Method for making microcapsules
专利摘要:
This invention relates to a process for encapsulation, and particularly to the production of small or minute capsules constituted by a skin or thin wall of polyurea, which involves bringing together an aqueous phase containing a lignin sulfonate emulsifier and a water-immiscible phase containing a water-immiscible material, the material to be encapsulated, plus polymethylene polyphenylisocyanate, dispersing the water-immiscible phase in the aqueous phase followed by addition of a polyfunctional amine. Polymethylene polyphenylisocyanate reacts with the amine to form a solid polyurea shell wall about the encapsulated material. The capsules formed may be directly used as aqueous suspensions. In the practice of the preferred embodiment of the present invention, the material to be encapsulated is a herbicide, particularly an acetanilide or thiocarbamate herbicide and more particularly alachlor, butachlor, propachlor, triallate and diallate hebicides. 公开号:SU1039436A3 申请号:SU802896355 申请日:1980-03-25 公开日:1983-08-30 发明作者:Бернард Бистмен Джордж;Майлей Деминг Джон 申请人:Монсанто Компани (Фирма); IPC主号:
专利说明:
SAE 1CE . | ь 00 cr: The picture is from Osten to obtain microcapsules, which are widely used for encapsulating complex lipids that are not miscible with water. such as dyes, inks, chemical reagents, pharmaceutical nj Paratov, flavoring agents, pesgicides. herbicides, etc. A method of making a microcapture; the formation of amines, which, in turn, react with non-hydrolyzed isocyanate monomers to form a microcapsule The disadvantage of this method is the possibility of proceoll: enn reaction of the monomial jX) B after packaging. Although the reaction of monomers is quantitative, the hydrolysis of isocyanate monomers can be even further with the elimination of CO, which was at an elevated pressure in the packaged preparation. The closest to the irs-to-be is the method of obtaining crocapsules by dispersion in water (a mixture containing an emulsifier (water)) organic phase alcohol from polymethylenepiphenyl isocyanate and substances, but not mixed with water at a temperature from room to 7 ° C, by the addition of a polyfuicocyoyl amine selected from 1.6 - hexamethylenediami1 .., 5c-hexa ™ methylene triamine, cyetherteramide, trK ethylaminetetramine, tetraethylethylene pentamine, pentamethylenehexams -1 2, However, attempts thus kapsupirovani high concentrations, not miscible with water, for example on the basis gerbitsitsov aueTaHiinnaa and tiokar- mat (480-600 g / l), tsayut nautsovletveritelnye rezultatg due to sintering or solidification of the finished suspensions, incomplete encapsulation of the herbicidal agents, permeation small amounts of herbicides through the polymer walls ki capsules. The purpose of the invention is to prevent agglomeration, reduce permeability and increase the yield of microcapsules. This goal is achieved by the fact that, according to the method of massaging the capsules, by dispersing in the aqueous phase, containing e-thallotor, the organic phase from polymethylene polyphenyl isocyanate and the substance, not mixed with heat, at a temperature of 7PC, added with the addition of 7% of an additive, with the addition of added salt, at an additional temperature of 7PC, added with the addition of 7CPP, added with the addition of heat to the mixture. Hexamethylenetriamine, CET, triethylaminetetramine, tetraethylenepentamine, pentamethylenehexamine, 1,6,5-52,2% by weight of the components of both phases of the substance, do not mix the mixture with water , as an emulsifier of 0.8-1.7% of sodium, potassium, calcium or magnesium ligninsulfonate, with a content of polymethylene polyphenyl isocyanate and polyfoot: 1 of the national amine, 1.6-9.2% and 1, 9, respectively, GRIMER 1. Baseline data:% g 96% technical trialall30.5 200.0 PAPl-135 2,713.9 4O% G; MDA 3.0 i5, i .t Reci to 88 V 4.0 0.8 Ammonium sulfate 26,1132,0 Vatsa27.9 141.3 2OO g of technical triallate containing 13.9 g of polymethylene-phenyliso cyan and mark.and PAP1 - 135, emulgir -ot in 141.3 g of WATER; containing 88 lignixulphonate sodium grade 88B, and the th shical triallate and PAP1 - 135 are flashed {} are sewed at 50 ° C, and the temperature of the aqueous toacTBOpa containing the lignivulphonate emulsifier is The emulsification is carried out with a Waring blender at a high shear rate. To the emulsion, reducing the speed of the star, 15.1 g of 1,6-hexamethylenediamine (HMDA) is added, another 132.0 g of ammonium sulfate is added to the Ceraz for 20 minutes, after which the preparation is bottled. The diameter of the obtained microcapsules fluctuates J3 of 1 H 1. 1O mk. The resulting preparation contains 500 g of capsules and a given T; aiH4ecKoro triallate per liter of aqueous solution, 4ef 3 for a certain period of elongation, neither agglomeration, nor crystal formation is observed. Example 2 The source components are as follows; 91% - 1st technical alachlor chloroperbenzyl Reax 88 B 2OO g. Technical alachlor, Byae 1a 1 va at 50 ° C and socialized 15.0 g of PAP1 is poured into 168.0 warmers containing 3.8 g of ligninsulfone sodium brand Reax 88 V as an emulsifier, at a high shear rate, after which the temperature inside the vessel rises to 60 C. Then 20 g of 35% - but 1 GL, G1A; ots} reduction of speed. Poguchae /; th drug contains 527 g of encapsulated technical alachlor per liter of aqueous solution. The diameter of the resulting l composition; em I-IO K. The approximately liquid layer that is formed is recovered by gentle agitation. Example 3 The initial components are as follows: 91 o-ny tehniche S cia alachlor PAP 4O% Ethylene glycol 200 g of} P1ical alachlor, with a scaling 15.0 g PAP1, emulsified with 155.9 g of water containing 3.8 g of sodium lippsulfonate brand Reax 88, with technical alachlor and PAP1 being higher than | r-kivat1 at 50 ° C, and a solution containing ligninsulfonate emulsifier at room temperature. The emulsification is carried out at a high shear rate, to the emulsion, reducing the rate of - shear, adding 17.1 g of ethylene glycol to the south, after which the preparation is bottled, the osseous layer is completely resuspended from time to time by placing the drug through sieve in 325 broom (| zazmer hole 45 m on the sieve, there is only a small number of particles larger than 45 m. Over time} and the IL1 does not agglomerate the formation of herbicide crystals. Example 4. The initial components are as follows; / 96, 6% - nish technical prop ahlor46,4100, RA P1 f 35.8 ° l. GMLA Rea 88 V Water Raw materials and vessels of the Waring blender are kept at 70 C. 100.0 g 96.6 ° of technical propalor, containing 7.5 g PAPl , emulsified into 96.6 g of water containing 2.0 g of Reax 88 V sodium chloride ligninsulfonate using a Waring blender operating at high speed. 9.3 g of 35.8% HMDA , I In this case, the shear rate is cMecHTedin. Capsule capsules 1 to 60 microns; most of them are D-20 microns in diameter. Example 5, Source components are as follows; 35.5% of hacha chloropolymer Reax 88 V 100.0 g of technical butachlor (90 ° o-th), 7.5 g PAP1 and kept at room temperature, emulsified with 152.4 g of water containing 2, 0 g, sodium aigninsulfonate brand Rea x 88 V, with a high shear rate of the mixer. To the emulsion, add 9.3 g of 35.8 about-HMDA, while reducing the shear rate of the mixer. Particles having a spherical or non-evolute form are obtained with a diameter of 1.- 30 microns, the diameter of most i3 is 1-hr 20 microns. Example Source Components. % you are following; .-ny technical alachlor PAPl 4O °, HMDA Reox 88 V Water E: 1.:: glycol G-work cor / iacHO example 2 for cs: i 048HiieM that the vessel is obstructed; -: under the heated bath, therefore the temperature n., 2c. 50 C, for 20 min;; ; high shear rate; after; 17.1 g ethylene glycol is added. V; th spill the drug on buto., -:, ..,. The diameter of almost all particles is co-cTt; i: r ..-, GT is less than 45 microns, only a very insignificant amount of the product is left on a 325 mesh screen (the maximum hole size is 45 microns). Example. Initial components of the following:% g 93% avhnicheky alachlor PAPl-135 70% BGMTA Reatt 88 V 200.0 g technical alachlor containing 13.9 g PAP1 "-135, emulsify B 166.1 g water (x of 48 ligninsulfonate sodium Vl, all components being kept at 50 ° C, emulsification is carried out using a Waring blender operating with a high shear rate, 15.1 g of 70danthan 5T -G-x-methylene triamine are added to the emulsion (BGM TA), at the same time reducing the shear rate of the mixers. After 2O minutes to 5 degrees Celsius, 41.0 sodium chloride and the product is poured into bottles. The microcapsules that are read are mostly spherical in shape, only the more definite is the number of irregular shapes. The particle diameter is 1-15 microns, and the diameter is approximately 1 micron. Example 8. The initial components are as follows:% g 90% technical alachlor /vloHD.yp M. R HMDA {40% ny) ReaK 88 V Water thylene glycol 4,117,1 2OO, 0 g of 90% technical technical chlorine containing 15.0 g of polymethyl polyphenyl isocyanate Mondur M R at 50 s, is emulsified into 165.4 g waters containing 3.8 rReax 88 V (at room temperature). Emulsified to carry out; shyut at high shear rate. 16.7 g of 40% HMDA are added to the emulsion, at the same time reducing the shear rate and ensuring a minimal mixing. Mepsa 20 minutes added ethylene glycol. The resulting particles have irregular odds; Their diameter is 1-20 MKj in most cases 1-10 microns. Source components Example 9 nentsy the following: 907th technical alachlor PAPl HMDA () Rea. 88 V Ethylene Glycol 45.4 kg of a technical apachlor QO ° o Horo at 60 ° C is placed in a drum with a capacity of 208 l and 3.4 kg of PAP1 is dissolved in it, Then, without stirring the mixture, add 34.3 kg of water, containing Oj9 kg Re ah 88 V. After that, emulsify, stirring the mixture with the help of a specified homogenizer. Then 4.1 kg of 4O% HMDA is added to the emulsion. After 20 minutes, 3.9 g of ethylene glycol is added and the preparation is packed in one-liter containers. The resulting microcapsules are mostly spherical in shape and only a small number of them. wrong form we are. The particle diameter is microns, in most cases microns. Example 10, Source components are as follows; 90% - a new technical alachlor PAP1 135 HMDA- () The starting materials, except for sodium chloride and 4O% HMDA., Are backed out at 50 s. 200 g 90% - log of technical alachlor; containing 7.0 g of PAP1.135, emulsified with 169 g of water, containing 3.8 rReax 88, with the use of NA on the mixer. Varinga. working melting with high shear rate. In the event of a simultaneous reduction of the shear rate, which ensures a smooth placement of the emulsion, 7.7 g of 10% of a single HMDA is applied to the bottom end. After 2 minutes, 39.7 g of sodium chloride are added to reduce the density of the water phase and the density of the expanded micro capsules. I get microcapsules. having a spherical silt of irregular shape and a diameter in the range of 1–20 microns, with the diameter of an opreseleshugo number, the particles reach 80 microns. Example 10 is repeated. the use of cyethylene triamine, triethylen, then tramine and pentamethylene, either alone or in combination with 1.6- 7 gaxmethylenyamine. In tab. 1 lead eight 1039436 Continued table. one PAPI 8.3 9.811.212.513.915.3 16.7 2O, 927.8 41.7 (40%) 9.1 10.612D13.615.016.6 18.2 22.830.0 45.3 . 166,6164,0161,5159,0156,7154,2151.4 142.8132.1125.4 Example 12 nnty following: Monochlorobenzene Papl hmda () 1.0 4.0 Reax 8-8 V "39.3 150.0 Eo :: a 55This example illustrates the encapsulation of an organic solvent. The sequential nature of the addition of individual components corresponds to Example 1, 910, with the ii "s stations performed at room temperature. With the help of the mixer, Waring sets the average shear rate with the lower last in the SOFT stirring after addition of the diamine. The diameter of the obtained 8 # 1 x mp roap soup is 1.15 microns. Example 13 of the Original slurry nentsy:% g alahpor 33.8 1351.4 m buayin11, 0 44O; 6 PAP1-.135 ZD124.6 HMDA (40%) 3.4135 3 eax 88, 935.8 g L P11 l i g. NaCC11 3 Vatsa36,3. A solution of 1351.4 g of ala., 410.6 megabytes and 1214.6 g of PAPl-i3b, taken out at a time, emulsified to B 1459.6 g of water containing 35.8 g of CBDH 88 V sodium emulgrog. Helping homogenizer in square squirt. 135.3 g of HMDA is added to the emulsion and immediately decomposed. Via S M1SH, 452.7 g of sodium chloride is dissolved in the suspension of B. which is time. They have a bottle-type bottle., The diameter of the beam of the spherical M51krk-shpsul is l - lO micron, and is equal to 14. As a source of CSMC, the following% 93% ..; 1st alcalore 32.0 1254.4 92 i- "bi:; i linuron 12d1 4cc) .2 PAPl. GMDL (40%) 3, and ReaX 88, 9 NC (C, Voca Work as in Example 1 i R H M er A; nytenie staying: 98.5%. - paratyon 38.8 200.0 РАР1-135 2 , GMLA (40%. -Ny) 2,915.1 Reax 88, 78, B | .JC (N0317.7 91.1 Wots 36.2 A solution of 13.9 g of PAP1- ™ 135- in 200.0 parathion is emulsified in 187 , 0 g of water, containing 8.6 gCea 88, prncheyG all components are drained at 5 ° C.Protection is carried out using 3610 mixtures of Ba-rtzh gel, nt jibyyacb homogenous ™ to HcKqiror type jams; Stsvig, to the emulsion 14 add p | gkreishk1T razk snvenke. Use the mixture with gel and pi to-dkhoks razmes; -yyCH: 1Ya, b suspensions rass tpor 9.1, i gd-d-d, dysme; j .ic-rays-1x spherical v: i- i: pO i: anc) J composition / 1–1 µ micron / rn Mayor 16, nnty slopus: 2; -pa-f ", butnl 2.-oslor-.1-; Metoxülstl-O methyl.,,. I.,, -, rio: -.- r ego: Esaore; kie, .iu: ii: oro "еринrintzica ..; .. .-;.. .....- / g jcRieci ia}, 21, g NDR1 -. 1ooo, emulkkru; o; i vouy, coaep.:iiiiuicn g. o ...-:; -, g: .iag; -ly1ot;.) o,;: ... il schercy. L.;: .. With | :. -j Get C4 ep Numbers; and P- 4-10 NK, r5il: r-- Kspku ig-lm; - ..:.:., -: o, 5ots .. All wsachtsnsl..suslovi ss-opetts . lt example 1G per l.;: k, .yyu1yum gogs, cht- dog doagolti lr,: imenu1 at .. ohlagoy temzratughe. Dalgeter oolshshyugaata lakopo syk.krychosk; to hl; iro: ca1; sul is 4-10 microns, npeiLiUKT is nete; one hundred, .., 1 1 cyclohexene / (i -1-IL - 3- (2-fluoro)) -1-methylms chevina (95%) 44.03 304.00, 07 21.22 GMLA (43 , 26%) 3.0721.22 Reax 88 V 0.94 6.50 Warts39.14 270.24 NqCE9.74 67.24 The reaction data is equivalent to Example 16. The diameter of most micro capsules is 4-15 microns. The drug is stable. Example 19. The starting components are the following;% g 5-thiazole rhonoic acid, 2-chloro-4- (trifluoromethyl) (phenylmethyl) ether (98%) 39.08 DL, 4.0 PAPl-135 2.7321 , 22 HMDA (43.26%) 2.7321.22 Reax 88, 84 6.50 Vaca41.49 322.77 KaSe13.14 102.20 The reaction conditions are as in Example 16 with the exception that the starting components are used at 6 0 The diameter of most spherical micro capsules is 4 to 10 microns. The preparation is stable. JD 20. The initial components are as follows: "/ oG oi, -chloro-H (2-meta- xy-1 methyl phenyl) - -K - ({- methyl ethoxymethyl) acetamide (93%) 51.53 2O63, PAP1-135 3.58143.4 HMDA (4O, 0%) - 3.89155.8 Reax 88 v1.03 41.3 Boa39.00 1,561.2 WaCg.0.96 38.5 The size of the spherical microcapsules is 1-10 microns. The preparation is stable. Example 21 The starting components are as follows: c / OH C-chloro-.K (ethoxymethyl) -. C- (2-methyl- -6-) trifluoromethyl (phenyl) -acetamide (92.4%) 42.58 266, 66 PAP1-135 2.97 18.61 HMDA (43.26%) 2.9718.61 Reax 88, 855.33 Warts37.97237.7 MaSe12.6579.24 The reaction conditions correspond to measure 16. The diameter of spherical microscopes is 4 -10 microns The drug is stable. Example 22 The source components are as follows :,. oi-chloro-M-ethyl- - (2-methyl 6) 3-methylbutoxy (phenyl) acetamide (92.5%) 46.83222.50 PAP1-.135 3.2715.53 HMDA (43.26%) 3.2715 , 53 Reav 88 to 1.004.76 Water 39.02185.4 O 6.6O31.38 The reaction conditions correspond to 16 except that their reagents are used at room temperature. The diameter of most spherical microcapsules is 4-10 microns. The drug is stable. Example 23.-Source components are as follows:% g and -chlor-M-methyl- / (2-methyl-6-propoxyphenyl) aceta MFA (96.2%) 44.11 225.0. PAP1-135 3.08 15.71 HMDA (43.26%) 3.0815.71 Reax 88, 94 4.81 Voda4O, 14,204.74 NoiCe8.65 44.12 All reaction conditions correspond to example 16. Diameter of most serial microcapsules was 4 ™ 10 microns. The drug is stable. Example 24 The following are the following sources of acid:%; {- (2-utoxy-6-methylphenyl) -ui-chloro-K-methyl / acetamide (92.2%) 47.93 225.00 PAPl-135 3.3515.71 Reax 88 , 02 4.81 HMDA (43.26%) 3.3515.71 Boa39.31 184.54 Macs5.04 23.68 The reaction conditions correspond to 16, except that their components are used in rooms; sherature The diameter of most eccentric microcapsules is 1O microns. The drug is stable, Example 25, Ishoana components are as follows:% g Izobu tilovy ether (2 5 4-a1 chlorine " phenoxy) acetic acids (76.4%) PAP1-135 HMDA (43.26%). Rficjvr 88 In Woz Macs C ce 2 G and jvs in p 26, s following; Alachlor (92.4%) Propachlor (95.0%) . (43.26%) Rea .88 in In oaa, Na Sat The conditions of the method are the same as in example 16. After the addition of the amine, the shear rate of the mixture is ;;% Ishotsglye materials are used (three 60 C. D) :) is the stabilization of the surface. Example 27, The Exept Compounds are as follows;% g A groin ENT (92.4%) 17,40 - Propachlor (95, O9) 2,8,25 6.20 Xylen R 3,61 .135 HMDA (43.26%) 3.61 Cesa 88 B-1pO VOP, and No se 6.2O the drug is in it stabilized to detect the smell of solvent. Example 26 nenty following: Alachlor technical (91%) Papl HICA (40%) ReaX, 9 Water38,2 Ethylene glycol4,2 This example is prozocyte in accordance with example 3, Reel and. С-й - emulgak / p based on calcium ligm of the resultant. Example 29, Investigative components of the following;% g The order of addition of the ingredients is not different from that of Example 1. BCQ steps can be done at room temperature. The size of the particles obtained, microlapsules fluctuate in samples of μ and diameter. Iskhoanib kombsm p and VI ep 30 li sp & % g Lutiz-7 re t. 2 tox - ..metal 6 -metig-aceT Sh5gLia (93%) HMDA (43.26%) Tgeah ITS Water 92 8.11 about: j P In this example, the temperature of the rec-s. yutsyuet loader in pretse-CI, -} l, a.; -: --18--5O p.304.0 g of acetanilic GT; rb) 1c (93% of technical material) ; containing 21.22 g of PAP1--135, emulsified with 257.66 g of warmer, co-err Zgheshey 6.50 gTgeO: X UTS - potassium oxide;: s; x) nata ... 20 seconds after the formation of the emulsion, 21, 22 rTMLA oag.Obromenno remove Savig. Chemically, 53 are added (92 g of sodium chloride) and dissolved using a Zersh1g mixer with scvag. Image spherical pimet particles. 1 4: .0 microns. R Ishokanke kompo and oah Chlorische CAT riy9d4 67,24 The reactive conditions correspond to the shunt. -Places of Gfimer 30, except to the extent that all re-hives are drained at room temperature. Dimensions mhro saisul fluctuate in ppeae micron diameter.Tgeah LTTS the emulsifier on the basis of magnesium-sulfo-one, PRECIMER 32, Raw materials of the following components |% g Alachlor (92.4%) 17.4 O Propachlor (98.0%) 28.25 114.4 Xylene 6.20 PAP1-135. 3.61 HMDA (43.26%): 3.61 Re ax C-21 1.00 Water 33.73 136.6 Chloride sodium 6, 2025.11 This example is carried out in accordance with the method described in Example 3, except that the reaction vatsu at. Example 33 Baseline components blind: i Alachlor (93.0%) 200.0 RLR1-135. 13.95 3.16 GMLA (43.26%) 3.16 13.95 Reax C-21 0.97 4.28 38.49 169.9 Woцаc NaCl chloride 10.10 35.76 Calcium chloride, 813, 58 The conditions for the Ventsen 11 reaction are identical to those of Example 32. Example 34 (comparative), Poly-Steroyl alcohol is used as emulsifier. Air defense Oo ° / o Hbifi (gelvatol 20-90), g126.7 (total Alachlor chloroplast (90%), g 40.0 (first addition Ethylene cyamine, g 18.1 Diethylenetriamine, g 18.1 (second addition) Alachlor concentrations give a very thick emulsion or dispersion after the first addition. After the second addition, i.e., after the addition of the diamine, the mixture immediately solidifies, the mass becomes much hotter than the capsule does not form. Example 35 (comparative). This example is carried out analogously to example 34, except that the components of the coating shell, i.e. PAP1 and, reduce in number tva, obtaining a 10% .al covering coat relative to the encapsulated herbicide. PVA 0.5 s (gelvatol 20 "90), g (in a mixing cup) Alachlor technical (90%), g PAP, g 13.9 (first addition) Ethylenediamine, g 6.2 DIETEPPENT ;;; -. (second aoba & amine, glenie) 10.0 Water, g 17.1 (third to ethylene glycol. more) After adding amines, i.e. after III, a thickener emulsion and mixing vessel should be shaken in order to separate the mix evenly. After 24 hours, the water micro wet is so thick that it flows. Under a microscope, a certain number of spherical arcs with a diameter of 1 to 10 microns were found, and the capsules have an irregular shape. The presence of pore residues with their associated alachlor crystals is observed. Example 36 (comparative), 0.5 ° / о.нъ1к gelvatol 2O-90 G (in a mixing cup) Monochloroben-200.0 (left to ash, hot water) PAPl, g 13.0 Hexamine 15 D (second dodiamine (40) suppression An emulsion is easily formed, during the administration of ciamine there is no change, a uniform thin bone is formed. After 24 hours, the entire composition is convincing and does not leach out to e with rapid agitation. Experience continues. Thus, when using a batten, otgt. microcapsules suspended in water can be as they are; agglomerate the microcapsule solution even after a certain xti time or after exposure to high temperatures; encapsulate 17 103943618 can be concentrated amounts | or thiocarbamagic herbicides in blatant no increase in viscosity, no solution of gerbitsktsngg x those. solidification of the mixture with a mixture of water crystal) h | mshsrokapsupy remain gc in after a certain amount of time or fluid, in a suspended state, the effects are increased. temperature | s nickname or in case of precipitation easily in the case of encapsulated, the acetanilanes are weighed again.
权利要求:
Claims (1) [1] METHOD FOR PRODUCING MICRO »CAPSULE by dispersing in an aqueous phase containing an emulsifier, an organic phase from polymethylene polyphenyl isocyanate and a substance not miscible with water, at a temperature from room temperature to 70 ° C, by adding a polyfunctional amine selected from the group 1,6-hexamethipentiamine, 6 ° C -hexa methylene tiramin, cytylenetriamine, triethylamine tetramine, tetraethylene pentamine, pentamethylenehexmin, characterized in that 30 are used to prevent agglomeration, reduce permeability and increase microcapsule yield , 552.2% of the weight of the components of both phases of a water-immiscible substance, 0.8- ^ 1.7% of sodium, potassium, calcium or magnesium ligninsulfonate as an emulsifier, with polymethylene-g polyphenylisocyanate and polyfunctional amine 1, 6-9.2% and 1.8 ^, 9%, respectively. oo smiling
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同族专利:
公开号 | 公开日 CA1165581A|1984-04-17| AU5682880A|1980-10-02| JPS55129146A|1980-10-06| DK155574C|1989-10-09| NO800856L|1980-09-29| ZA801750B|1981-08-26| NO150424C|1984-10-17| IL59510A|1983-03-31| IN152084B|1983-10-15| CS249110B2|1987-03-12| UA5920A1|1994-12-29| GR67254B|1981-06-26| AU532474B2|1983-09-29| YU42504B|1988-10-31| US4280833A|1981-07-28| PH17996A|1985-02-28| AR224644A1|1981-12-30| NZ193261A|1982-11-23| JPS6332761B2|1988-07-01| YU83180A|1984-02-29| BR8001786A|1980-11-18| FI800920A|1980-09-27| IL59510D0|1980-05-30| DK155574B|1989-04-24| NO150424B|1984-07-09| HUT36324A|1985-09-30| ES8101906A1|1980-12-16| DK127780A|1980-09-27| EP0017409B1|1983-03-16| PL222988A1|1981-01-02| US4417916A|1983-11-29| PT71010A|1980-04-01| KR830001606A|1983-05-18| PL134937B1|1985-09-30| PL134710B1|1985-09-30| DD149471A5|1981-07-15| ES489855A0|1980-12-16| AT2774T|1983-04-15| EP0017409A1|1980-10-15| HU191324B|1987-02-27| DE3062315D1|1983-04-21| FI67789C|1985-06-10| RO81047B|1983-05-30| RO81047A|1983-06-01| FI67789B|1985-02-28| KR840000114B1|1984-02-16|
引用文献:
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申请号 | 申请日 | 专利标题 US06/023,566|US4280833A|1979-03-26|1979-03-26|Encapsulation by interfacial polycondensation, and aqueous herbicidal composition containing microcapsules produced thereby| 相关专利
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