TW200831180A - Method for preventing crystallization - Google Patents
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- TW200831180A TW200831180A TW96129947A TW96129947A TW200831180A TW 200831180 A TW200831180 A TW 200831180A TW 96129947 A TW96129947 A TW 96129947A TW 96129947 A TW96129947 A TW 96129947A TW 200831180 A TW200831180 A TW 200831180A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
- A01N25/28—Microcapsules or nanocapsules
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Abstract
Description
200831180 九、發明說明： 【發明所屬之技術領域】 本發明包括一種藉由微膠囊方法的使用，纟延遲或防 止易受結晶影響之材料結晶的方法。特別是本發明包括一 種經由貫質上不溶於水性條件下的經微囊化的活性材料溶 液液滴的使用，來延遲或防止結晶的方法，其中該微膠囊 化劑為一種由改性尿素-甲醛聚合物形成的薄膜。 、 【先前技術】200831180 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention includes a method of retarding or preventing crystallization of materials susceptible to crystallization by the use of a microcapsule process. In particular, the present invention includes a method for delaying or preventing crystallization via the use of droplets of a microencapsulated active material solution that is substantially insoluble in aqueous conditions, wherein the microencapsulating agent is a modified urea- A film formed from an oxymethylene polymer. [Prior Art]
薄膜、塗層及膠囊在液體材料受控制的釋放上之用途， 在農藥及非農藥之技藝中皆廣為人知。農業上，受控制的 釋放技術已改善除草劑、殺蟲劑、殺真菌齊卜殺菌劑及肥 料之效率。非農業之用途包括微膠囊化的染料、油墨、藥 物、芳香劑及香水。 卞 最常見之受控制的材料釋放型式為塗佈後的液滴或微 膠囊；塗佈後的固冑’包括孔洞及非孔洞顆粒兩者；以： 塗佈後的固體顆粒聚集物。在某些實例中需要水可溶的膠 囊化薄膜，其當膠囊與水接觸時會釋放膠囊化的材料。^ 它塗層係没計為當該塗層被外力破壞時會釋放被封入的材 儘管如此，進一步的塗層在本質上為孔洞性的，且以 低速藉擴散穿越孔洞而將封入的材料釋放至周遭的介所 中。除了提供受控制的釋放外，這樣的塗層亦用來促進= 不互混的液體在水及例如濕土的含水介質中之分散、 方式膠囊化的液滴，於頻繁存在來自灌溉、雨水及灑水的 5 200831180 水之辰業上係特別有用。種種製造此類膠囊的方法係為已 知0 、-種製造具有均勻且易控制之大小、適合使用而不需 進一步處理的微膠囊之方法，係揭露於美國專利號 4’956，129及美國專利號5,332,584中。敘述於這些專利中 的微膠囊實質上為在孔洞性殼層内的水不溶性液體材料。 該專利揭露了該微膠囊化材料透過殼層經由擴散的材 慢釋放速率。 然而，某些材料並不適合為受控制釋放的調配物，特 別疋在水 >谷液相中具有結晶傾向的材料。因此，在該技藝 中存在對種藉由將具有低熔點或低的水溶解度之材料， 亦即在水相中具有結晶傾向的材料之溶液膠囊化，來防止 這些材料結晶的方法之需求。 【發明内容】 現已發現具有低溶點或在水相中具有結晶傾向的活性 成份材料之溶液的結晶，可使用微膠囊化之方法防止或延 遲，其中該⑨性材料係藉一種方法而膠囊化於孔洞性殼層 内，其包含： (a) 提供具有活性成份的飽和或過飽和溶液（活性溶 液），其包含該活性溶液及一種溶解於其中的醚化尿素-甲 醛預聚物’其中大約50 %至大約98 %的該預聚物之羥甲 基已使用C4-C10的醇類醚化； (b) 在含水及表面活性劑的連續相水溶液中，產生該活 性溶液的乳液，其*該乳液包含分散於該連續相水溶液中 6 200831180 的該活性溶液之不連續液滴，其因此在活性溶液之不連續 液滴及周遭的連續相水溶液之間形成一界面；以及 (C)藉由隨即加熱該乳液至大約20 °C至大約100 〇c之 間的溫度，接著將酸化劑添加至該乳液中，並維持該乳液 在大力0至大約4的pH下足夠的時間，使該樹脂預聚物 的原地縮合反應大體完成，而在鄰接該界面具有該不連續 液滴之有機相中原地引起自縮合反應並固化該尿素甲醛預 聚物，從而將該活性溶液的液體液滴轉換為由包封該活性 /合液液體材料之固體可滲透聚合物殼層所構成的膠囊。 藉此方法形成的微膠囊提供對結晶的穩定性，且可藉 透過殼層至周遭介質之擴散，實現膠囊化液體活性溶液之 慢速釋放。本發明在於藉使用敘述於上之方法形成的微膠 囊來防止或延遲這些材料結晶之能力。 本發明可立即適用於適應使用之活性 的種類，以及一般經濟因素上的變化。如下文所示 法之必要及非必要特徵及其產物皆可在廣範圍内變化。 Α·核心液體 作為形成膠囊内部液體的溶液（亦即核心液體）之基礎 的活丨生材料（亦即基底固體）具有足夠小的顆粒大小係為必 要的、，顆粒大小應介於i微米及i⑽微米之間，較佳介於 2 U米及20 Μ米之間。該核心液體可由溶於惰性溶劑中的 單活丨生基底固體，或一或多個活性基底固體材料之溶液 組成。該核心液體溶液可為飽和或過飽和的，但該固體基 底材料為具有低溶點或低的水溶解度者，#即該固體在水 7 200831180 相中具有結晶傾向。 多種活性液體可藉本方法而膠 田 不與預聚物、纟自縮合反應用的液體為 統中任何其它組份反應者1此，二 ==酸’或系 艇的非反隸《料適合。該㈣可 ^ 者二或更多化合物的混合物。其可擴散進水、泥土 L或 或任何其它周遭的介質中。鲂件$人λ 二乳， 孝乂侄適合經本發明之方法而 於膠囊化的液體應在3〇下為固鲈The use of films, coatings and capsules in the controlled release of liquid materials is well known in the art of pesticides and non-pesticides. In agriculture, controlled release techniques have improved the efficiency of herbicides, insecticides, fungicides and fertilizers. Non-agricultural uses include microencapsulated dyes, inks, pharmaceuticals, fragrances and perfumes.卞 The most common controlled material release profile is coated droplets or microcapsules; the coated solids' includes both voids and non-porous particles; to: coated solid particle aggregates. In some instances, a water soluble gelatinized film is required which releases the encapsulated material when the capsule is in contact with water. ^ Its coating system does not count to release the enclosed material when the coating is destroyed by external force. Nevertheless, the further coating is porous in nature and diffuses through the hole at a low speed to release the enclosed material. To the surrounding media. In addition to providing controlled release, such coatings are also used to promote the dispersion of non-mixed liquids in water and aqueous media such as wet soil, in the form of encapsulated droplets, which are frequently present from irrigation, rainwater and Sprinkling water 5 200831180 The water industry is particularly useful. A variety of methods for making such capsules are known as methods for making microcapsules of uniform size and controllable size suitable for use without further processing, as disclosed in U.S. Patent No. 4'956,129 and U.S.A. Patent No. 5,332,584. The microcapsules described in these patents are essentially water insoluble liquid materials within the porous shell. This patent discloses a slow release rate of the microencapsulated material through the shell through the diffused material. However, certain materials are not suitable for controlled release formulations, particularly those having a tendency to crystallize in the water > trough liquid phase. Accordingly, there is a need in the art for a method of preventing crystallization of materials by a material having a low melting point or low water solubility, i.e., a solution having a tendency to crystallize in an aqueous phase. SUMMARY OF THE INVENTION It has now been discovered that crystallization of a solution of an active ingredient material having a low melting point or a tendency to crystallize in an aqueous phase can be prevented or delayed using a method of microencapsulation, wherein the ninth material is encapsulated by a method In the porous shell, comprising: (a) providing a saturated or supersaturated solution (active solution) having an active ingredient comprising the active solution and an etherified urea-formaldehyde prepolymer dissolved therein 50% to about 98% of the methylol of the prepolymer has been etherified with a C4-C10 alcohol; (b) an emulsion of the active solution is produced in an aqueous solution of a continuous phase containing water and a surfactant, * The emulsion comprises discrete droplets of the active solution dispersed in the aqueous phase of the continuous phase 6 200831180, which thus form an interface between the discrete droplets of the active solution and the surrounding aqueous phase of the continuous phase; and (C) The emulsion is then heated to a temperature between about 20 ° C and about 100 ° C, followed by addition of an acidulant to the emulsion, and maintaining the emulsion at a pH of from 0 to about 4 for a sufficient period of time, The in-situ condensation reaction of the resin prepolymer is substantially completed, and in the organic phase adjacent to the interface having the discontinuous droplets, a self-condensation reaction is caused in situ and the urea-formaldehyde prepolymer is solidified, thereby liquidating the active solution. The droplets are converted into capsules composed of a solid permeable polymer shell encapsulating the active/liquid combining liquid material. The microcapsules formed by this method provide stability to crystallization and can be slowly released by the diffusion of the encapsulating liquid active solution by diffusion through the shell layer to the surrounding medium. The present invention resides in the ability to prevent or retard the crystallization of these materials by using the microcapsules formed by the methods described above. The present invention is immediately applicable to the types of activities that are suitable for use, as well as changes in general economic factors. The necessary and non-essential characteristics of the method and its products as shown below can vary widely. Α· core liquid as a basis for forming a solution of the internal liquid of the capsule (ie, the core liquid), the living biomaterial (ie, the base solid) has a sufficiently small particle size, and the particle size should be between i microns and Between i (10) microns, preferably between 2 U meters and 20 mm. The core liquid may consist of a single living twin base solid dissolved in an inert solvent or a solution of one or more active substrate solid materials. The core liquid solution may be saturated or supersaturated, but the solid substrate material has a low melting point or low water solubility, i.e., the solid has a tendency to crystallize in the water 7 200831180 phase. A variety of active liquids can be used in this method, and the liquid used in the self-condensation reaction of the prepolymer and the ruthenium is the reaction of any other component in the system. The second == acid' or the non-reciprocal of the boat . The (four) can be a mixture of two or more compounds. It can diffuse into water, soil L or any other surrounding medium. $$人λ二乳, 孝乂侄 is suitable for the method of the invention, and the liquid encapsulated should be solid at 3〇
下為固體、在水中具有低溶解 度’且在水不互混的有機溶劑中具有至少中等的溶解度。 適合用於勝囊化的液體包括生化藥劑，例如除草劑、 殺蟲劑、殺真菌劑、殺線蟲劑、殺菌劑、滅鼠劑、除螺劑、 殺蟎劑、殺幼蟲劑、驅動物、昆蟲、鳥劑、植物生長調節 劑、肥料、費洛蒙、性誘及吸引劑、藥物，以及香料及氣 味組成物。本發明之微膠囊係特別適用於農藥，包括硫代 胺基甲酸酯、二硫代胺基甲酸酯、乙醯胺、苯胺化物、磺 酉&胺、雙聽胺、三嗓、有機碟化合物、天然發酵產物，以 及除蟲菊精。接下來為這類化合物之實例。具有俗名的各 農藥之細節（例如結構、化學名、商品名等等）可在k version 3.1，13th Edition，Ed· CDC Tomlin， British Crop Protection Council，2004-05 中找到。 除草劑 氟丁醯草胺（Beflubutamid)、 溴丁醯草胺 (bromobutide)、σ坐草胺（cafenstrole)、大芬滅（diphenamid)、 四σ坐草胺（fentrazamide)、氟胺草嗤（Hupoxam)、氟磺胺草 8 200831180 醚（fomesafen)、草特靈（isocarbamid)、異 σ惡草胺（isoxaben)、 烯草胺（pethoxamid)、戊炔草胺（propyzamide)、稗草胺 (clomeprop)、吼氟草胺（dmufenican)、乙氧苯草胺 (etobenzanid)、氟噻草胺（flufenacet)、苯噻草胺 (mefenacet)、伏草胺（mefluidide)、吩它味（fetamifop)、庚 醯草胺（monalide)、萘丙胺（naproanilide)、戊酸苯草胺 (pentanochlor)、氟 u比醯草胺（pic〇iinafen)、新燕靈 (benzoylprop)、高效麥草伏酯（flampr〇p_M)、拉草 (alachlor)、毒草胺（pr〇pachlor)、異丙草胺（propisochlor)、 欣克草（thenylchlor)、氯酯磺草胺（cloransulam)、雙氟磺草 胺（floransulam)、苯氟石黃胺（perfluidone)、石黃草靈（asulam)、 安石黃靈（oryzalin)、草克樂（chlorthiamid)、草滅平 (chloramben)、σ密草 _ (pyriminobac-methyl)、曱基敵草索 (chlorthal-methyl)、氯氨基 ϋ比咬酸（aminopyralid)、二氯口比 0疋酸（clopyralid)、石肖草酮（mesotrione)、績草酮 0 (sulcotrione) 、 °夫草黃（benfuresate)、乙咬草黃 (ethofume sate)、卡靈草（karbuti late)、卡草胺（carbetamide)、 氯本胺靈（chlorpropham)、甜菜安（desmedipham)、棉胺寧 (phenisopham)、甜菜寧（phenmedipham)、乙基甜菜寧 (phenmedipham-ethyl)、苯胺靈（propham)、丁 苯草酮 (butroxydim)、環殺草（cyeioxydim)、得殺草（tepraloxydim)、 本月亏草_ (tralkoxydim)、異鳴嗅草酮（丨3〇乂&€1111:〇16)、1|引0朵 酮草酉旨（cinidon-ethyl) '氟烯草酸（fiuiniclorac)、丙炔氣草 月女（flumioxazin)、炔草胺（flumipropyn)、氟草胺 9 200831180The lower is a solid, has a low solubility in water' and has at least moderate solubility in an organic solvent in which the water is not miscible. Liquids suitable for use in sacs include biochemical agents such as herbicides, insecticides, fungicides, nematicides, bactericides, rodenticides, snails, acaricides, larvicides, drivers, Insects, avians, plant growth regulators, fertilizers, pheromones, sexual attractants and attractants, drugs, and perfume and odor compositions. The microcapsules of the present invention are particularly suitable for use in pesticides, including thiourethanes, dithiocarbamates, acetamides, anilides, sulfonamides, amines, amines, triterpenes, organic Disc compounds, natural fermentation products, and pyrethrins. Next are examples of such compounds. Details of each of the commonly known pesticides (e.g., structure, chemical name, trade name, etc.) can be found in k version 3.1, 13th Edition, Ed. CDC Tomlin, British Crop Protection Council, 2004-05. Herbicide Beflubutamid, bromobutide, cafenstrole, diphenamid, fentrazamide, halopoxam ), flufenamide 8 200831180 ether (fomesafen), isocarbamid, isoxaben, pethoxamid, propyzamide, clomeprop, Dmufenican, etobenzanid, flufenacet, mefenacet, mefluidide, fetamifop, gypsum Monalide, naproanilide, pentanochlor, picu iinafen, benzoylprop, flampr〇p_M, pull Alachlor, pr〇pachlor, propisochlor, thenylchlor, cloransulam, floransulam, phenoflavin Perfluidone, asulam, oryzalin, grass (chlorthiamid), chloramben, pyriminobac-methyl, chlorthal-methyl, aminopyralid, dichlorohydrin Clopyralid), mesotrione, sulcotrione, benfuresate, ethofume sate, karbuti late, carbeamide , chlorpropham, desmedipham, phenisopham, phenmedipham, phenmedipham-ethyl, propham, butyl ketone (butroxydim) ), cyeioxydim, tepraloxydim, tralkoxydim, olfactory ketone (丨3〇乂&€1111:〇16), 1|#0 ketone Cinidon-ethyl 'fiuiniclorac, flumioxazin, flumipropyn, fluramide 9 200831180
(benfluralin)、比達寧（butralin)、撻乃安（dinitramine)、浠 氟靈（ethalfluralin)、氯氟靈（fluchloralin)、磺樂靈 (nitralin)、安石黃靈（oryzalin)、二甲戍樂靈（pendimethalin)、 氨基氟樂靈（prodiamine)、環丙氟靈（profluraiin)、氟樂靈 (trifluralin)、達諾殺（dinoseb)、特樂酯（dinoterb)、曱基特 樂酯（medinoterb acetate)、苯草醚（aclonifen)、比芬諾 (bifenox)、消草 it (fluorodifen)、乙羧氟草醚 (fluoroglycofen-ethyl)、氟磺胺草醚（fomesafen)、乳氟禾草 靈（lactofen)、護谷（nitrofen)、復祿芬（oxyfluorfen)、邁隆 (dazomet)、口米草酸(imazamethabenz-methyl)、甲氧咪草煙 (imazamox)、曱咪唑於酸（imazapic)、依滅草（imazapyr)、 咪草煙（imazethapyr)、溴苯腈（bromoxynil)、歒草腈 (dichlobenil)、°惡唾隆（dimefuron)、滅草定（methazole)、快 惡草酮（oxadiargyl)、樂滅草（oxadiazon)、澳酴將 (bromofenoxim)、chomeprop、2,4·滴（2,4-D)、MCPA、 2,4,5-T、草殺淨（ametryn)，以及撲草淨（prometryn)。 殺蟲劑 阿巴、汀(abamectin)、因滅汀（emamectin)、密滅汀 (milbemectin)、倍脈心（milbemycin oxime)、印楝素 (azadirachtin)、魚藤酮(rotenone)、免敵克（bendiocarb)、 加保利（carbaryl)、加保扶（carbofuran)、滅繩威（dimetilan)、 比加普（pirimicarb)、棉鈴威（alanycarb)、洋滅威（aldicarb)、 涕滅氧威（aldoxycarb)、滅多威（methomyl)、硫敵克 (thiodicarb)、久效威（thiofanox)、滅害威（aminocarb)、畜 200831180(benfluralin), butralin, dinitramine, ethalfluralin, fluchloralin, nitralin, oryzalin, dimethylhydrazine Pendimethalin, prodiamine, profluraiin, trifluralin, dinoseb, dinoterb, medinoterb Acetate), alexifen, bifenox, fluorodifen, fluoroglycofen-ethyl, fomesafen, lactofen ), nitrofen, oxyfluorfen, dazomet, imazamethabenz-methyl, imazamox, imidazol, acid, imazapic (imazapyr), imazethapyr, bromoxynil, dichlobenil, dimefuron, methazole, oxadiargyl, music Oxdiazon, bromofenoxim, chomeprop, 2,4 drops (2,4-D), MCP A, 2, 4, 5-T, ametryn, and prometryn. Insecticides Aba, abumectin, emamectin, milbemectin, milbemycin oxime, azadirachtin, rotenone, bendiocarb ), carbaryl, carbofuran, dimetilaan, pirimicarb, alanycarb, aldicarb, aldoxycarb, Methomyl, thiodicarb, thiofanox, aminocarb, livestock 200831180
蟲威（butacarb)、除線威（cloethocarb)、二氧威（dioxacarb)、 乙硫苯威（ethiofencarb)、仲丁威（fenobucarb)、滅必蟲 (isoprocarb)、滅賜克（methiocarb)、速滅威（metolcarb)、治 克威（mexacarbate)、猛殺威（promecarb)、安丹（propoxur)、 混滅威（trimethacarb)、XMC、滅殺威（xylylcarb)、DNOC、 氟蟲胺（sulfluramid)、雙甲脒（Amitraz)、殺蟲脒 (chi or dime form)、布芬淨（buprofezin)、芬諾克（fenoxycarb)、 百利普芬（pyriproxyfen)、硫賜安（thiocyclam)、可尼丁 (clothianidin)、達特南（以11〇1^1\^11)、益達胺（111^(13〇1〇口1^(5)、 賽速安（thiamethoxam)、亞滅培（acetamiprid)、嗟蟲琳 (thiacloprid)、林丹（lindane)、甲氧滴滴洋（methoxychlor)、 五氣紛（pentachlorophenol)、水揚硫磷（dioxabenzofos)、丁 苯硫填（fosmethilan)、大滅松（dimethoate)、福木松 (formothion)、發硫磷：（prothoate)、曱基 11 比0定石粦 (azamethiphos)、繩毒石粦（coumaphos)、滅虫牙松（menazon)、 必芬松（pyridaphenthion)、乙基谷硫鱗（azinphos-ethyl)、曱 基谷硫碗（azinphos-methyl)、氯亞胺硫碟（dialifos)、益滅 松（phosmet)、白粉松（pyrazophos)、陶斯松（chlorpyrifos)、 甲基陶斯松 （chlorpyrifos-methyl) 、 丁 哺硫麟 (tebupirimfos)、口奎石危磷（quinalphos)、滅大松（methidathion)、 溴硫填（bromophos)、伐滅磷（fampliur)、皮题填 (fenchlorphos)、鐵硫磷（jodfenphos)、曱基巴拉松 (parathion-methyl)、亞培松（temephos)、三氯松 (trichlorfon)、四曱填（mecarphon)、施力松（cyanofenphos)、 11 200831180Butacarb, cloethocarb, dioxacarb, ethiofencarb, fenobucarb, isoprocarb, metiocarb, speed Metalcarb, mexacarbate, promecarb, propoxur, trimethacarb, XMC, xylylcarb, DNOC, sulfluramid , Amitraz, chi or dime form, buprofezin, fenoxycarb, pyriproxyfen, thiocyclam, cotinine (clothianidin), Datnam (to 11〇1^1\^11), etadamine (111^(13〇1〇口1^(5), thiamethoxam, acetamiprid) , thiacloprid, lindane, methoxychlor, pentachlorophenol, dioxabenzofos, fosmethilan, dimethoate ), formothion, thiophene: (prothoate), sulfhydryl 11 than 0 dynasty (azamethiphos), scorpion venom (coumaphos), menazon, pyridaphenthion, azinphos-ethyl, azinphos-methyl, dialifos, benefit Phosmet, pyrazophos, chlorpyrifos, chlorpyrifos-methyl, tebupirimfos, quinalphos, methidathion, bromine Bromophos, fampliur, fenchlorphos, jodfenphos, parathion-methyl, temephos, trichlorfon ), mecarphon, cyanofenphos, 11 200831180
EPN福賜松（leptophos)、芬滅松（€6職111丨口11〇8)、硫環磷 (phosfolan)、毆殺松（acephate)、水胺硫磷（isocarbophos)、 達馬松（Methamidophos)、因得克（indoxacarb)、惡虫酮 (metoxadiazone)、氯亞胺硫磷（dialifos)、益滅松（phosmet)、 胺菊酉旨（tetramethrin)、芬普尼（fipronil)、ϋ比螨胺 (tebufenpyrad)、嗤蟲醯胺（tolfenpyrad)、阿納寧 (acrinathrin)、畢芬寧（bifenthrin)、賽扶寧（cyfluthrin)、高 效氯氟氰菊酯（gamma-cyhalothrin)、賽洛寧（lambda-cyhalothrin)、氯氰菊酯（cypermethrin)、亞滅寧（alpha-cypermethrin)、乙體氯氰菊酯（beta_cypermethrin)、高效反 式氯氰菊酯（theta-cypermethrin)、Z —氯氰菊酯（zeta-cypermethrin)、第滅寧（deltamethrin)、五 IL 菊酯 (fenfluthrin)、芬普寧（fenpropathrin)、芬化利（fenvalerate)、 益化利（esfenvalerate)、氯菊醋（Permethrin)、滅蟲菊 (resmethrin)、生物苄吱菊酉旨（bioresmethrin)、七氟菊酉旨 (tefluthrin)、胺菊酯（tetramethrin)、四漠菊酉旨 (tralomethrin)、四敗苯菊酷（transHuthrin)、依芬寧 (etofenprox)、 三氟醚菊酉旨（flufenprox)、合芬寧 (halfenprox)、畢汰芬（pyrimidifen)、克凡派（chlorfenapyr)、 螺曱蜗酯（spiromesifen)、汰芬隆（diafenthiuron)、5 -氯- 2-[4-氯-2-[(3,4-二氯苯基）氨基]醯胺苯氧基]苯磺酸鈉 (sulcofuron sodium)、愛美松（hydramethylnon)、亞賜圃 (isoprothiolane)、特燏腈（malonoben)、畢達本（pyridaben)、 °定蟲丙醚（pyridalyl)、°坐虫牙威（triazamate)、Rynaxypyr(杜 12 200831180 ♦ 邦）。 殺真菌劑EPN blessings (leptophos), fentansone (€6 jobs, 111 mouths, 11〇8), phosfolan, acephate, isocarbophos, and methamidophos ), indoxacarb, metoxadiazone, dialifos, phosmet, tetramethrin, fipronil, dipyridamole Amine (tebufenpyrad), tolfenpyrad, acrinathrin, bifenthrin, cyfluthrin, cyhalothrin (gamma-cyhalothrin), cylonine (lambda-cyhalothrin) ), cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, deltamethrin, five Fenfluthrin, fenpropathrin, fenvalerate, esfenvalerate, permethrin, resmethrin, bioresmethrin Hexagram Tefluthrin, tetramethrin, trolomethrin, transHuthrin, etofenprox, flufenprox, fenfenin (halfenprox), pyrimidifen, chlorfenapyr, spiromesifen, diafenthiuron, 5-chloro-2-[4-chloro-2-[(3, 4-dichlorophenyl)amino]decyl phenoxy] sodium sulcofuron sodium, hydramethylnon, isoprothiolane, malonoben, pyridaben , ° pyridalyl (pyridalyl), ° sita tooth (triazamate), Rynaxypyr (Du 12 200831180 ♦ state). Fungicide
克絕（cymoxanil)、多果定（dodine)、雙胍辛乙酸鹽 (guazatine)、克熱淨（iminoctadine)、氯環丙醯胺 (carpropamid) 、 chloraniformethan 、 環 氟菌胺 (cyflufenamid)、雙氯氰菌胺（diclocymet)、°塞嗅菌胺 (ethaboxam)、稻瘦酿胺（fenoxanil)、福拉比（furametpyr)、 雙炔醯菌胺（mandipropamid)、σ比 σ塞菌胺（penthiopyrad )、 撲克拉（prochloraz)、石夕嗟菌胺（silthiofam)、賽福寧 (triforine)、本達樂（benalaxyl)、右本達樂（benalaxyl-M)、 呋霜靈（furalaxyl)、滅達樂（metalaxyl)、右滅達樂 (metalaxyl-M)、白克列（boscalid)、萎銹靈（carboxin)、環 醯菌胺（fenhexamid)、°塞菌胺（metsulfovax)、曱吱醯胺 (ofurace)、惡霜靈（oxadixyl)、嘉保信（oxycarboxin)、賽氟 滅（thifluzamide)、噻醯菌胺（tiadinil)、鄰碘醯苯胺 (benodanil)、福多寧（flutolanil)、鄰醯胺（mebenil)、曱口夫 酸苯胺（fenfuram)、三曱吱菌胺（methfuroxam)、氣硫滅 (Husulfamide)、揚菌胺（trichlamide)、氰菌胺（zarilamid)、 草醯胺（zoxamide)、茂谷樂（furmecyclox)、益發靈 (dichlofluanid)、甲基益發靈（t〇iyifiuanid)、賽座滅 (cyazofamid)、苯°塞菌胺（1^111:111&¥3148]：13-13〇@1：(^71)、異丙 菌胺（iprovalicarb)、亞托敏（azoXyStrobin)、醚菌胺 (dimoxystrobin)、氟嘧菌酯（flu〇xastrobin)、克收欣 (kresoxim-methyl)、苯氧菌胺（metominostrobin)、肟醚菌胺 13 200831180Cymoxanil, dodine, guazatine, iminoctadine, carpropamid, chloraniformethan, cyflufenamid, chlordane Diclocymet, ethaboxam, fenoxanil, furametpyr, mandipropamid, σ σ sputum (penthiopyrad), poker Prochloraz, silthiofam, triforine, benalaxyl, benalaxyl-M, furalaxyl, metalaxyl ), metalaxyl-M, boscalid, carboxin, fenhexamid, metsulfovax, ofurace, Oxedixyl, oxycarboxin, thifluzamide, tiadinil, benodanil, fluolanil, mebenil, Fenfuram, methfuroxam, Husulf Amide), trichlamide, zarilamid, zoxamide, furmecyclox, dichlofluanid, methyl phenylephrine (t〇iyifiuanid), 赛赛灭( Cyazofamid), benzocrecoside (1^111:111&¥3148]: 13-13〇@1:(^71), iprovalicarb, azoXyStrobin, ethenamide Dimoxystrobin), flu〇xastrobin, kresoxim-methyl, metominostrobin, and epothilone 13 200831180
(orysastrobin)、。定氧菌酯（picoxystrobin)、百克敏 (pyraclostrobin)、三氟敏（trifloxystrobin)、聯苯（biphenyl)、 地茂散（chloroneb)、四氯異苯腈（chlorothalonil)、大克爛 (dicloran)、六氯苯（1^义3(：]11〇1*〇3七1120116)、五氣紛 (pentachlorophenol)、五氯石肖基苯（quintozene)、四氯石肖基 苯（tecnazene)、免賴得（benomyl)、腐絕（thiabendazole)、 曱基多保淨（thiophanate-methyl)、雙氯酸（dichlorophen)、 二苯基胺（diphenylamine)、乙黴威（diethofencarb)、甘寶素 (Climbazole)、撲克拉（prochloraz)、賽福座（triflumizole)、 戊環 °坐（azaconazole)、溴克座（bromuconazole)、環克座 (cyproconazole)、苄氯三唾醇（diclobutrazol)、待克利 (difenoconazole)、浠 σ坐醇（diniconazole)、達克利 (diniconazole-M)、依普座（epoxiconazole)、乙環嗤· (etaconazole)、腈苯嗤(fenbuconazole)、敗 σ奎 11 坐 (fluquinconazole)、護碎得（flusilazole)、護汰芬（flutriafol)、 σ夫菌唾（furconazole)、川員式吱菌口坐（furconazole，cis)、菲克 利（hexaconazole)、種菌唾（ipconazole)、滅特座 (metconazole)、邁克尼（myclobutanil)、平克座 (penconazole)、 普克利(propiconazole)、 丙石I 菌峻 (prothioconazole)、石夕氟嗤(simeconazole)、得克利 (tebuconazole)、四克利(tetraconazole)、三泰芬 (triadimefon)、三泰隆（triadimenol)、滅菌口坐（triticonazole)、 稀效峻（uniconazole)、烯效 °坐-P(uniconazole-P)、σ惡峻菌酮 (famoxadone)、氟蓖驢胺（fluorimide)、乙菌利 200831180(orysastrobin),. Picoxystrobin, pyraclostrobin, trifloxystrobin, biphenyl, chloroneb, chlorothalonil, dicloran, Hexachlorobenzene (1^义3(:]11〇1*〇3七1120116), pentachlorophenol, pentachlorobenzene, quinnazene, benomyl , thiabendazole, thiophanate-methyl, dichlorophen, diphenylamine, diethofencarb, Climbazole, prochloraz , triflumizole, azaconazole, bromuconazole, cyproconazole, diclobutrazol, difenoconazole, 浠σ sitol Diniconazole), diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, care Fluflufol, σ夫Furconazole, fluconazole (cis), hexaconazole, ipconazole, metconazole, myclobutanil, penconazole, Propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, sterilized mouth Triticonazole, uniconazole, uniconazole-P, famoxadone, fluorimide, acetaminophen 200831180
(chlozolinate)、依普同（iprodione)、甲菌利（myclozolin)、 撲滅寧（procymidone)、免克寧（vinclozolin)、四氯丹 (captafol)、蓋普丹（captan)、普得松（ditalimfos)、福爾培 (folpet)、樂殺蠕（binapacryl)、敵端通（dinobuton)、DNOC、 賽座滅（cyazofamid)、味吐菌酮（fenamidone)、果綠定 (glyodin)、peflurazoate、達滅芬（dimethomorph)、十二環 口馬琳（dodemorph)、氟 口馬淋（flumorph)、白粉松（pyrazophos)、 三苯醋錫（fentin acetate)、乙菌利（chlozolinate)、肼菌酮 (drazoxolon)、凡殺同（famoxadone)、殺紋寧（hymexazol)、 曱菌利（myclozolin)、免克寧（vinclozolin)、福拉比 (furametpyr) 、 0 比 σ塞菌胺（penthiopyrad)、得滅多 (buthiobate)、扶吉胺（fluazinam)、賽普洛（cyprodinil)、二 氟林（diflumetorim)、乙。密紛（ethirimol)、芬瑞莫 (fenarimol)、。密菌腙（ferimzone)、滅派林（mepanipyrim)、 尼瑞莫（nuarimol)、。密霉胺（pyrimethanil)、拌種洛 (fenpiclonil)、洛菌腈（fludioxonil)、氟蓖酸胺（fluorimide)、 丙稀酸啥琳醋（halacrinate)、快諸芬（quinoxyfen)、腈硫酉昆 (dithianon)、喧菌酮（chinomethionat)、ethoboxam、石黃菌威 (methasulfocarb)、敵菌靈（anilazine)、比多農（bitertanol)、 三氟苯嗤（fluotrimazole)、賓克隆（pencycuron)、苯丙嗟重 氮（acibenzolar-methyl)、酜菌酯（nitrothal-isopropyl)、熱必 斯（phthalide)、撲殺熱（probenazole)、百快隆（pyroquilon)、 σ塞菌腈（thicyofen)、三賽唾（tricyclazole)、具有式A的化 合物： 15 200831180(chlozolinate), iprodione, myclozolin, procymidone, vinclozolin, captafol, captan, and ditalimfos ), folfet, binapacryl, dinobuton, DNOC, cyazofamid, fenamidone, glyodin, peflurazoate, Dimethomorph, dodemorph, flumorph, pyrazophos, fentin acetate, chlozolinate, sputum (drazoxolon) ), famoxadone, hymexazol, myclozolin, vinclozolin, furametpyr, 0 σ sputum (penthiopyrad), 得灭多( Buthiobate), fluazinam, cyprodinil, diflumetorim, B. Ethirimol, fenarimol, fenarimol. Ferimzone, mepanipyrim, nuarimol. Pyrimethanil, fenpiclonil, fludioxonil, fluorimide, halacrinate, quinoxyfen, nitrile quinone (dithianon), chinomethionat, ethoboxam, methasulfocarb, anilazine, bitertanol, fluotrimazole, pencycuron, benzene Acibenzolar-methyl, nitrothal-isopropyl, phthalide, probenazole, pyroquilon, thysone, thicyofen (tricyclazole), compound of formula A: 15 200831180
ch3 WO 的化 或此化合物的異構物或互變異構物（敎述、 03/074491，在此以引用方式納入本文中、、 、Ch3 WO or an isomer or tautomer of this compound (Description, 03/074491, herein incorporated by reference herein,
} 井有式B 合物··} Well has a formula B ··
或此化合物的異構物或互變異構物（登記為 214706-53-3)，或者具有式c的化合物：Or an isomer or tautomer of this compound (registered as 214706-53-3), or a compound of formula c:
或此化合物的異構物或互變異構物（敘述於 122 且登記在 CAS_291771_99_8 及 CAS-29i77i_83_〇 之下 可用於本組成物的許多不同類型核心液體中，較佳者 16 200831180 為殺蟲劑，且某些類型的殺蟲劑尤其為較佳。其中一類為 唑類殺真菌劑。此類化合物包括揭露於美國專利號 4,243,405中者，在本文特別提出作為參考資料完整納入。 此類中的具體化合物包括戊環唑（azaconaz〇le)、比多農 (bitertanol)、溴克座（1)1*〇]1111(：〇11^〇16)、環克座 (cyproconazole)、待克利（difenoconazole)、烯唑醇 (diniconazole)、腈苯唑（fenbuconazole)、氟嗅唑 (fluquinconazole)、護矽得（flusilazole)、護汰芬（flutriaf〇1)、 呋菌唑（furconazole)、菲克利（hexac〇naz〇le)、種菌唑 (ipconazole)、滅 4寸座（metconazole)、邁克尼（myclobutanil)、 平克座（penconazole)、撲克拉（prochl〇raz)、普克利 (propiconazole) > 得克利（tebUCOnaz〇le)、四克利 (tetraconazole)、三泰芬（triadimefon)、三泰隆（triadimen〇1)、 賽福座（triflumizole)、滅菌唑（triticonaz〇le)，以及烯效唑 (uniconazole)。包括於可用於本發明之核心液體類型中者， 尤其亦包括亞托破（azoxystrobin)、三氟敏（trifloxystrobin)、 氟唯囷酉曰（fluoxastrobin)、右滅達樂（metaiaXyi_]yj)、 benalazy卜呋霜靈（furalaxyi)、七氟菊酯（tefluthrin)、賽速 安（thiamethoxam)、益達胺（imidacl〇prid)、可尼丁 (clothianidin)、噻蟲啉（thiacloprid)、阿巴汀（abamectin)、 赉洛 f (lambda-cyhalothrin)、弟滅威（aidicarb)、芬普尼 (fipronil) 〇 任何人可擴展作物的多樣性，其中某些殺蟲劑，尤其 是除草劑’可藉由在組成物中包括解毒劑而有效地使用。 17 200831180 該解毒劑幫助保護作物免於除草 刃％告，而除草劑對於 不想要的雜草物種之效力無可觀的影燮。 、 丄 曰邊解毒劑因此使 除旱劑在其作用上更具選擇性。 吐η 了用的解毒劑包括乙隨 細，例如二烯丙基-2,2_二氯乙醯胺及二烯丙基2 氯乙酸胺卜惡嗤琳，例如2,2,5_三甲基I二氯乙酿喔=琳 及2,2-螺環己基-ΑΓ-二氯乙醯噁唑啉 ^ Α1，、萘酐。為得 到最大的效用，該解毒劑係以無植物毒性、可有效解毒的Or an isomer or tautomer of this compound (described in 122 and registered under CAS_291771_99_8 and CAS-29i77i_83_〇) can be used in many different types of core liquids of the present composition, preferably 16 200831180 is an insecticide And certain types of insecticides are especially preferred. One type is an azole fungicide. Such compounds include those disclosed in U.S. Patent No. 4,243,405, which is incorporated herein by reference in its entirety. Specific compounds include aconazole (azaconaz〇le), specificon (bitertanol), bromide (1) 1*〇]1111 (:〇11^〇16), cyproconazole, diknoconazole ), diniconazole, fenbuconazole, fluquinconazole, flusilazole, flutriaf〇1, furconazole, hexac 〇naz〇le), ipconazole, metconazole, myclobutanil, penconazole, prochl〇raz, propiconazole > (tebUCOnaz Le), tetraconazole, triadimefon, triadimen〇1, triflumizole, triticonaz〇le, and uniconazole. Among the core liquid types of the present invention, in particular, it includes azoxystrobin, trifloxystrobin, fluoxastrobin, metaaXyi_yy, and benalazy. Furalaxyi), tefluthrin, thiamethoxam, imidacl〇prid, clothianidin, thiacloprid, abamectin, 赉洛f (lambda-cyhalothrin), aidicarb, fipronil 〇 anyone can expand crop diversity, some of which can be included in the composition by some pesticides, especially herbicides It is effectively used as an antidote. 17 200831180 The antidote helps protect crops from weeding, while herbicides have no appreciable effect on the effectiveness of unwanted weed species.丄 曰 解 解 detoxification agent makes the desiccant more selective in its role. Antidote for vomiting includes B, such as diallyl-2,2-dichloroacetamide and diallyl 2 chloroacetic acid, such as 2,2,5_3 Base I dichloroethane 喔 = 琳 and 2, 2- spirocyclohexyl-fluorene-dichloroethane oxazoline ^ Α 1, naphthalene anhydride. For maximum utility, the antidote is phytotoxic and detoxifying.
量存在於組成物中。，，無植物毒性”意謂一個對作物產2最 輕微傷害的量。，，可有效解毒”音 取 ^ 唧毋w明個大體上降低除草劑 對作物產生之傷害程度的量。除簟匈 里咏早劑對解毒劑的較佳重量 比為大約0· 1 : 1至大約3〇 : 1匕 此比例的取佳範圍為大約 3 : 1至大約20 : 1。 許多殺蟲劑的效用亦可藉在殺蟲劑組成物中增效劑的 包括而擴展。增效劑為-種其本身具有小的或無殺蟲活 性’但當與殺蟲劑合併時產生—種組合，其具有顯著多於 化合物獨自施用之效力加總的效力之化合物。I用的增效 劑!^括Γ1-[2♦乙氧乙氧基）乙氧基]乙氧基十3-苯並二氧 雜環戊烯（sesamex)、苯並二噁唑_5_基）四氫呋喃 並[3,4-c]t南（sesamin)、^甲基士…-亞甲基二氧苯基）： 基辛基亞碾，以及5-[2_(2•丁氧乙氧基）乙氧甲基]_6_丙基_ 1’3-苯亚一噁唑（胡椒基丁醚）。當包括時，增效劑以有效量 存在’亦即任何觀察到增強效果的殺錢對增效劑之比 例。此比例隨種種組合廣泛變化。 B·預聚物 18 200831180 適合本發明之預聚物為部份醚化的尿素甲醛預聚物， 其在有機相中具有高溶解度且在水中具有低溶解度。在其The amount is present in the composition. , “No phytotoxicity” means an amount that is the least harmful to crop production 2. It can be effectively detoxified. ^ 明 明 明 明 明 明 明 明 明 明 明 明 明 明 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上 大体上Preferably, the weight ratio of the antimony agent to the antidote is about 0.1:1 to about 3:1. The preferred range for this ratio is from about 3:1 to about 20:1. The utility of many insecticides can also be extended by the inclusion of synergists in the insecticide composition. Synergists are compounds which, by themselves, have little or no insecticidal activity' but when combined with insecticides, produce a combination of compounds which have significantly more potency than the efficacy of the compound alone. Synergist for I!^Γ1-[2♦ ethoxyethoxy)ethoxy]ethoxytris-3-benzodioxole (sesamex), benzobisoxazole_5_ Tetrahydrofuro[3,4-c]t south (sesamin), ^methyls...-methylenedioxyphenyl): kesinyl argon, and 5-[2_(2•butoxyethoxy) Ethyloxymethyl]_6_propyl-1'3-phenylene oxazole (piperonyl butoxide). When included, the synergist is present in an effective amount, i.e., any ratio of killer to synergist that observes the enhancing effect. This ratio varies widely with various combinations. B. Prepolymer 18 200831180 A prepolymer suitable for the present invention is a partially etherified urea formaldehyde prepolymer which has high solubility in the organic phase and low solubility in water. In its
非醚化型式時，該預聚物含大量的羥甲基_CI^〇H在其分 子結構中。醚化為羥基氫與烷基的置換，且係藉預聚物與 醇的縮合反應而達成。當院基包含四個碳原子或更多，且 其已置換預聚物分子上多於大約50 %的羥基氫原子時，該 預聚物變得可溶於有機相中。然而需避免完全的醚化，因 經基對在成壁殼步驟中發生的原地自縮合聚合反應係為必 須的。因此，可用於本發明的預聚物為大約5〇%至大約％ %的經基氫原子已被各具有4至1Q個碳原子的烧基置換 者。在較佳實例中’大約7〇 %至大約9〇 %的該基團已被 C4_C0的醇類醚化。直鏈及支鏈的醇類皆可用於本發明， 且所有在本文引述的碳原子範圍係包括其上及下限。 醚化的尿素-甲搭預聚物，在商業上可以醇類或醇類及 二甲苯之混合物中的溶液而得到。用作溶劑的醇類一般盥 用作趟化劑者相同。最常使用者為正丁醇及異丁醇。這此 商品中的喊化(丁基化)度介於7〇 %及9〇 %之間，且該溶液 以重量計含5G %至85%的預聚物。亦常存在微量的游離 、二冷液係典^{地以用於醇酸樹月旨的交聯劑而販 售，且係主要用於塗佈及加工產品之調配物，例如顏料及 漆0 作為黏著劑之用途且未 論疋以水溶液或以水可溶的 這些可藉在弱酸性醇類溶液 曾醚化的尿素·甲醛預聚物，無 固體’其亦為商業上可得的。 中’與需要的醇類進行縮合反 19 200831180 應而醚化。縮合反應的水係作為與醇類的共溥物而蒸出， 直到達成需要的縮合（醚化）度。 尿素-甲駿預聚物本身可藉已知技術而製備，尤立是在 阳^至化^⑼^至列义的溫卜以重量計以以 至1.3份甲酸對一份尿素的重量比（基於莫耳為】對 2.6 : 1)下’於水中在尿素及甲路之間的鹼催化反應。謎化 於是如先前段落中所述而達成。 醚化度可藉在蒸鶴期間除去的水量而監測。雖然醚化 度可在廣泛範圍内變化而適應反應系統之需求，在隨後的 成壁殼步驟中聚合反庫之^ 愿之連辜隨醚化度的增加而降低。太 高的_化度因此傾向於抑制成 I利凤璧设的進展。然而，預聚物 的對水溶解度亦隨增加的w # 、 通㈢加的醚化度而降低。既然低的對水溶 解度為该預聚物的一種需餐胜料 禋而衣特徵，最好是避免太低的醚化 度。因此’適合且較佳的範圍為那些記載於上文中者。 包含核心液體及醚化的預聚物之有機溶液，當後者預 溶於溶劑中時係最方便地开^忐 更也开/成，正如其在商業上販售而用 於塗佈及加工業時一槎。A A/ 、 一 ’ 备夫乏這樣的溶劑時，在經基間 曾有南度的氮鍵’且該子音聲私乂么 預來物係為難溶於膠囊核心液體中 的臘狀固體。極性有機、、交劍#丄、4 百機-合劑係尤其可用於防止氳鍵並溶化 預XK物，其貫例包括醇、g 、 # 一 酉曰及方香知化合物。當使用 具有鬲鍵長的鱗化劑日年 -A--p ^ Μ ^，亦可使用脂肪族及其它非極性溶 劑。最有用的溶劑為與用作 ^ 、 乍^化鈉者相同的醇類，且該溶 液係直接從醚化步驟的反應混合物中直接取出。 在有機相中預聚物的濃度對本發明之實施並非關鍵， 20 200831180 仁可視在加工後的膠囊中需要的膠囊壁殼強度及需要的核 心液體量’而在廣泛的範圍内變化。，然而，其將最方便使 用具有以重量計大約1 %至大約70 %，較佳大約5 %至大 約50 %之預聚物濃度的有機相。 C·選擇性添加劑 選擇性添加劑包括溶劑、聚合反應催化劑，以及壁殼 改性劑。 土开 洛劑提供了一種控制形成壁殼反應的方法。如 落E中所闡明，當質子與尿素_甲醛預聚物接觸時反應： 有枝;相必肩足夠地親水而從水相主體中吸引質子至界 面、需足夠地疏水而防止大量的質子跨越該界面，並導 致遍及液滴主體而發生聚合反應。添加至有機相之 :Γ!可修正有機相的特性而達到這些效果。顯二，、 :;二：求及需要的溶劑類型-疏水或親水-取決於核心液 “…天十生。脂肪族及非環狀之溶劑為疏水性溶劑之實 二醇及_為親水性溶劑之實例。溶劑量可隨需求變化 而達到需要的效果。 而j又化 催化^㈣成錢反應的催化劑可置^或有機相中。 ^般係當核心材料過於疏水時使用，因它們# #男 引質子？古德4 u匕們係供吸 攜帶質子的任何水可溶之催化劑如可 y:包括鄰氯苯甲酸、2_苯…二氯醋酸、二用： 杨I、對-甲苯磺酸，以及十二烷基苯磺酸 ：7 果可Μ、、突紐、上， I』樣的催化效 —解這些酸的鹽類於水或有機相中，然後酸化水相 21 200831180 而達成。酸型式係藉離子交換而產生。In the non-etherified form, the prepolymer contains a large amount of methylol_CI^〇H in its molecular structure. Etherification is a substitution of a hydroxy hydrogen with an alkyl group and is achieved by a condensation reaction of a prepolymer with an alcohol. When the yard contains four carbon atoms or more and it has displaced more than about 50% of the hydroxyl hydrogen atoms on the prepolymer molecule, the prepolymer becomes soluble in the organic phase. However, complete etherification needs to be avoided, as it is necessary for the in-situ self-condensation polymerization reaction occurring in the step of forming the shell. Accordingly, the prepolymer useful in the present invention is from about 5% to about 7% by weight of a transradical hydrogen atom which has been replaced by a calcining group each having 4 to 1 Q carbon atoms. In a preferred embodiment, from about 7% to about 9%, this group has been etherified with an alcohol of C4_CO. Both linear and branched alcohols can be used in the present invention, and all of the carbon atom ranges recited herein include upper and lower limits. The etherified urea-mesh prepolymer is commercially available as a solution of an alcohol or a mixture of an alcohol and xylene. Alcohols used as solvents are generally the same as those used as deuterators. The most common users are n-butanol and isobutanol. The degree of shunting (butylation) in this product is between 7〇% and 9%, and the solution contains 5G% to 85% of the prepolymer by weight. There are also a small amount of free and two cold liquids that are sold as cross-linking agents for alkyd trees, and are mainly used for coating and processing products, such as pigments and paints. As a binder, it is not considered to be an aqueous solution or a water-soluble urea-formaldehyde prepolymer which has been etherified in a weakly acidic alcohol solution, and is solid-free, which is also commercially available. Concentrate the condensation with the desired alcohol in the middle of the period. The water of the condensation reaction is distilled off as a conjugate with an alcohol until the desired degree of condensation (etherification) is achieved. The urea-methyl precursor prepolymer itself can be prepared by a known technique, and the weight ratio of the weight of the sulphate to the weight of one part of the weight of the sulphur Mohr is a base-catalyzed reaction between urea and a road in water under 2.6: 1). The mystery was then achieved as described in the previous paragraph. The degree of etherification can be monitored by the amount of water removed during steaming the crane. Although the degree of etherification can be varied within a wide range to accommodate the needs of the reaction system, the tendency of the polymerization anti-reservoir in the subsequent wall-forming shell step decreases as the degree of etherification increases. Too high a degree of _degree is therefore tending to inhibit the progress of the formation of the phoenix. However, the water solubility of the prepolymer also decreases with increasing degrees of etherification of w# and (3). Since the low water solubility is a desirable feature of the prepolymer, it is preferred to avoid too low a degree of etherification. Thus, 'suitable and preferred ranges are those recited above. An organic solution comprising a core liquid and an etherified prepolymer which is most conveniently opened and formed when the latter is pre-dissolved in a solvent, as it is commercially sold for coating and processing industries. A moment. A A / , a solvent such as sufficiency, has a south nitrogen bond between the bases and the sound is private. The precursor is a waxy solid that is insoluble in the core liquid of the capsule. The polar organic, cross sword #丄, 4 hundred machine-mixer system can be especially used to prevent the hydrazine bond and dissolve the pre-XK substance, and its examples include alcohol, g, #一酉曰 and Fangxiangzhi compounds. Aliphatic and other non-polar solvents can also be used when a scaler having a ruthenium bond length is used -A--p ^ Μ ^. The most useful solvent is the same alcohol as that used for ^, sodium hydride, and the solution is taken directly from the reaction mixture of the etherification step. The concentration of the prepolymer in the organic phase is not critical to the practice of the present invention, and the temperature of the capsule wall shell required in the processed capsule and the amount of core liquid required is varied within a wide range. However, it will be most convenient to use an organic phase having a prepolymer concentration of from about 1% to about 70% by weight, preferably from about 5% to about 50% by weight. C. Selective Additives Selective additives include solvents, polymerization catalysts, and wall shell modifiers. The soil opener provides a means of controlling the formation of the wall shell reaction. As stated in Fall E, when the proton is in contact with the urea-formaldehyde prepolymer, it reacts: it has branches; it must be sufficiently hydrophilic to attract protons from the main body of the water phase to the interface, and it must be sufficiently hydrophobic to prevent a large number of protons from crossing. This interface causes polymerization to occur throughout the body of the droplet. Add to the organic phase: Γ! Correct the properties of the organic phase to achieve these effects.显二,, :; 2: The type of solvent needed to obtain - hydrophobic or hydrophilic - depends on the core liquid "... Tiansheng. Aliphatic and acyclic solvents are hydrophobic solvents and diols are hydrophilic An example of a solvent. The amount of solvent can be changed according to the demand to achieve the desired effect. The catalyst of the catalyst can be placed in the organic phase or the organic phase. ^The system is used when the core material is too hydrophobic, because they# #男引质子?古德4 u匕 are any water-soluble catalysts for the absorption of protons, such as y: including o-chlorobenzoic acid, 2-benzene, dichloroacetic acid, two-purpose: Yang I, p-toluene Sulfonic acid, and dodecylbenzenesulfonic acid: 7 can be ruthenium, rhodium, on, the catalytic effect of the solution - the salt of these acids in water or organic phase, and then acidify the aqueous phase 21 200831180 The acid form is produced by ion exchange.
壁殼改性劑係藉變化壁殼對核心材料的滲透性，而供 修飾其特性之用。適合的壁殼改性劑含有可與預聚物上的 經甲基反應的大量經或疏基。壁殼改性劑可在有機溶液中 使用’用以增加複數個龍甲基的連接而增加交聯度，或 者用以耗盡預聚物上的活性位置而減低交聯度。因此，視 使用的改性劑種類及改性劑對預聚物的比例而定，可增加 或減少壁殼的滲透性（且結果是核心液體之釋放速率）。曰萬° 麻油為此類試劑的一個實例。較佳的交聯壁殼改性劑為由 Cmc聰atl MilaCron Chemicals 以商品名 mercaptate 43 ESTER販售的新戊四醇四（巯基丙酸酯 有類似性質的多官能硫醇醋。 更用/、匕具 !>·乳液的形成 一旦有機溶液形成， 及表面活性劑的水溶液中 量對本發明之實施並非關 文限於方便性及操作便利 包含總乳液體積的最大大 中的有機溶液不連續液滴 可藉將該有機溶液分散於包含水 而形成乳液。有機及水相的相對 鍵且可在廣泛範圍内變化，但最 性。在實際使用中，該有機相將 約55 %，且將包含分散於水溶液 2活性劑可為任何已知可用於降低液體界面之表面 種化合物。非離子及離子型皆為有㈣。非離子 氧^貫例為長聽基及硫料乙氧⑽、料芳基聚乙 二、k基方基聚St醇、燒基聚輯、聚氧伸乙基去水 一肪酸醋、聚敦伸乙基_’以及聚伸乙基乙二醇與 22 200831180 脂肪或松香酸的酯。陰離子續南丨 一 于' d之貫例為烷基及烷基芳基 磺酸鹽的鈣、胺、醇胺及鹼金屬 峨孟屬鹽，植物的磺酸鹽；以及 乙氧化及丙氧化的磷酸單-及-齡 久一鍵。表面活性劑之混合物亦 為有用的。較佳的表面活性劑為直鏈醇的聚伸乙基乙二醇 醚，以及炫基及烧基芳基石黃酸鹽的驗金屬鹽。 表面活性劑的量對本發明 & 个&明而3亚非關鍵，且可在廣泛 範圍内變化。& 了方便性，該試劑通常包含以重量計大約 0.1 /〇至大約5.0 /〇的水相。該試劑可在乳液形成前或後添 加0The wall shell modifier is used to modify the properties of the core material by changing the wall shell. Suitable wall shell modifiers contain a large amount of or a thiol group which is reactive with the methyl group on the prepolymer. The wall shell modifier can be used in organic solutions to increase the degree of crosslinking by increasing the number of linkages of the dragon methyl groups, or to deplete the active sites on the prepolymer to reduce the degree of crosslinking. Thus, depending on the type of modifier used and the proportion of modifier to prepolymer, the permeability of the wall shell can be increased or decreased (and as a result the release rate of the core liquid).曰 ° sesame oil is an example of such a reagent. A preferred cross-linked wall shell modifier is neopentyltetraol (manufactured by Merctate 43 ESTER, sold under the trade name Mercaptate 43 ESTER by Cmc Cong atl MilaCron Chemicals, a polyfunctional thiol vinegar having similar properties. Utensils!>·Formation of Emulsions Once the organic solution is formed, and the amount of aqueous solution of the surfactant is not limited to the implementation of the present invention, it is limited to convenience and ease of operation. The organic solution can be dispersed in water to form an emulsion. The relative bonds of the organic and aqueous phases can vary widely, but most. In practical use, the organic phase will be about 55% and will contain dispersion. The active agent in aqueous solution 2 can be any surface compound known to be useful for reducing the liquid interface. Both non-ionic and ionic types are (IV). Non-ionic oxygen is a long-based base and sulfur ethoxy (10), aryl. Poly(ethylene), k-based poly(St-alcohol), calcined base, polyoxy-extension ethyl dehydrated fatty acid vinegar, polydendron ethyl-' and polyethylidene glycol and 22 200831180 fat or rosin acid Ester贯 于 于 ' ' 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基And - a long-lasting one-key. A mixture of surfactants is also useful. Preferred surfactants are polyethylidene glycol ethers of linear alcohols, and fluorenyl and alkyl aryl rhodamines. The amount of surfactant. The amount of surfactant is not critical to the present invention &&&>> and can vary widely. & Convenience, the reagent typically comprises from about 0.1 / Torr to about 5.0 by weight. /〇Aqueous phase. This reagent can be added before or after the emulsion is formed.
在二系統中’礼液穩定性可藉添加保護性膝體至水 相中而提高。保護性膠體穩定分散系統免於聚集、凝聚及 合併：許多材料係已知可作為保護性膠體之功用且為商業 上可付的，包括聚乙烯醇、褐藻酸鹽、-及-蛋白質、 酪A白、甲基纖維素、羧曱基纖維素、明膠、膠、天然膠、 多元酸，以及澱粉。該膠體可在乳液形成前添加至水相中， 或在其形成後添加至乳液本身。雖然該膠體為一種選擇性 力J車又仫為包括其在本系統中。聚乙烯醇保護性膠體 尤其為較佳。 可供作為保護性膠體的額外化合物為木質素磺酸鹽的 =，例如鈉、鉀、鎂、鈣或銨鹽。所有市售的木質素磺酸 鹽之中為 Scott Paper Co.，F〇rest Chemical Pr〇ducts 的 、LTS、LTK及LTM ’其分別為木質素續酸鹽⑼ /o水/谷液）的鉀、鎂及鈉鹽；American Can c〇.的木質素碏 酸鈉 MARASPERSE CR® 及 Merasperse CB〇s_3(g) ’· 23 200831180In the second system, the stability of the ritual fluid can be increased by adding a protective knee to the aqueous phase. Protective colloid-stable dispersion systems are free of aggregation, aggregation, and combination: many materials are known to function as protective colloids and are commercially viable, including polyvinyl alcohol, alginate, -and-protein, cheese A White, methyl cellulose, carboxymethyl cellulose, gelatin, glue, natural rubber, polybasic acid, and starch. The colloid may be added to the aqueous phase prior to emulsion formation or added to the emulsion itself after it has formed. Although the colloid is a selective force, the J car is included in the system. Polyvinyl alcohol protective colloids are especially preferred. An additional compound available as a protective colloid is the lignosulfonate =, for example, a sodium, potassium, magnesium, calcium or ammonium salt. Among the commercially available lignosulfonates are the potassium of Scott Paper Co., F〇rest Chemical Pr〇ducts, LTS, LTK and LTM 'which are lignin hydrochloride (9) / o water / gluten, respectively) , magnesium and sodium salts; American Can c〇. lignin sodium sulphate MARASPERSE CR® and Meraspers CB〇s_3(g) '· 23 200831180
Westvaco P〇lyChemicals 的木質素磺酸鈉鹽 Polyfon Ο®、 Polyfon Τ®、Reax 88Β®、Reax 85Β®，以及木質素磺酸 姜弓鹽Reax C21® ; ITT Rayonier Inc.的木質素石黃酸鈉及録 鹽 Orzan S 及 Orzan A。 膠體的實際量並非關鍵，且可使用在增強乳液穩定性 上有效的任何量。就水相重量而論，使用介於大約Ο·〗％ 及大約5·0 %之間的膠體為最方便的。 在乳液中液滴的大小對本發明而言並非關鍵。為了最 終產物的最大效用，液滴的大小將落於直徑大約〇·5微米 至大約4000微米的範圍内。為了多數殺蟲劑之應用，較 佳的範圍為直徑大約1微米至大約10〇微米。該乳液係藉 任何常用的高扭力攪拌裝置之使用而製備。一旦獲得需要 的液滴大小，溫和的攪動一般係足以防止在該步驟從頭到 尾的平衡中液滴之成長。 Ε·壁殼的形成 一旦獲得該分散液以及需要的液滴大小，該系統係酸 化至介於大約0及大約4.0之間的ρΗ，較佳介於大約1〇 及大約3 ·0之間。此導致醚化的尿素_甲醛預聚物經原地自 縮合反應而聚合，且形成完全封入各液滴的殼層。酸化可 藉任何適當的方法而達成，包括添加任何水可溶的酸，包 括甲酸、檸檬酸、鹽酸、硫酸、磷酸，以及類似者。酸化 亦可藉酸性分散劑或表面活性劑的使用而達成，前提是這 樣的組成成份係在乳液已形成後才添加至系統中。 當聚合物壁殼變得更堅固時’在預聚物上的活性基之 24 200831180 間的接觸逐漸地變得更困難。因此，原地自縮合聚合反應 係自動終止，且一般係允許反應完全。然而，該反應可在 元成前藉提咼pH而遏止。以此方法可控制壁殼的緊密性、 堅固性，以及滲透性。此在大多數實例中亦可藉如上文所 述之壁殼改性劑而達成。Westvaco P〇lyChemicals sodium lignin sulfonate Polyfon®, Polyfon®, Reax 88®, Reax 85®, and Rex C21® lignin sulfate; ITT Rayonier Inc. lignin sodium sulphate And recorded salt Orzan S and Orzan A. The actual amount of colloid is not critical and any amount effective to enhance emulsion stability can be used. In terms of the weight of the aqueous phase, it is most convenient to use a colloid between about 〗·〗 and about 5.00%. The size of the droplets in the emulsion is not critical to the invention. For maximum utility of the final product, the droplet size will fall within the range of from about 〇5 microns to about 4000 microns in diameter. For most insecticide applications, a preferred range is from about 1 micron to about 10 microns in diameter. The emulsion is prepared by the use of any conventional high torque agitation device. Once the desired droplet size is achieved, gentle agitation is generally sufficient to prevent the growth of droplets in the balance from head to tail in this step. Formation of the crucible wall Once the dispersion and the desired droplet size are obtained, the system is acidified to a pH between about 0 and about 4.0, preferably between about 1 and about 3.0. This results in the etherification of the urea-formaldehyde prepolymer which is polymerized by in-situ condensation reaction and forms a shell which is completely enclosed in each droplet. Acidification can be accomplished by any suitable method, including the addition of any water soluble acid, including formic acid, citric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and the like. Acidification can also be achieved by the use of acidic dispersants or surfactants, provided that such components are added to the system after the emulsion has formed. The contact between the active groups on the prepolymer 24 200831180 gradually becomes more difficult as the polymer wall shell becomes stronger. Therefore, the in situ self-condensation polymerization is automatically terminated and generally allows the reaction to be complete. However, the reaction can be suppressed by raising the pH before the formation. In this way, the tightness, robustness, and permeability of the wall shell can be controlled. This can also be achieved in most instances by a wall shell modifier as described above.
原地自縮合聚合反應的速率，取決於pH會隨酸度及 溫度而增加。反應因此可在大約20 〇c至大約1〇〇範 圍之内於任何地方實施，較佳介於大約4〇 〇c及大約% =間。反應-般將在數小時内完成，雖然、隨著高酸度及高 溫度，反應可在數分鐘内完成。 M q〜叫丨啕廿汉1之用，或 ::遽並回收為乾朦囊。在任-型式中，該膠囊在核心液 體的緩慢釋放上為有用且有八 、查婊4 Α 頁欢的刀政液係較佳藉溶解於 連，相的分散劑穩定。既麸 液中…， L、、大夕數分散劑在"生或鹼性溶 = 旦壁殼形成後較佳提高分散液的阳。此可The rate of in situ self-condensation polymerization depends on the pH increasing with acidity and temperature. The reaction can therefore be carried out anywhere from about 20 〇c to about 1 Torr, preferably between about 4 〇 〇 c and about % =. The reaction will generally be completed in a few hours, although, with high acidity and high temperature, the reaction can be completed in a matter of minutes. M q~ is called 丨啕廿汉1, or ::遽 and is recycled as a dry sac. In the arbitrarily-typed form, the capsule is useful in the slow release of the core liquid and is preferably lysed by a dispersant that dissolves in the phase. In the bran solution..., L, and the large number of dispersing agents are preferred to increase the yang of the dispersion after the formation of the raw or alkaline solution. This can
精任何水可溶的鹼而達成。 J 型0八4 M h 1 戚了使用任何常用的分散劑。典 i的分散劑包括木質素續酸 續酸納、聚亞甲基雙-…：“的炫基奈續酸鹽、蔡 牛石黃酸納。 “滅鹽，以及W甲基，長鏈酸） 渗透=二方法:::特徵為封入有機相液滴的_ 之間形成之二有機相液滴及水相溶液 方法而形成。此為尿素·甲盤:二駿預聚物的縮合反應之 果。 、_預聚物溶解於有機相中的結 25 200831180 在界面的有機侧形成聚合物殼層之優點有許多。第一 =該方去本身較涉及在水相中的成壁殼縮合反應之先前技 π方法而車乂易於控制。當縮合反應在水相中發生時，除了 w^液滴上之外，成壁殼聚合物可沈積在乳液存在的容 口。土成上、在攪拌葉上，或者在任何可能存在的其它結構 上。相反的，在界面之有機侧縮合的成壁殼聚合物不會沈 積在任何容器壁殼或其它結構上。 另外，當縮合反應發生在水相中時，正如先前技術一 般，必須使用減量的分散有機才目，因為若利用較高的分散 有機相含量，M,j會使得分散液太黏並膠化，因此實際上遏 了微膠囊的形成。在界面有機侧之縮合反應因此可得到 車又n的分散有機相載荷，因在水相中並未形成凝膠。 在本文提出之有機相含殺蟲劑的實例中，較高載荷的 :機相產生更濃的殺蟲劑調配物。這使可達成在製造、包 衣及運輸上大量的費用節省。 以下實施例係提供作為本發明之方法及產物之解釋， 且亚非意圖以任何方式定義或限定本發明。 【實施方式】 實施例1 製備含309.6克水、4_〇克烷基萘磺酸鈉鹽（CAS號碼 乃1〇3_93-8)，以及lh2克萘磺酸聚合物與甲醛之鈉鹽（cas 唬碼50-〇〇-〇)的水溶液。然後以濃硫酸降低卩11至<2.〇。 藉混合320克殺真菌劑普克利（pr〇pic〇naz〇le：^ rs/sr 及RR/SS非鏡像異構物對混合物及8〇克2_甲基萘，接著 26 200831180 知南溫度至50 αΓ*二制μ π。。，接著…:古飽和的有機溶液。然後冷卻此至 ；y：eI —^ 為70-90 %)。 /°正7Ί谷液’其中丁基化程度 隨著攪動緩慢添加有機相 度至得到SI m 機相至水相中。然後增加檀動速Achieved with any water-soluble base. Type J 0 8 M H 1 戚 Use any commonly used dispersant. The dispersing agent of the formula i includes lignin, sodium phthalate, polymethylene bis-...: "Hyunse naphthate, chlorsulfuric acid sodium." Salt, and W methyl, long chain acid Permeation = two methods::: characterized by a method of encapsulating two organic phase droplets and an aqueous phase solution formed between the _ of the organic phase droplets. This is the result of the condensation reaction of urea·A plate: Erjun prepolymer. , _ prepolymer dissolved in the organic phase of the junction 25 200831180 There are many advantages to form a polymer shell on the organic side of the interface. The first = the party itself is more controllable than the prior art π method involving the condensation reaction of the wall-shell in the aqueous phase. When the condensation reaction occurs in the aqueous phase, in addition to the w^ droplets, the wall-shell polymer can be deposited in the presence of the emulsion. Soil, on agitating leaves, or on any other structure that may be present. Conversely, the walled shell polymer condensed on the organic side of the interface will not deposit on any of the container wall shells or other structures. In addition, when the condensation reaction occurs in the aqueous phase, as in the prior art, it is necessary to use a reduced amount of dispersed organic matter, because if a higher dispersed organic phase content is utilized, M, j will make the dispersion too viscous and gelatinized. Therefore, the formation of microcapsules is actually suppressed. The condensation reaction on the organic side of the interface thus results in a dispersed organic phase loading of the vehicle n, since no gel is formed in the aqueous phase. In the examples of organic phase insecticides proposed herein, higher loading: the machine phase produces a more concentrated pesticide formulation. This allows for substantial cost savings in manufacturing, packaging and shipping. The following examples are provided to illustrate the methods and products of the present invention, and the present invention is intended to define or define the invention in any manner. EXAMPLES Example 1 A sodium salt containing 309.6 g of water, 4 g of alkyl naphthalenesulfonate (CAS number 1〇3_93-8), and 1 h of g of naphthalenesulfonic acid polymer and formaldehyde (cas) was prepared. An aqueous solution of weight 50-〇〇-〇). Then, 卩11 is reduced to <2.〇 with concentrated sulfuric acid. By mixing 320 grams of the fungicide Ppkley (pr〇pic〇naz〇le:^ rs/sr and RR/SS non-mirror isomer mixture and 8 g of 2-methylnaphthalene, followed by 26 200831180 50 αΓ*二制μ π., then...: an ancient saturated organic solution. Then cool this to; y:eI —^ is 70-90%). /°正7Ί谷液' The degree of butylation The organic phase was slowly added with stirring to obtain the SI m phase into the aqueous phase. Then increase the speed of the sandal
二：：液滴之平均顆粒大小“微未及2〇微米之 …在恤和攪動下，加熱混合 斷加熱並以氫氧蝴提高阳至9。 。中 實施例2 製備· 3 09 6 古 791〇3 、·水、4·0克烷基萘磺酸鈉鹽（CAS號碼 以及U·2克萘磺酸聚合物與甲醛之鈉踏（CAS —、 ）尺，谷液。然後以濃硫酸降低pH至<2.〇。 错混合1 6 0昔将吉·^十，社丄 見杈真囷劑邁克尼（mycl〇bUtanil)及24〇克 甲基奈，接著提高溫 夕 ,、 又至50 c而衣備飽和的有機溶液。 八、、後θ部此至30 Qr^ ,. ^ ，接者添加52克Cymel ϋ-105(Μ0樹 月日（口 (Μ分丁基化的尿辛 Κ京-甲备預聚物之60 %正丁醇溶 直 中丁基化度為70-90 %)。 隨著攪動緩慢添&古^ s ^ A i 又〇、、加有機相至水相中。然後增加攪動速 又至知到乳液液滴之平& @ + i / '^十构顆粒大小在2微米及20微米之 間。然後在溫和擾動下 士 #、曰人k 謂1勒下，加熱混合物至55 °C三小時。中 斷加熱並以氫氧化銨提高pH至9。 …雖,然可在以上方法中達成多種改變而不背離本發明之 範田壽，以上敘述中路 斤有包含的事項係意圖且應理解為說明 而非限制之意義。 27 200831180Two: The average particle size of the droplets is “not less than 2 μm.... Under the shirt and agitation, the heating is mixed and heated to increase the yang to 9 with hydrogen hydroxide. Example 2 Preparation · 3 09 6 Ancient 791 〇3, · water, 4 · 0 g of alkyl naphthalene sulfonate sodium salt (CAS number and U · 2 g of naphthalene sulfonic acid polymer and formaldehyde sodium step (CAS —, ) ruler, valley liquid. Then reduce with concentrated sulfuric acid pH to <2.〇. Mismixed 1 6 0 将吉·^10, 丄 丄 杈 迈 迈 迈 迈 my my my my my my my my my my my my my my my my my my my my my my my my my my my my my my my my my my my my my my 50 c and ready to saturate the organic solution. VIII, after the θ part to 30 Qr ^,. ^, add 52 grams of Cymel ϋ-105 (Μ0 tree month day (mouth (Μ 丁基 butyl urinary xin 60% n-butanol in the Jing-A premix has a degree of butylation of 70-90%.) As the agitation slowly adds & ancient ^ s ^ A i and 〇, add organic phase to the water Then increase the agitation speed and then know that the emulsion droplets are flat & @ + i / '^ 构 颗粒 颗粒 颗粒 2 2 2 2 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 温 温 温 温 温 温 温 温 温 温 温 温 温 温 温 温Next, heat the mixture to 55 °C three The heating is interrupted and the pH is raised to 9 with ammonium hydroxide. Although a variety of changes can be achieved in the above method without departing from the scope of the present invention, the above-mentioned items are intended to be understood and should be understood as Explain, not limit the meaning. 27 200831180
【圖式簡單說明】 (無） 【主要元件符號說明】 (無） 28[Simple description of the diagram] (none) [Description of main component symbols] (none) 28
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| ES2480343B1 (en) * | 2013-01-25 | 2015-05-20 | Ecopol Tech, S.L. | Process for the manufacture of a corresponding microencapsulated and reactive amphiphilic compound, microencapsulated and composition |
| CN103190436A (en) * | 2013-04-26 | 2013-07-10 | 柳州市惠农化工有限公司 | Insecticidal composition |
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