JPS6358801B2 - - Google Patents
Info
- Publication number
- JPS6358801B2 JPS6358801B2 JP57007834A JP783482A JPS6358801B2 JP S6358801 B2 JPS6358801 B2 JP S6358801B2 JP 57007834 A JP57007834 A JP 57007834A JP 783482 A JP783482 A JP 783482A JP S6358801 B2 JPS6358801 B2 JP S6358801B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- parts
- weight
- agricultural chemical
- ethylene glycol
- 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
- 239000000203 mixture Substances 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000003905 agrochemical Substances 0.000 claims description 28
- -1 polyoxyethylene Polymers 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000009472 formulation Methods 0.000 claims description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 25
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 23
- 239000003995 emulsifying agent Substances 0.000 claims description 19
- 239000004615 ingredient Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 239000000575 pesticide Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 239000004480 active ingredient Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- BCTQJXQXJVLSIG-UHFFFAOYSA-N mepronil Chemical compound CC(C)OC1=CC=CC(NC(=O)C=2C(=CC=CC=2)C)=C1 BCTQJXQXJVLSIG-UHFFFAOYSA-N 0.000 claims description 5
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 claims description 5
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- VOEYXMAFNDNNED-UHFFFAOYSA-N metolcarb Chemical compound CNC(=O)OC1=CC=CC(C)=C1 VOEYXMAFNDNNED-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- DQJCHOQLCLEDLL-UHFFFAOYSA-N tricyclazole Chemical compound CC1=CC=CC2=C1N1C=NN=C1S2 DQJCHOQLCLEDLL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- 239000003090 pesticide formulation Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims description 2
- WCMMILVIRZAPLE-UHFFFAOYSA-M cyhexatin Chemical compound C1CCCCC1[Sn](C1CCCCC1)(O)C1CCCCC1 WCMMILVIRZAPLE-UHFFFAOYSA-M 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 description 25
- 239000007788 liquid Substances 0.000 description 18
- 239000002518 antifoaming agent Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 17
- 229920001296 polysiloxane Polymers 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 12
- 238000005507 spraying Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- YWPOLRBWRRKLMW-UHFFFAOYSA-M sodium;naphthalene-2-sulfonate Chemical compound [Na+].C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 YWPOLRBWRRKLMW-UHFFFAOYSA-M 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- OVLGNUHSJCCFPG-UHFFFAOYSA-N nonoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCOC1=CC=CC=C1 OVLGNUHSJCCFPG-UHFFFAOYSA-N 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 4
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 3
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ODCWYMIRDDJXKW-UHFFFAOYSA-N simazine Chemical compound CCNC1=NC(Cl)=NC(NCC)=N1 ODCWYMIRDDJXKW-UHFFFAOYSA-N 0.000 description 2
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 244000215068 Acacia senegal Species 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 241000589634 Xanthomonas Species 0.000 description 1
- BGFURDBGMRKOTL-UHFFFAOYSA-N [1,2,4]triazolo[3,4-b][1,3]benzothiazole Chemical compound C1=CC=C2N3C=NN=C3SC2=C1 BGFURDBGMRKOTL-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- CKJFPVNRRHVMKZ-UHFFFAOYSA-L calcium;naphthalene-1-sulfonate Chemical compound [Ca+2].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 CKJFPVNRRHVMKZ-UHFFFAOYSA-L 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- PBSNFUYVULLJCY-UHFFFAOYSA-N dodecoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOC1=CC=CC=C1 PBSNFUYVULLJCY-UHFFFAOYSA-N 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- FCOAHACKGGIURQ-UHFFFAOYSA-N iprobenfos Chemical compound CC(C)OP(=O)(OC(C)C)SCC1=CC=CC=C1 FCOAHACKGGIURQ-UHFFFAOYSA-N 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003986 organophosphate insecticide Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- JLABKOUORPVZCA-UHFFFAOYSA-N sodium;1,4-dibutoxy-1,4-dioxobutane-2-sulfonic acid Chemical compound [Na+].CCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCC JLABKOUORPVZCA-UHFFFAOYSA-N 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
この発明は常温で固体かつ難水溶性の農薬原体
を、散布剤に適した剤型に製剤した水中懸濁型農
薬製剤に関するものである。
農薬には粉剤、粒剤、水和剤、乳剤など、種々
の剤型の製剤がある。このうち、粉剤は散布に際
して周囲への飛散が多いなどの欠点を有する。ま
た水和剤は散布に用いる希釈液を調製してから散
布するまでの間に沈降現象を起こし、安定性に乏
しい欠点がある。さらに乳剤は原体が溶剤類に容
易に溶解する必要があるため、乳剤化できる原体
が挟く限られること、有機溶剤を用いるため引火
性を有すること、ならびに作物によつては薬害を
招来することなどの欠点がある。
最近は散布作業の省力化の観点からも、液剤に
よる空中散布が行われる場合が多いが、上記従来
の剤型は必ずしもこれに適しているとはいえず、
新しい剤型の製剤が望まれている。これに適した
製剤として、溶媒類に難溶で、乳剤化できない農
薬原体を水または親水性媒質中で懸濁状に製剤し
た散布剤（特公昭46−20519号）、液状有機リン殺
虫剤に疎水性有機溶媒、界面活性剤、増粘剤等を
配合し、有機リン殺虫剤を高濃度で含有する水中
油滴型マヨネーズ状の製剤（特公昭46−18514
号）、水不溶性の殺生剤に非イオン界面活性剤、
ヘテロポリサツカライドゴムおよび水を配合した
流動性の水性殺生剤組成物（特公昭53−46889
号）、ならびに難水溶性固体農薬、または難水溶
性固体農薬と水溶性固体農薬を同時に含む系にお
いて、水を分散媒とし、界面活性剤および水溶性
高分子からなる懸濁状農薬（特公昭58−24401号）
などが知られている。
しかしながら、これらの従来の製剤は、農薬原
体を極微細粒子とするために、溶媒に懸濁させた
状態で湿式粉砕し、乳化剤、分散剤などの添加に
より物理性状の安定化を行うが、粉砕粒子が均一
に分散した状態や、溶媒中に安定に懸濁した状態
を表わす懸垂性などにおいて、必ずしも安定な性
状が得られず、懸濁性農薬製剤として十分な特性
を有するとはいえない欠点があつた。
この発明は上記のような従来品の欠点を除去す
るためになされたもので、特殊な乳化剤および増
粘剤を配合することにより、常温で固体かつ難水
溶性の農薬原体を均一かつ安定に懸濁させ、取扱
が容易で貯蔵安定性に優れ、散布時の分散性およ
び懸垂性の面でも優れ、散布剤としての使用に適
した水中懸濁型農薬製剤を提供することを目的と
している。
この発明は、有効成分として、常温で固体かつ
難水溶性の農薬原体を50重量％以下、β−ナフタ
レンスルホン酸ホルマリン縮合物塩を0.3〜３重
量％、その他の乳化剤を５〜12重量％およびヘテ
ロポリサツカライドゴムを0.05〜0.5重量％含有
する水中懸濁型農薬製剤である。
この発明に適用可能な有効成分としての農薬原
体は、常温で固体であり、かつ水に難溶性（不溶
性を含む）のものであれば特に制限はなく、例え
ば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）、
２−メチル−3′−イソプロポキシベンズアニライ
ド（メプロニル）などの殺菌剤、０，0′−ジメチ
ル２−クロロ−１−（２，４−ジクロルフエニル）
ビニルホスフエート、ｍ−トリルＮ−メチルカー
バメート、トリシクロヘキシルチンヒドロオキサ
イドなどの殺虫剤、２−クロロ−４，６−ビス
（エチルアミノ）−１，３，５−トリアジン、２−
クロロ−４−エチルアミノ−６−イソプロピルア
ミノ−１，３，５−トリアジンなどの除草剤など
が挙げられる。
これらの農薬原体は用途により単独で用いる場
合もあり、２種以上の混合剤として用いる場合も
あり、また他の農薬原体、例えば液状または水溶
性のものとの混合剤として用いる場合もある。上
記農薬原体の配合割合は50重量％以下、好ましく
は10〜50重量％である。
β−ナフタレンスルホン酸ホルマリン縮合物塩
は陰イオン性の界面活性剤であり、例えばβ−ナ
フタレンスルホン酸ホルマリン縮合物のナトリウ
ム塩、カルシウム塩、アンモニウム塩、マグネシ
ウム塩、トリエタノールアミン塩などがある。
β−ナフタレンスルホン酸ホルマリン縮合物塩
の配合割合は0.3〜３重量％、好ましくは0.5〜１
重量％である。
その他の乳化剤としては、ジアルキルスルホコ
ハク酸塩、アルキルアリールスルホン酸塩、リグ
ニンスルホン酸塩などの陰イオン性界面活性剤、
ならびにポリオキシエチレンアリールフエニルエ
ーテル、ポリオキシエチレンアルキルアリールエ
ーテルサルフエートなどが望ましい。
これらの乳化剤は１種だけ単独で配合してもよ
く、また２種以上混合してもよく、混合する場合
の混合比も任意に選択できる。乳化剤の配合割合
は５〜12重量％である。
ヘテロポリサツカライドゴムは増粘剤として配
合されるものであり、一般にキサンタンゴムと呼
ばれ、キサントモナス属のバクテリア作用で製造
される高分子量の線状細胞外物質で、20000ない
し1000000の分子量あるいはそれを越える分子量
を有している。
この発明の水中懸濁型農薬製剤に使用する溶媒
としては水が主体となり、水単独でもよいが、耐
寒性、耐熱性、比重などの物理化学的性状を考慮
する必要がある場合は、イソプロピルアルコー
ル、グリセリン、ポリエチレングリコール、エチ
レングリコール、エチレングリコールモノメチル
エーテル、エチレングリコールモノエチルエーテ
ルなどの親水性溶剤、または場合によつてはキシ
レン、オルソクロルトルエン、ケロシン、鉱油、
植物油、流動パラフインなどの疎水性溶剤から選
ばれる１種以上の有機溶剤を配合してもよい。溶
剤を配合する場合の配合割合は１〜30重量％、好
ましくは10〜20重量％である。
この発明の水中懸濁型農薬製剤は、上記成分の
ほかに５重量％以下の消泡剤、例えばジメチルポ
リシロキサンを主成分とするシリコーン系消泡剤
を配合してもよく、さらに必要に応じて他の成分
を配合してもよい。
次にこの発明の製剤の製造工程の一例を示す。
まず増粘剤としてのヘテロポリサツカライドゴム
の所定量を、撹拌機により0.1〜0.6重量％となる
ように水に溶解混合させる。次に農薬原体、界面
活性剤、消泡剤、有機溶剤および追加する水の順
で、所定量を計量して混合槽に入れ、高速撹拌機
により30〜90分間破砕混合する。次にこれらの混
合物を湿式粉砕機により、農薬原体が4μｍ以下、
好ましくは0.5〜3μｍになるように微粉砕し、製
品を得る。
本発明の水中懸濁型農薬製剤は、特殊な乳化剤
および増粘剤を組合せて配合したので、常温で固
体かつ難水溶性の農薬原体を均一かつ安定に懸濁
させるとともに散布性を良くし、これにより製造
および使用の期間を通じて取扱が容易であり、長
期間の貯蔵においても沈降が極めて少なく、貯蔵
安定性に優れ、散布時の分散性および懸垂性の面
でも優れ、散布剤として極めて優れたものであ
る。
次に本発明の実施例および試験例について説明
する。なお、各例中、部は重量部を示す。
実施例 １
水62.2部にヘテロポリサツカライドゴム0.2部
を加え、通常撹拌機（特殊機化工業株式会社製：
ホモミキサーHV−Ｍ型）により20分間溶解混合
し、次に５−メチル−〔１，２，４〕トリアゾロ
〔３，４−ｂ〕ベンゾチアゾール20部、β−ナフ
タレンスルホン酸ナトリウムホルマリン縮合物
0.5部、ポリオキシエチレンスチリルフエニルエ
ーテル／ポリオキシエチレンノニルフエニルエー
テルサルフエート／ジオクチルスルホコハク酸ナ
トリウム混合物７部、エチレングリコール10部の
順にそれぞれ計量して混合槽に入れ、高速撹拌機
（株式会社島崎製作所製：RB型撹拌機）により
40分間粉砕混合し、これに0.1部の消泡剤（旭化
学工業株式会社製：シリコーンAF−128）を加
え、撹拌後1.0〜1.5mmの硬質ガラス製ビーズ４
を充填した８ベツセル容量の湿式粉砕機（五十
嵐機械製造株式会社製：2Gサンドグラインダー
SL型）により送液速度20／時間で微粉砕して
均一な水中懸濁型農薬製剤100部を得た。
実施例 ２
水42.8部にヘテロポリサツカライドゴム0.1部
を加えて通常撹拌機により20分間溶解混合し、次
に農薬原体として２−メチル−3′−イソプロポキ
シベンズアニライド40部、β−ナフタレンスルホ
ン酸カルシウムホルマリン縮合物１部、他の乳化
剤としてポリオキシエチレンノニルフエニルエー
テルサルフエート／ポルオキシエチレンスチリル
フエニルエーテル混合物７部、溶剤としてエチレ
ングリコールモノエチルエーテル９部の順にそれ
ぞれ計量して混合槽に入れ、高速撹拌機（株式会
社島崎製作所製：RB型撹拌機）により90分間粉
砕混合し、これに0.1部の消泡剤（旭化学工業株
式会社製：シリコーンAF−128）を加え、湿式粉
砕機の送液速度30／時間としたほかは実施例１
と同様にして製剤100部を得た。
実施例 ３
水57.3部にヘテロポリサツカライドゴム0.1部
を加えて通常撹拌機により20分間溶解混合し、次
に農薬原体として５−メチル−〔１，２，４〕ト
リアゾロ〔３，４−ｂ〕ベンゾチアゾール10部お
よびＳ−ベンジルジイソプロピルホスホロチオレ
ート20部、β−ナフタレンスルホン酸ナトリウム
ホルマリン縮合物0.5部、他の乳化剤としてポリ
オキシエチレンスチリルフエニルエーテル５部、
溶剤として流動パラフイン７部の順にそれぞれ計
量して混合槽に入れ、高速撹拌機（株式会社島崎
製作所製：RB型撹拌機）により90分間粉砕混合
し、これに0.1部の消泡剤（旭化学工業株式会社
製：シリコーンAF−128）を加え、湿式粉砕機の
送液速度30／時間としたほかは実施例１と同様
にして製剤100部を得た。
実施例 ４
水44.9部にヘテロポリサツカライドゴム0.3部
を加えて通常撹拌機により20分間溶解混合し、次
に農薬原体としてジメチル２−クロロ−１−（２，
４−ジクロルフエニル）ビニルホスフエート20部
およびｍ−トリルメチルカーバメート20部、β−
ナフタリンスルホン酸カルシウムホルマリン縮合
物0.7部、他の乳化剤としてポリオキシエチレン
スチリルフエニルエーテル／ジシクロヘキシルス
ルホコハク酸ナトリウム／ポリオキシエチレンノ
ニルフエニルエーテルサルフエート混合物８部、
溶剤としてケロシン３部、オルソクロルトルエン
３部の順にそれぞれ計量して混合槽に入れ、高速
撹拌機（株式会社島崎製作所製：RB型撹拌機）
により60分間粉砕混合し、これに0.1部の消泡剤
（旭化学工業株式会社製：シリコーンAF−128）
を加え、湿式粉砕機の送液速度30／時間とした
ほかは実施例１と同様にして製剤100部を得た。
実施例 ５
水44.3部にヘテロポリサツカライドゴム0.3部、
農薬原体として２−クロロ−４，６−ビス（エチ
ルアミノ）−１，３，５−トリアジン40部を加え
て通常撹拌機により30分間溶解混合し、次にβ−
ナフタレンスルホン酸ナトリウムホルマリン縮合
物0.3部、他の乳化剤としてポリオキシエチレン
スチリルフエニルエーテル／ポリオキシエチレン
ベンジルフエニルエーテル／ポリオキシエチレン
ドデシルフエニルエーテルサルフエート混合物６
部、溶剤としてイソプロピルアルコール４部、ポ
リエチレングリコール（平均分子量200）５部の
順にそれぞれ計量して混合槽に入れ、高速撹拌機
（株式会社島崎製作所製：RB型撹拌機）により
70分間粉砕混合し、これに0.1部の消泡剤（旭化
学工業株式会社製：シリコーンAF−128）を加
え、湿式粉砕機の送液速度20／時間としたほか
は実施例１と同様にして製剤100部を得た。
実施例 ６
水56.1部にヘテロポリサツカライドゴム0.3部、
農薬原体としてトリシクロヘキシルチンヒドロキ
シオキサイド25部、β−ナフタレンスルホン酸ナ
トリウムホルマリン縮合物0.5部、他の乳化剤と
してポリオキシエチレンスチリルフエニルエーテ
ル／ジブチルスルホコハク酸ナトリウム混合物８
部、溶剤としてエチレングリコール10部の順にそ
れぞれ計量して混合槽に入れ、高速撹拌機（株式
会社島崎製作所製：RB型撹拌機）により30分間
粉砕混合し、これに0.1部の消泡剤（旭化学工業
株式会社製：シリコーンAF−128）を加え、湿式
粉砕機の送液速度30／時間としたほかは実施例
１と同様にして製剤100部を得た。
実施例 ７
水72.2部にヘテロポリサツカライドゴム0.2部
を加えて通常撹拌機により20分間溶解混合し、次
に農薬原体として５−メチル−〔１，２，４〕ト
リアゾロ〔３，４−ｂ〕ベンゾチアゾール20部、
β−ナフタレンスルホン酸ナトリウムホルマリン
縮合物0.5部、他の乳化剤としてポリオキシエチ
レンスチリルフエニルエーテル／ポリオキシエチ
レンノニルフエニルエーテルサルフエート／ジオ
クチルスルホコハク酸ナトリウム混合物７部の順
にそれぞれ計量して混合槽に入れ、高速撹拌機
（株式会社島崎製作所製：RB型撹拌機）により
40分間粉砕混合し、これに0.1部の消泡剤（旭化
学工業株式会社製：シリコーンAF−128）を加
え、湿式粉砕機の送液速度20／時間としたほか
は実施例１と同様にして製剤100部を得た。
参考例 １
水59.7部にヘテロポリサツカライドゴム0.2部
を加えて通常撹拌機により20分間溶解混合し、次
に農薬原体として５−メチル−〔１，２，４〕ト
リアゾロ〔３，４−ｂ〕ベンゾチアゾール20部、
他の乳化剤としてポリオキシエチレンスチリルフ
エニルエーテル／ポリオキシエチレンノニルフエ
ニルエーテルサルフエート／ジオクチルスルホコ
ハク酸ナトリウム混合物10部、エチレングリコー
ル10部の順にそれぞれ計量して混合槽に入れ、高
速撹拌機（株式会社島崎製作所製：RB型撹拌
機）により40分間粉砕混合し、これに0.1部の消
泡剤（旭化学工業株式会社製：シリコーンAF−
128）を加え、実施例１と同様にして製剤100部を
得た。
参考例 ２
水69.2部にヘテロポリサツカライドゴム0.2部
を加えて通常撹拌機により20分間溶解混合し、次
に農薬原体として５−メチル−〔１，２，４〕ト
リアゾロ〔３，４−ｂ〕ベンゾチアゾール20部、
β−ナフタレンスルホン酸ナトリウムホルマリン
縮合物0.5部、エチレングリコール10部の順にそ
れぞれ計量して混合槽に入れ、高速撹拌機（株式
会社島崎製作所製：RB型撹拌機）により40分間
粉砕混合し、これに0.1部の消泡剤（旭化学工業
株式会社製：シリコーンAF−128）を加え、実施
例１と同様にして製剤100部を得た。
参考例 ３
水43.8部にヘテロポリサツカライドゴム0.1部
を加えて通常撹拌機により20分間溶解混合し、次
に農薬原体として２−メチル−3′−イソプロポキ
シベンズアニライド40部、他の乳化剤としてポリ
オキシエチレンノニルフエニルエーテルサルフエ
ート／ポリオキシエチレンスチリルフエニルエー
テル混合物７部、溶剤としてエチレングリコール
モノエチルエーテル９部の順にそれぞれ計量して
混合槽に入れ、高速撹拌機（株式会社島崎製作所
製：RB型撹拌機）により90分間粉砕混合し、こ
れに0.1部の消泡剤（旭化学工業株式会社製：シ
リコーンAF−128）を加え、湿式粉砕機の送液速
度30／時間としたほかは実施例１と同様にして
製剤100部を得た。
参考例 ４
水45.6部にヘテロポリサツカライドゴム0.3部
を加えて通常撹拌機により20分間溶解混合し、次
に農薬原体としてジメチル２−クロロ−１−（２，
４−ジクロルフエニル）ビニルホスフエート20部
およびｍ−トリルメチルカーバメート20部、他の
乳化剤としてポリオキシエチレンスチリルフエニ
ルエーテル／ポリオキシエチレンノニルフエニル
エーテルサルフエート／ジシクロヘキシルスルホ
コハク酸ナトリウム混合物８部、溶剤としてケロ
シン３部、オルソクロルトルエン３部の順にそれ
ぞれ計量して混合槽に入れ、高速撹拌機（株式会
社島崎製作所製：RB型撹拌機）により60分間粉
砕混合し、これに0.1部の消泡剤（旭化学工業株
式会社製：シリコーンAF−128）を加え、湿式粉
砕機の送液速度30／時間としたほかは実施例１
と同様にして製剤100部を得た。
参考例 ５
水58.4部にアエロジル200（日本アエロジル製：
二酸化硅素）１部を加えて通常撹拌機により20分
間溶解混合し、次に農薬原体として５−メチル−
〔１，２，４〕トリアゾロ〔３，４−ｂ〕ベンゾ
チアゾール20部、β−ナフタレンスルホン酸ナト
リウムホルマリン縮合物0.5部、他の乳化剤とし
てポリオキシエチレンスチリルフエニルエーテ
ル／ポリオキシエチレンノニルフエニルエーテル
サルフエート／ジオクチルスルホコハク酸ナトリ
ウム混合物10部、エチレングリコール10部の順に
それぞれ計量して混合槽に入れ、高速撹拌機（株
式会社島崎製作所製：RB型撹拌機）により40分
間粉砕混合し、これに0.1部の消泡剤（旭化学工
業株式会社製：シリコーンAF−128）を加え、実
施例１と同様にして製剤100部を得た。
参考例 ６
水59.7部にヘテロポリサツカライドゴム0.2部
を加えて通常撹拌機により20分間溶解混合し、次
に農薬原体として５−メチル−〔１，２，４〕ト
リアゾロ〔３，４−ｂ〕ベンゾチアゾール20部、
ポリオキシエチレンノニルフエニルエーテル10
部、エチレングリコール10部の順にそれぞれ計量
して混合槽に入れ、高速撹拌機（株式会社島崎製
作所製：RB型撹拌機）により40分間粉砕混合
し、これに0.1部の消泡剤（旭化学工業株式会社
製：シリコーンAF−128）を加え、実施例１と同
様にして製剤100部を得た。
参考例 ７
水77.7部にカルボキシメチルセルロース１部を
加えて通常撹拌機により20分間溶解混合し、次に
農薬原体として５−メチル−〔１，２，４〕トリ
アゾロ〔３，４−ｂ〕ベンゾチアゾール20部、ポ
リオキシエチレンノニルフエニルエーテル0.2部、
アルキルナフタレンスルホン酸ナトリウム１部の
順にそれぞれ計量して混合槽に入れ、高速撹拌機
（株式会社島崎製作所製：RB型撹拌機）により
40分間粉砕混合し、これに0.1部の消泡剤（旭化
学工業株式会社製：シリコーンAF−128）を加
え、実施例１と同様にして製剤100部を得た。
参考例 ８
水77.7部にアラビアゴム１部を加えて通常撹拌
機により20分間溶解混合し、次に農薬原体として
５−メチル−〔１，２，４〕トリアゾロ〔３，４
−ｂ〕ベンゾチアゾール20部、ポリオキシエチレ
ンノニルフエニルエーテル0.2部、β−ナフタレ
ンスルホン酸ナトリウムホルマリン縮合物１部の
順にそれぞれ計量して混合槽に入れ、高速撹拌機
（株式会社島崎製作所製：RB型撹拌機）により
40分間粉砕混合し、これに0.1部の消泡剤（旭化
学工業株式会社製：シリコーンAF−128）を加
え、実施例１と同様にして製剤100部を得た。
試験例 １
物理性状試験
上記実施例および参考例により得られた製剤に
ついて、比重、耐寒性、耐熱性および分離度を次
の方法により測定した。
比重：JISK−4101により測定する。
耐寒性、耐熱性：50ml容ロウソクビンに各組成物
40mlを入れて密栓を行い、−50℃および50℃に
７日間保存し、分離沈降性を測定する。結果は
液全体の高さに対する上澄液の高さの割合
（％）で表わす。
分離度：超遠心分離機備え付の100ml容器に各組
成物80mlを入れたのち栓をし、回転数12000回
転で25分間回転させて沈降性を測定する。結果
は液全体の高さに対する上澄部の高さの割合
（％）で表わす。
試験結果を第１表に示す。
This invention relates to a water-suspended agrochemical formulation in which a pesticide active substance that is solid at room temperature and poorly water-soluble is formulated into a dosage form suitable for use as a spraying agent. Pesticides come in a variety of formulations, including powders, granules, wettable powders, and emulsions. Among these, powder agents have disadvantages such as a large amount of scattering to the surroundings when being sprayed. In addition, hydrating powders have the disadvantage of poor stability, as they tend to settle between the time they are prepared and the time they are applied. Furthermore, emulsions require the active ingredients to be easily dissolved in solvents, so the types of active ingredients that can be emulsified are limited, and since they use organic solvents, they are flammable, and some crops may suffer from chemical damage. There are drawbacks such as: Recently, aerial spraying using liquid agents is often used to save labor in spraying work, but the conventional formulations mentioned above are not necessarily suitable for this purpose.
A new formulation is desired. Suitable preparations for this purpose include spraying agents (Special Publication No. 20519, 1972), which are formulated into suspensions of agricultural chemical ingredients that are poorly soluble in solvents and cannot be emulsified in water or a hydrophilic medium, and liquid organophosphorus insecticides. An oil-in-water mayonnaise-like preparation containing a high concentration of organophosphorus insecticide by blending hydrophobic organic solvents, surfactants, thickeners, etc.
No.), water-insoluble biocides and nonionic surfactants,
Fluid aqueous biocide composition containing heteropolysaccharide rubber and water (Japanese Patent Publication No. 53-46889
In systems containing poorly water-soluble solid pesticides, or poorly water-soluble solid pesticides and water-soluble solid pesticides at the same time, water is used as a dispersion medium, and suspension pesticides (Tokuko Showa) consisting of a surfactant and a water-soluble polymer are used. 58-24401)
etc. are known. However, in these conventional formulations, in order to make the agricultural chemical ingredient into ultrafine particles, it is suspended in a solvent and wet-pulverized, and the physical properties are stabilized by adding emulsifiers, dispersants, etc. It is not always possible to obtain stable properties in terms of the state in which pulverized particles are uniformly dispersed or the state in which they are stably suspended in a solvent, and it cannot be said that they have sufficient properties as a suspension pesticide formulation. There were flaws. This invention was made to eliminate the drawbacks of conventional products as described above, and by blending special emulsifiers and thickeners, it is possible to make agricultural chemical ingredients that are solid at room temperature and poorly water-soluble uniformly and stably. The object of the present invention is to provide a water-suspended agrochemical formulation that is easy to suspend and handle, has excellent storage stability, has excellent dispersibility and suspension properties during spraying, and is suitable for use as a spraying agent. In this invention, the active ingredients include 50% by weight or less of a pesticide active ingredient that is solid at room temperature and poorly water-soluble, 0.3 to 3% by weight of β-naphthalenesulfonic acid formalin condensate salt, and 5 to 12% by weight of other emulsifiers. and a water-suspended agricultural chemical formulation containing 0.05 to 0.5% by weight of heteropolysaccharide rubber. The agricultural chemical active ingredient as an active ingredient applicable to this invention is not particularly limited as long as it is solid at room temperature and poorly soluble (including insoluble) in water; for example, 5-methyl-[1,2 ,4] triazolo[3,
4-b] Benzothiazole (tricyclazole),
Fungicides such as 2-methyl-3'-isopropoxybenzanilide (mepronil), 0,0'-dimethyl 2-chloro-1-(2,4-dichlorophenyl)
Insecticides such as vinyl phosphate, m-tolyl N-methyl carbamate, tricyclohexyltin hydroxide, 2-chloro-4,6-bis(ethylamino)-1,3,5-triazine, 2-
Examples include herbicides such as chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine. These agricultural chemical ingredients may be used alone depending on the purpose, or may be used as a mixture of two or more types, or may be used as a mixture with other agricultural chemical ingredients, such as liquid or water-soluble ones. . The blending ratio of the agricultural chemical ingredient is 50% by weight or less, preferably 10 to 50% by weight. The β-naphthalenesulfonic acid formalin condensate salt is an anionic surfactant, and includes, for example, the sodium salt, calcium salt, ammonium salt, magnesium salt, and triethanolamine salt of the β-naphthalenesulfonic acid formalin condensate. The blending ratio of β-naphthalene sulfonic acid formalin condensate salt is 0.3 to 3% by weight, preferably 0.5 to 1% by weight.
Weight%. Other emulsifiers include anionic surfactants such as dialkyl sulfosuccinates, alkylaryl sulfonates, and lignin sulfonates;
Also preferred are polyoxyethylene arylphenyl ether, polyoxyethylene alkylaryl ether sulfate, and the like. These emulsifiers may be used alone or in combination of two or more, and the mixing ratio when mixed can be selected arbitrarily. The blending ratio of the emulsifier is 5 to 12% by weight. Heteropolysaccharide rubber is compounded as a thickening agent and is generally called xanthan gum. It is a high molecular weight linear extracellular substance produced by the action of bacteria of the genus Xanthomonas, and has a molecular weight of 20,000 to 1,000,000 or more. It has a molecular weight exceeding Water is the main solvent used in the water-suspended agricultural chemical formulation of this invention, and water alone may be used, but if physicochemical properties such as cold resistance, heat resistance, and specific gravity need to be considered, isopropyl alcohol is used. , hydrophilic solvents such as glycerin, polyethylene glycol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, or in some cases xylene, orthochlorotoluene, kerosene, mineral oil,
One or more organic solvents selected from hydrophobic solvents such as vegetable oil and liquid paraffin may be blended. When a solvent is added, the mixing ratio is 1 to 30% by weight, preferably 10 to 20% by weight. In addition to the above-mentioned components, the water-suspended agricultural chemical formulation of the present invention may contain up to 5% by weight of an antifoaming agent, such as a silicone antifoaming agent whose main component is dimethylpolysiloxane. Other ingredients may also be added. Next, an example of the manufacturing process of the formulation of this invention will be shown.
First, a predetermined amount of heteropolysaccharide rubber as a thickener is dissolved and mixed in water to a concentration of 0.1 to 0.6% by weight using a stirrer. Next, predetermined amounts of the pesticide raw material, surfactant, antifoaming agent, organic solvent, and additional water are weighed in this order and placed in a mixing tank, and the mixture is crushed and mixed using a high-speed stirrer for 30 to 90 minutes. Next, these mixtures are processed using a wet grinder to reduce the pesticide ingredients to 4 μm or less.
The product is preferably pulverized to a particle size of 0.5 to 3 μm. The water-suspended agricultural chemical formulation of the present invention is formulated with a combination of special emulsifiers and thickeners, so it can uniformly and stably suspend agricultural chemical ingredients that are solid at room temperature and are poorly water-soluble, and improves dispersibility. As a result, it is easy to handle throughout the period of manufacture and use, has extremely low sedimentation even during long-term storage, has excellent storage stability, and has excellent dispersibility and suspension when spraying, making it extremely excellent as a dispersing agent. It is something that Next, Examples and Test Examples of the present invention will be described. In each example, parts indicate parts by weight. Example 1 0.2 parts of heteropolysaccharide rubber was added to 62.2 parts of water, and a regular stirrer (manufactured by Tokushu Kika Kogyo Co., Ltd.:
Dissolve and mix for 20 minutes using a homomixer (model HV-M), then add 20 parts of 5-methyl-[1,2,4]triazolo[3,4-b]benzothiazole and sodium β-naphthalenesulfonate formalin condensate.
0.5 parts of polyoxyethylene styryl phenyl ether/polyoxyethylene nonyl phenyl ether sulfate/sodium dioctyl sulfosuccinate mixture, and 10 parts of ethylene glycol were weighed in this order into a mixing tank, and placed in a high-speed stirrer (Co., Ltd.). By Shimazaki Seisakusho: RB type stirrer)
Grind and mix for 40 minutes, add 0.1 part of antifoaming agent (Silicone AF-128 manufactured by Asahi Chemical Industry Co., Ltd.), and after stirring, add 4 hard glass beads of 1.0 to 1.5 mm.
A wet grinder with a capacity of 8 cells (manufactured by Igarashi Machine Manufacturing Co., Ltd.: 2G Sand Grinder)
SL type) was used to obtain 100 parts of a homogeneous water-suspended agricultural chemical formulation by finely pulverizing the mixture at a liquid feeding rate of 20/hour. Example 2 0.1 part of heteropolysaccharide rubber was added to 42.8 parts of water, dissolved and mixed for 20 minutes using a regular stirrer, and then 40 parts of 2-methyl-3'-isopropoxybenzanilide and β-naphthalene were added as pesticide ingredients. Weigh and mix 1 part of calcium sulfonate formalin condensate, 7 parts of polyoxyethylene nonyl phenyl ether sulfate/polyoxyethylene styrylphenyl ether mixture as another emulsifier, and 9 parts of ethylene glycol monoethyl ether as a solvent. The mixture was placed in a tank and pulverized and mixed for 90 minutes using a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.), and 0.1 part of an antifoaming agent (Silicone AF-128 manufactured by Asahi Chemical Industries, Ltd.) was added to this. Example 1 except that the liquid feed rate of the wet crusher was set to 30/hour.
100 parts of the preparation were obtained in the same manner as above. Example 3 0.1 part of heteropolysaccharide rubber was added to 57.3 parts of water, dissolved and mixed for 20 minutes using a regular stirrer, and then 5-methyl-[1,2,4]triazolo[3,4-b] was added as the agricultural chemical ingredient. ] 10 parts of benzothiazole and 20 parts of S-benzyl diisopropyl phosphorothiolate, 0.5 part of sodium β-naphthalene sulfonate formalin condensate, 5 parts of polyoxyethylene styryl phenyl ether as another emulsifier,
Weighed 7 parts of liquid paraffin as a solvent and placed them in a mixing tank, pulverized and mixed for 90 minutes using a high-speed stirrer (Shimazaki Manufacturing Co., Ltd.: RB type stirrer), and added 0.1 part of an antifoaming agent (Asahi Chemical Co., Ltd.). 100 parts of a preparation was obtained in the same manner as in Example 1, except that Silicone AF-128 (manufactured by Kogyo Co., Ltd.) was added and the liquid feed rate of the wet grinder was set to 30/hour. Example 4 0.3 parts of heteropolysaccharide rubber was added to 44.9 parts of water, dissolved and mixed for 20 minutes using a regular stirrer, and then dimethyl 2-chloro-1-(2,
20 parts of 4-dichlorophenyl) vinyl phosphate and 20 parts of m-tolylmethylcarbamate, β-
0.7 parts of calcium naphthalene sulfonate formalin condensate, 8 parts of polyoxyethylene styrylphenyl ether/sodium dicyclohexyl sulfosuccinate/polyoxyethylene nonyl phenyl ether sulfate mixture as other emulsifiers,
Weigh out 3 parts of kerosene and 3 parts of orthochlorotoluene as a solvent, put them into a mixing tank, and add them to a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.).
Grind and mix for 60 minutes, and add 0.1 part of antifoaming agent (Silicone AF-128, manufactured by Asahi Chemical Industry Co., Ltd.) to this.
100 parts of a preparation was obtained in the same manner as in Example 1, except that the liquid feed rate of the wet grinder was changed to 30/hour. Example 5 0.3 parts of heteropolysaccharide rubber in 44.3 parts of water,
Add 40 parts of 2-chloro-4,6-bis(ethylamino)-1,3,5-triazine as a pesticide raw material, dissolve and mix for 30 minutes using a regular stirrer, and then add β-
0.3 parts of sodium naphthalene sulfonate formalin condensate, other emulsifiers: polyoxyethylene styrylphenyl ether/polyoxyethylene benzyl phenyl ether/polyoxyethylene dodecyl phenyl ether sulfate mixture 6
1 part, 4 parts of isopropyl alcohol as a solvent, and 5 parts of polyethylene glycol (average molecular weight 200) were weighed in this order into a mixing tank, and mixed with a high-speed stirrer (model RB stirrer manufactured by Shimazaki Manufacturing Co., Ltd.).
The procedure was the same as in Example 1, except that the mixture was pulverized and mixed for 70 minutes, 0.1 part of an antifoaming agent (Silicone AF-128, manufactured by Asahi Chemical Industry Co., Ltd.) was added, and the liquid feed rate of the wet pulverizer was set to 20/hour. 100 parts of the preparation were obtained. Example 6 0.3 parts of heteropolysaccharide rubber in 56.1 parts of water,
25 parts of tricyclohexyltine hydroxyoxide as agricultural chemical ingredients, 0.5 parts of sodium β-naphthalene sulfonate formalin condensate, and 8 parts of polyoxyethylene styryl phenyl ether/sodium dibutyl sulfosuccinate mixture as other emulsifiers.
1 part and 10 parts of ethylene glycol as a solvent were weighed into a mixing tank, pulverized and mixed for 30 minutes using a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.), and 0.1 part of an antifoaming agent ( 100 parts of a formulation was obtained in the same manner as in Example 1, except that silicone AF-128 (manufactured by Asahi Chemical Industry Co., Ltd.) was added and the liquid feed rate of the wet grinder was set to 30/hour. Example 7 0.2 parts of heteropolysaccharide rubber was added to 72.2 parts of water, dissolved and mixed for 20 minutes using a regular stirrer, and then 5-methyl-[1,2,4]triazolo[3,4-b] was added as the agricultural chemical raw material. ] 20 parts of benzothiazole,
Weigh out 0.5 parts of sodium β-naphthalene sulfonate formalin condensate and 7 parts of polyoxyethylene styrylphenyl ether/polyoxyethylene nonyl phenyl ether sulfate/sodium dioctyl sulfosuccinate mixture as other emulsifiers and add them to a mixing tank. and stirred using a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.).
The procedure was the same as in Example 1 except that 0.1 part of an antifoaming agent (Silicone AF-128, manufactured by Asahi Chemical Industry Co., Ltd.) was added to the mixture for 40 minutes, and the liquid feed rate of the wet pulverizer was set to 20/hour. 100 parts of the preparation were obtained. Reference Example 1 Add 0.2 parts of heteropolysaccharide rubber to 59.7 parts of water, dissolve and mix for 20 minutes using a regular stirrer, and then add 5-methyl-[1,2,4]triazolo[3,4-b] as the agricultural chemical ingredient. ] 20 parts of benzothiazole,
As other emulsifiers, 10 parts of a polyoxyethylene styryl phenyl ether/polyoxyethylene nonyl phenyl ether sulfate/sodium dioctyl sulfosuccinate mixture and 10 parts of ethylene glycol were weighed and placed in a mixing tank in this order. Grind and mix for 40 minutes using an RB type stirrer (manufactured by Shimazaki Seisakusho), and add 0.1 part of an antifoaming agent (manufactured by Asahi Chemical Industry Co., Ltd.: Silicone AF-) for 40 minutes.
128) was added, and 100 parts of a preparation was obtained in the same manner as in Example 1. Reference Example 2 Add 0.2 parts of heteropolysaccharide rubber to 69.2 parts of water, dissolve and mix for 20 minutes using a stirrer, and then add 5-methyl-[1,2,4]triazolo[3,4-b] as the agricultural chemical ingredient. ] 20 parts of benzothiazole,
0.5 parts of sodium β-naphthalene sulfonate formalin condensate and 10 parts of ethylene glycol were weighed in this order and placed in a mixing tank, and pulverized and mixed for 40 minutes using a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.). 0.1 part of an antifoaming agent (Silicone AF-128, manufactured by Asahi Chemical Industry Co., Ltd.) was added to the mixture, and 100 parts of a formulation was obtained in the same manner as in Example 1. Reference Example 3 Add 0.1 part of heteropolysaccharide rubber to 43.8 parts of water, dissolve and mix for 20 minutes using a regular stirrer, then add 40 parts of 2-methyl-3'-isopropoxybenzanilide as the agricultural chemical raw material and other emulsifiers. Weigh out 7 parts of polyoxyethylene nonyl phenyl ether sulfate/polyoxyethylene styryl phenyl ether mixture as a solvent and 9 parts of ethylene glycol monoethyl ether as a solvent, put them into a mixing tank, and place them into a mixing tank using a high-speed stirrer (Shimazaki Manufacturing Co., Ltd.). The mixture was pulverized and mixed for 90 minutes using an RB type stirrer (manufactured by Manufacturer: RB type stirrer), and 0.1 part of an antifoaming agent (manufactured by Asahi Chemical Industry Co., Ltd.: Silicone AF-128) was added to this, and the liquid feed rate of the wet pulverizer was adjusted to 30/hour. Otherwise, 100 parts of the preparation was obtained in the same manner as in Example 1. Reference Example 4 Add 0.3 parts of heteropolysaccharide rubber to 45.6 parts of water, dissolve and mix for 20 minutes using a regular stirrer, and then add dimethyl 2-chloro-1-(2,
20 parts of 4-dichlorophenyl) vinyl phosphate and 20 parts of m-tolyl methyl carbamate, 8 parts of polyoxyethylene styrylphenyl ether/polyoxyethylene nonyl phenyl ether sulfate/sodium dicyclohexyl sulfosuccinate mixture as other emulsifiers, as solvent Weigh 3 parts of kerosene and 3 parts of orthochlorotoluene in order, put them into a mixing tank, grind and mix for 60 minutes using a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.), and add 0.1 part of an antifoaming agent to this. Example 1 except that silicone AF-128 (manufactured by Asahi Chemical Industry Co., Ltd.) was added and the liquid feeding rate of the wet grinder was set to 30/hour.
100 parts of the preparation were obtained in the same manner as above. Reference example 5 Aerosil 200 (manufactured by Nippon Aerosil) in 58.4 parts of water.
Add 1 part of silicon dioxide) and dissolve and mix for 20 minutes using a regular stirrer.
[1,2,4]triazolo[3,4-b]benzothiazole 20 parts, β-naphthalenesulfonate sodium formalin condensate 0.5 part, polyoxyethylene styryl phenyl ether/polyoxyethylene nonylphenyl as other emulsifiers Weigh out 10 parts of the ether sulfate/sodium dioctyl sulfosuccinate mixture and 10 parts of ethylene glycol in that order, put them into a mixing tank, pulverize and mix for 40 minutes using a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.). 0.1 part of an antifoaming agent (Silicone AF-128, manufactured by Asahi Chemical Industry Co., Ltd.) was added to the mixture, and 100 parts of a formulation was obtained in the same manner as in Example 1. Reference Example 6 Add 0.2 parts of heteropolysaccharide rubber to 59.7 parts of water, dissolve and mix for 20 minutes using a stirrer, and then add 5-methyl-[1,2,4]triazolo[3,4-b] as the agricultural chemical ingredient. ] 20 parts of benzothiazole,
Polyoxyethylene nonyl phenyl ether 10
10 parts of ethylene glycol and 10 parts of ethylene glycol were weighed and placed in a mixing tank, and ground and mixed for 40 minutes using a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.). Silicone AF-128 (manufactured by Kogyo Co., Ltd.) was added, and 100 parts of a preparation was obtained in the same manner as in Example 1. Reference Example 7 Add 1 part of carboxymethylcellulose to 77.7 parts of water, dissolve and mix for 20 minutes using a regular stirrer, and then add 5-methyl-[1,2,4]triazolo[3,4-b]benzo as the agricultural chemical ingredient. 20 parts of thiazole, 0.2 parts of polyoxyethylene nonyl phenyl ether,
Weigh out 1 part of sodium alkylnaphthalene sulfonate and place it in a mixing tank, and use a high-speed stirrer (RB type stirrer manufactured by Shimazaki Manufacturing Co., Ltd.).
After pulverizing and mixing for 40 minutes, 0.1 part of an antifoaming agent (Silicone AF-128, manufactured by Asahi Chemical Industry Co., Ltd.) was added, and 100 parts of a formulation was obtained in the same manner as in Example 1. Reference Example 8 Add 1 part of gum arabic to 77.7 parts of water, dissolve and mix for 20 minutes using a stirrer, and then add 5-methyl-[1,2,4]triazolo[3,4] as the agricultural chemical ingredient.
-b] 20 parts of benzothiazole, 0.2 parts of polyoxyethylene nonyl phenyl ether, and 1 part of sodium β-naphthalene sulfonate formalin condensate were weighed in this order and placed in a mixing tank, using a high-speed stirrer (manufactured by Shimazaki Seisakusho Co., Ltd.: (RB type stirrer)
After pulverizing and mixing for 40 minutes, 0.1 part of an antifoaming agent (Silicone AF-128, manufactured by Asahi Chemical Industry Co., Ltd.) was added thereto, and 100 parts of a formulation was obtained in the same manner as in Example 1. Test Example 1 Physical Property Test The specific gravity, cold resistance, heat resistance, and degree of separation of the preparations obtained in the above Examples and Reference Examples were measured by the following methods. Specific gravity: Measured according to JISK-4101. Cold resistance, heat resistance: Each composition in a 50ml candle bottle
Pour 40 ml into the solution, seal it, store it at -50°C and 50°C for 7 days, and measure the separation and sedimentation properties. The results are expressed as the ratio (%) of the height of the supernatant liquid to the height of the entire liquid. Separation degree: After putting 80 ml of each composition into a 100 ml container equipped with an ultracentrifuge, stopper the container, rotate at 12,000 rpm for 25 minutes, and measure sedimentation. The results are expressed as the ratio (%) of the height of the supernatant to the height of the entire liquid. The test results are shown in Table 1.
【表】
以上の結果より、本発明のゾル剤は過酷な温度
条件下においても、また長期保存にかえる過酷な
重力を加えた加速試験においても分離沈降が少な
く、貯蔵安定性に優れることがわかる。
試験例 ２
貯蔵安定性試験
ゾル製剤500ｇを500ml容のガラス瓶に入れて室
温下に１年間静置保存し、製剤の分離沈降性を測
定した。結果は液全体の高さに対する上澄部の高
さの割合（％）で表わした。また測定終了後、ガ
ラス棒を静かに入れ、ハードケーキング層の形成
の有無を観察した。
貯蔵安定性は上澄部の割合が小さいほど良好で
あり、またハードケーキング層の形成はゾル製剤
として不適である。
結果を第２表に示す。[Table] From the above results, it can be seen that the sol of the present invention exhibits excellent storage stability with little separation and sedimentation even under severe temperature conditions and in accelerated tests that apply severe gravity for long-term storage. . Test Example 2 Storage Stability Test 500 g of the sol preparation was placed in a 500 ml glass bottle and stored at room temperature for one year, and the separation and sedimentation properties of the preparation were measured. The results were expressed as the ratio (%) of the height of the supernatant to the height of the entire liquid. Furthermore, after the measurement was completed, a glass rod was gently inserted and the presence or absence of the formation of a hard caking layer was observed. The smaller the proportion of the supernatant, the better the storage stability, and the formation of a hard caking layer is unsuitable for use as a sol preparation. The results are shown in Table 2.
【表】
の発生を示す。
以上の結果より、本発明のゾル剤は長期間保存
しても分離沈降が少なく、貯蔵安定性に優れるこ
とがわかる。
試験例 ３
水中における分散性試験および懸垂性試験
分散性試験：250ml容メスシリンダーに水250mlを
入れ、ピペツトより製剤を滴下して分散状態を
観察し、次に４段階の評価を行つた。
◎：分散状態が極めて良好で、製剤は水の中で容
易に拡散し分散する。最も好ましい製剤であ
る。
〇：分散状態が良好で、製剤は水の中で一部拡散
しながら液滴の形で水中を落下するが、底に着
くまでには概ね分散してしまう。好ましい製剤
である。
△：分散状態がやや悪く、製剤の大部分が液滴の
形で底まで落下するが、メスシリンダーを振れ
ば分散する。実用場面において問題となる場合
がある。
×：分散状態が悪く、製剤は液滴の形で底まで落
下し、メスシリンダーを振つても分散しない。
実用製剤として不適である。
懸垂性試験：250ml容のメスシリンダーに水約200
mlを入れ、組成物12.5ｇを加える（このときの
有効成分はAg）。水を加えて250mlとした後、
１分間静置する。次に25mlホールピペツトを液
の中央部に保ち、25mlを吸い取り、有機溶媒で
抽出した後、ガスクロマトグラフイーまたは液
体クロマトグラフイーにより有効成分の含有量
を測定する（Bg）。次の式により懸垂率を算出
する。
懸垂率（％）＝Ｂ×10／Ａ×100
結果を第３表に示す。[Table] shows the occurrence of.
From the above results, it can be seen that the sol of the present invention exhibits less separation and sedimentation even when stored for a long period of time, and has excellent storage stability. Test Example 3 Dispersibility test and suspension test in water Dispersibility test: 250 ml of water was placed in a 250 ml measuring cylinder, and the formulation was added dropwise with a pipette to observe the dispersion state, and then evaluated on a 4-grade scale. ◎: The dispersion state is extremely good, and the formulation easily diffuses and disperses in water. This is the most preferred formulation. ○: The dispersion state is good, and the formulation falls into the water in the form of droplets while partially dispersing in the water, but it is mostly dispersed by the time it reaches the bottom. A preferred formulation. Δ: The state of dispersion is somewhat poor, and most of the formulation falls to the bottom in the form of droplets, but it is dispersed by shaking the measuring cylinder. This may cause problems in practical situations. ×: The dispersion state is poor, the formulation falls to the bottom in the form of droplets, and is not dispersed even when the graduated cylinder is shaken.
Unsuitable as a practical preparation. Suspension test: Approximately 200ml of water in a 250ml graduated cylinder
ml and add 12.5 g of the composition (the active ingredient at this time is Ag). After adding water to make 250ml,
Let stand for 1 minute. Next, hold a 25 ml pipette in the center of the liquid, suck up 25 ml, extract with an organic solvent, and measure the active ingredient content by gas chromatography or liquid chromatography (Bg). Calculate the suspension rate using the following formula. Suspension rate (%)=B×10/A×100 The results are shown in Table 3.
【表】【table】
【表】
以上の結果より、本発明のゾル剤は水中に投下
した際の分散性が良好であり、かつ希釈液の懸垂
性が良好であること、即ち散布剤として優れるこ
とがわかる。
試験例 ４
いもち病防除効果試験
稲の種子（品種十石）を径９cmの素焼鉢で育成
させた４葉期のイネを１m2の木枠内に並べ、前記
実施例１および参考例２で製造したのち１ケ月間
室温に静置した製剤を、所定の希釈倍数になるよ
うに水で希釈調製し、１区あたり100mlを杓型噴
霧器で散布した。散布２日後湿室内でいもち病菌
胞子懸濁液を噴霧接種した。10日後に10葉あたり
の病斑数を調査し、次の判定基準により罹病指数
を判定した結果を第４表に示す。
判定基準 ５：罹病無 ４：罹病微
３：罹病少 ２：罹病多
１：罹病甚大[Table] From the above results, it can be seen that the sol of the present invention has good dispersibility when dropped into water, and also has good suspension properties of the diluted liquid, that is, it is excellent as a dispersing agent. Test Example 4 Rice blast control effect test Four-leaf stage rice grown from rice seeds (variety: Tokoku) in clay pots with a diameter of 9 cm was arranged in a 1 m 2 wooden frame, and the rice seeds of Example 1 and Reference Example 2 were The preparation was left at room temperature for one month after being manufactured, and then diluted with water to a predetermined dilution ratio, and 100 ml per area was sprayed using a ladle-type sprayer. Two days after spraying, a spore suspension of blast fungus was inoculated by spraying in a humid room. After 10 days, the number of lesions per 10 leaves was investigated, and the disease index was determined according to the following criteria. The results are shown in Table 4. Judgment criteria 5: No morbidity 4: Slight morbidity 3: Little morbidity 2: Major morbidity 1: Severe morbidity
【表】
以上の結果より、本発明の実施例のものは耐寒
耐熱性および分散性に優れ、農薬としての活性も
高いことがわかる。[Table] From the above results, it can be seen that the examples of the present invention have excellent cold and heat resistance and dispersibility, and have high activity as agricultural chemicals.
Claims (1)
農薬原体を50重量％以下、β−ナフタレンスルホ
ン酸ホルマリン縮合物塩を0.3〜３重量％、その
他の乳化剤を５〜12重量％およびヘテロポリサツ
カライドゴムを0.05〜0.5重量％含有する水中懸
濁型農薬製剤。 ２ 農薬原体は５−メチル−〔１，２，４〕トリ
アゾロ〔３，４−ｂ〕ベンゾチアゾール、２−メ
チル−3′−イソプロポキシベンズアニライド、
０，0′−ジメチル２−クロロ−１−（２，４−ジ
クロルフエニル）ビニルホスフエート、ｍ−トリ
ルＮ−メチルカーバメート、トリシクロヘキシル
チンヒドロオキサイド、２−クロロ−４，６−ビ
ス（エチルアミノ）−１，３，５−トリアジンお
よび２−クロロ−４−エチルアミノ−６−イソプ
ロピルアミノ−１，３，５−トリアジンから選ば
れる１種以上のものである特許請求の範囲第１項
記載の水中懸濁型農薬製剤。 ３ その他の乳化剤はジアルキルスルホコハク酸
塩、アルキルアリールスルホン酸塩、リグニンス
ルホン酸塩、ポリオキシエチレンアリールフエニ
ルエーテルおよびポリオキシエチレンアルキルア
リールエーテルサルフエートから選ばれる１種以
上のものを含む特許請求の範囲第１項または第２
項記載の水中懸濁型農薬製剤。 ４ 溶媒は水を主体とし、これに有機溶媒を配合
したものである特許請求の範囲第１項ないし第３
項のいずれかに記載の水中懸濁型農薬製剤。 ５ 有機溶媒はイソプロピルアルコール、グリセ
リン、ポリエチレングリコール、エチレングリコ
ール、エチレングリコールモノメチルエーテル、
エチレングリコールモノエチルエーテル、キシレ
ン、オルソクロルトルエン、ケロシン、鉱油、植
物油および流動パラフインから選ばれる１種以上
のものである特許請求の範囲第４項記載の水中懸
濁型農薬製剤。[Claims] 1. As active ingredients, 50% by weight or less of a pesticide active ingredient that is solid at room temperature and poorly water-soluble, 0.3 to 3% by weight of β-naphthalenesulfonic acid formalin condensate salt, and 5 to 5% of other emulsifiers. A water-suspended pesticide formulation containing 12% by weight and 0.05-0.5% by weight of heteropolysaccharide gum. 2 The pesticide ingredients are 5-methyl-[1,2,4]triazolo[3,4-b]benzothiazole, 2-methyl-3'-isopropoxybenzanilide,
0,0'-dimethyl 2-chloro-1-(2,4-dichlorophenyl) vinyl phosphate, m-tolyl N-methyl carbamate, tricyclohexyltin hydroxide, 2-chloro-4,6-bis(ethylamino) The water according to claim 1 is one or more selected from -1,3,5-triazine and 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine. Suspension type pesticide formulation. 3. Other emulsifiers include one or more selected from dialkyl sulfosuccinates, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene arylphenyl ethers, and polyoxyethylene alkylaryl ether sulfates. Range 1st or 2nd
The water-suspended agricultural chemical formulation described in Section 1. 4. Claims 1 to 3 in which the solvent is mainly water and an organic solvent is blended therein.
The water-suspended agricultural chemical formulation according to any of the above. 5 Organic solvents include isopropyl alcohol, glycerin, polyethylene glycol, ethylene glycol, ethylene glycol monomethyl ether,
5. The water-suspended agricultural chemical formulation according to claim 4, which is one or more selected from ethylene glycol monoethyl ether, xylene, orthochlorotoluene, kerosene, mineral oil, vegetable oil, and liquid paraffin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP783482A JPS58124702A (en) | 1982-01-21 | 1982-01-21 | Aqueous suspension of agricultural chemical composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP783482A JPS58124702A (en) | 1982-01-21 | 1982-01-21 | Aqueous suspension of agricultural chemical composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58124702A JPS58124702A (en) | 1983-07-25 |
| JPS6358801B2 true JPS6358801B2 (en) | 1988-11-17 |
Family
ID=11676628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP783482A Granted JPS58124702A (en) | 1982-01-21 | 1982-01-21 | Aqueous suspension of agricultural chemical composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58124702A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60214701A (en) * | 1984-04-05 | 1985-10-28 | Mitsubishi Petrochem Co Ltd | Suspended agricultural chemical composition |
| JP2579755B2 (en) * | 1986-07-17 | 1997-02-12 | 塩野義製薬株式会社 | New suspension pesticide formulation |
| JPS638301A (en) * | 1986-06-30 | 1988-01-14 | Kumiai Chem Ind Co Ltd | Fluid suspensionlike agricultural chemical composition |
| JP3804072B2 (en) * | 1991-08-07 | 2006-08-02 | 日産化学工業株式会社 | Aqueous suspension pesticide formulation |
| US5496845A (en) * | 1994-05-25 | 1996-03-05 | American Cyanamid Co. | Suspension concentrate compositions of arylpyrrole insecticidal and acaricidal agents |
| PT1018881E (en) | 1997-02-10 | 2006-07-31 | Sumitomo Chem Takeda Agro Co | SUSPENSION AQUOSA AGROQUIMICA |
| AUPP105497A0 (en) * | 1997-12-19 | 1998-01-15 | Schering-Plough Animal Health Limited | Aqueous insecticidal pour-on treatment |
| DE10036002A1 (en) * | 2000-07-25 | 2002-02-14 | Aventis Cropscience Gmbh | Herbicidal agents |
| KR102617619B1 (en) * | 2021-05-10 | 2023-12-27 | 케이지케미칼 주식회사 | liquid-type fertilizer composition having suspension function for drone spraying and method of manufacturing of the same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49133531A (en) * | 1972-11-09 | 1974-12-21 | ||
| FR2279338A1 (en) * | 1974-07-27 | 1976-02-20 | Fisons Ltd | Atrazine herbicide suspensions - contg Xanthomonas hydrophilic colloid and surfactant |
| JPS5261227A (en) * | 1975-11-12 | 1977-05-20 | Fisons Ltd | Weed killing water suspension |
| JPS5266633A (en) * | 1975-11-27 | 1977-06-02 | Hokko Chem Ind Co Ltd | Stable dispersion of agricultural chemicals |
| JPS5315426A (en) * | 1976-07-26 | 1978-02-13 | Dai Ichi Kogyo Seiyaku Co Ltd | Additive composition for agrichemical hydrating agents |
| JPS542328A (en) * | 1977-06-08 | 1979-01-09 | Nippon Nohyaku Co Ltd | Wettable herbicide |
| GB1593412A (en) * | 1978-05-24 | 1981-07-15 | Fisons Ltd | Herbicidal concentrate |
-
1982
- 1982-01-21 JP JP783482A patent/JPS58124702A/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49133531A (en) * | 1972-11-09 | 1974-12-21 | ||
| FR2279338A1 (en) * | 1974-07-27 | 1976-02-20 | Fisons Ltd | Atrazine herbicide suspensions - contg Xanthomonas hydrophilic colloid and surfactant |
| JPS5261227A (en) * | 1975-11-12 | 1977-05-20 | Fisons Ltd | Weed killing water suspension |
| JPS5266633A (en) * | 1975-11-27 | 1977-06-02 | Hokko Chem Ind Co Ltd | Stable dispersion of agricultural chemicals |
| JPS5315426A (en) * | 1976-07-26 | 1978-02-13 | Dai Ichi Kogyo Seiyaku Co Ltd | Additive composition for agrichemical hydrating agents |
| JPS542328A (en) * | 1977-06-08 | 1979-01-09 | Nippon Nohyaku Co Ltd | Wettable herbicide |
| GB1593412A (en) * | 1978-05-24 | 1981-07-15 | Fisons Ltd | Herbicidal concentrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58124702A (en) | 1983-07-25 |
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