mortar. Furthermore, 5 g of sodium lauryl sulfate (Alsoap ME, manufactured by Toho Chemical Co., Ltd.), 2 g of sodium lignin sulfonate (manufactured by Sanyo Pulp Co., Ltd.), and 23 g of clay were added and mixed well. Then, 50 g of bentonite-supported material with a TC content of 20% was added and mixed well in a mortar. do. Mix again using a flat mixer (manufactured by Takarakoki) to obtain a wettable powder. Example 7 Production of TC/MEP mixed hydration powder Add 10 g of MEP to 10 g of white carbon (Tokuseal GU-N, manufactured by Tokuyama Soda) and mix well in a mortar. Furthermore, add 5 g of sodium lauryl sulfate (Alsoap ME, manufactured by Toho Chemical), 2 g of sodium lignin sulfonate (manufactured by Sanyo Pulp), and 23 g of clay, and mix well. Then, add 50 g of bentonite support with a TC content of 20% and mix well. . Mix again using a flat mixer (manufactured by Takarakoki) to obtain a wettable powder. Note that the percentages described in Examples 1 to 7 are weight percentages. Production example 3 Production of comparative powder 3.3g of finely ground TC and 288.5g of clay were mixed,
Add 1.3 g of PAP (isopropyl acid phosphate, manufactured by Nippon Kagaku) and 6.9 g of MEP and thoroughly mix with a grinder to form a powder. Production example 4 Production of comparative granules 274.8g of clay was added to 3.3g of finely ground TC and PAP
(Isopropyl acid phosphate, manufactured by Nippon Kagaku)
Add 1.3 g, MEP 6.9 g, and 15 g of alpha starch (manufactured by Nippon Deka Chemical) and mix in a kneader (manufactured by Kikusui Seisakusho), then pour water and mix well. This was granulated with a 1 mmφ screen using a granulator (Kikusui Seisakusho RG-S type), and then a fluidized bed dryer (Fuji Electric, model RG-S).
MD-B-400 type) Dry with warm air at 70℃ to obtain granules. Production Example 5 Production of Comparative Hydrating Powder Add 5g of MEP to 10g of white carbon (Tokuseal GU-N, manufactured by Tokuyama Soda) and mix well in a mortar. Furthermore, 5 g of sodium lauryl sulfate (Arscope ME, manufactured by Toho Chemical Co., Ltd.), 2 g of sodium lignin sulfonate (Sanyo Pulp), and 73 g of clay are added and mixed well, and then 5 g of finely ground TC is added and mixed. Mix again with a flat mixer (manufactured by Takarakoki) to obtain a wettable powder. Stability test The results of a severe test at 40°C for each mixed solid formulation are as follows. 1 Powder
【表】【table】
【表】【table】
【表】 ２ 粒剤【table】 2 Granules
【表】 ３ 水和剤【table】 3 Hydrating agent
【表】【table】
【表】
以上の結果からTCとOPの混合固状製剤におい
て、TCをベントナイトまたは／および酸性白土
に担持せしめたものを用いることにより、両成分
の安定化がはかられていることは明らかである。[Table] From the above results, it is clear that in a mixed solid preparation of TC and OP, by using TC supported on bentonite and/or acid clay, both components are stabilized. be.
Claims (1)
くとも１個有する殺虫性有機リン酸化合物とベン
トナイトまたは／および酸性白土に担持せしめた
５―メチル―ｓ―トリアゾロ（３，４―ｂ）ベン
ゾチアゾールとを含有することを特徴とする安定
化された殺虫殺菌用固状農薬組成物。1 An insecticidal organic phosphoric acid compound having at least one CH 3 O- or CH 3 S- directly linked to P and 5-methyl-s-triazolo (3,4-b) supported on bentonite or/and acid clay. 1. A stabilized insecticidal and sterilizing solid agricultural chemical composition characterized by containing benzothiazole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15523879A JPS5677208A (en) | 1979-11-29 | 1979-11-29 | Stabilized solid agricultural chemical composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15523879A JPS5677208A (en) | 1979-11-29 | 1979-11-29 | Stabilized solid agricultural chemical composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5677208A JPS5677208A (en) | 1981-06-25 |
| JPS6332044B2 true JPS6332044B2 (en) | 1988-06-28 |
Family
ID=15601549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15523879A Granted JPS5677208A (en) | 1979-11-29 | 1979-11-29 | Stabilized solid agricultural chemical composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5677208A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0696447B2 (en) * | 1986-07-24 | 1994-11-30 | 株式会社資生堂 | Composite powder and its manufacturing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49101543A (en) * | 1973-02-06 | 1974-09-25 | ||
| JPS52134023A (en) * | 1976-04-28 | 1977-11-09 | Kumiai Chem Ind Co Ltd | Agricultural and horticultural fungicide |
-
1979
- 1979-11-29 JP JP15523879A patent/JPS5677208A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49101543A (en) * | 1973-02-06 | 1974-09-25 | ||
| JPS52134023A (en) * | 1976-04-28 | 1977-11-09 | Kumiai Chem Ind Co Ltd | Agricultural and horticultural fungicide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5677208A (en) | 1981-06-25 |
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