TW423958B

TW423958B - Fungicidal mixtures

Info

Publication number: TW423958B
Application number: TW86105284A
Authority: TW
Inventors: Hubert Sauter; Klaus Schelberger; Gisela Lorenz; Eberhard Ammermann; Siegfried Strathmann
Original assignee: Basf Ag
Priority date: 1996-04-26
Filing date: 1997-04-23
Publication date: 2001-03-01

Abstract

A fungicidal mixture comprising (a) an oxime ether of the formula I, where the substituents have the following meaning: X is amino (NH); Y is N; Z is oxygen or sulfur; R' is C1-C6-alkyl; and (b) a dithiocarbamate (II) selected from the group consisting of -manganese ethylenebis(dithiocarbamate) (zinc complex) (IIa), -manganese ethylenebis(dithiocarbamate) (IIb), -zinc ammoniate ethylenebis(dithiocarbamate) (IIc) and -zinc ethylenebis(dithiocarbamate) (IId) or (c) 1-(2-cyano-2-methoxyiminoacethyl)-3-ethylurea (III) H3CCH2-NHCONH-C(CN)=NOCH3 (III) in a synergistically active amount.

Description

4 2 3 9 5 8 A7 B74 2 3 9 5 8 A7 B7

1 ΟΠ3 j. 2-R· YOCH3 五、發明説明（1 本發明係有關一種殺眞菌混合物，包括協同活性量之· a)式I之肋醚： ch3 NOCH, gh3x^ . i 0) 其中取代基具有下列意義： X爲氧或胺基（NH);' Y爲CH或N ; Z爲氧、硫、胺基（NH)或Ci_4烷胺基（N-C,_4烷基）； R爲C | — 4从基、C 1 · 6卣,燒基、C 3 - 6婦基、由稀'基、〇3.6块基、C3-6鹵炔基、C3.6南炔基、（：3-6環燒基甲基或可部份或全部氛化及/或可帶有1至3個下列基之爷部氫化及/或可帶有1至3個下列基之苄基：氰基、C|_4燒基、Cb4鹵烷基、（V4烷氧基、C卜4鹵烷氧基及C!_4故硫基； ^ 及 b) 選自下列組群之二硫代胺基甲酸酯：」伸乙基雙（二硫代胺基甲酸）錳（鋅錯合物）（IIa)， -伸乙基雙（二硫代胺基曱酸）錳（lib)，、伸乙基雙（二硫代胺基曱酸）鋅氨绛物（lie)及 -伸乙基雙（二硫代胺基甲酸）鋅（lid)，及/或 c) 下式之1 -(2 -氨基-2 -甲氧基亞胺之乙酷基)-3 -乙基腿(III): H3CCH2-NHCONH-C(CN)=NOCH3 (III) 本紙張尺度適用中國國家榇準（CNS ) A4規格（210X 297公釐） -裝----·--訂------咸 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央椟準局員工消費合作社印裝 423958 Α7 Β7 經濟部中央楳準局貝工消費合作社印装五、發明説明（2 ) 再者，本發明係有關使用化合物丨，〖〖及/或〖〗〗之混合物控制有¥眞菌之方法，及有關化合物jj j及〗丨丨用以製備此種混合物之用途。式I化合物，其製法及其抗有害眞菌之作用已揭示於文獻中（WO-A 95/21，153，WO-A 95/21，154，DE 195 28 651.0)。二硫代胺基曱酸酯II，其製法及其抗有害眞菌之作用亦已經揭示（Ila:俗名：鋅錳乃蒲（mancozeb)，US-A 3,379,610; lib:俗名：錳乃蒲（maneb)，US-A 2,504,404 ; lie:先前俗名：免得爛（metiram)，US-A 3,248,400;IId:俗名：鋅乃蒲（2丨1^)，-US-A 2,457,674)。化合物III、其製法及其抗眞菌作用亦已揭示（us_A 3,957,847;俗名：西莫山寧（(^111〇^^1^1))0 本發明之一目的係提供一種具有改良之抗有害眞菌作用之混合物，其以降低總量之施用之活性成分組合（協同性混合物）’而可降低施用比例並改良已知化合物作用之菌譜。已發現此目的可藉前揭定義之混合物而達成。再者，亦發現可藉同時或分別施用化合物I、π&/或ΙΠ或依序施用化合物I、II及III而得到比使用個別化合物時更佳之控制有害眞菌之效果。本發明係有關化合物I及π或I及][u之混合物及包括化合物I、化合物11及化合物π丨之混合物。通式1尤其代表其中X爲氧及Υ或CH之Β醚或X爲胺基及 Υ爲Ν之肟醚^ 再者，較好爲其中ζ爲氧之化合物。 (請先閲讀背面之注意事項再填寫本頁) 本紙張认適财咖^準（CNS}如胁（2獻297公们 23 95 〇 A7 B7 五、發明説明（同樣地，較好爲其中R1爲境!墓或卞基之化合物I。依據其使用於本發明協同混合物之用途’特佳之化合物爲下表所列者：表1 其中各化合物ZR'相當於表A—欄之式IA化合物1 ΟΠ3 j. 2-R · YOCH3 V. Description of the invention (1 The present invention relates to a fungicidal mixture, including a synergistically active amount a) Rib ether of formula I: ch3 NOCH, gh3x ^. I 0) where substituted Has the following meanings: X is oxygen or amine (NH); 'Y is CH or N; Z is oxygen, sulfur, amine (NH) or Ci_4 alkylamino (NC, _4 alkyl); R is C | — 4 secondary, C 1 · 6 卣, alkynyl, C 3-6 alkynyl, dilute group, 〇3.6 block, C3-6 haloalkynyl, C3.6 alkynyl, (: 3-6 Cycloalkyl methyl groups may be partially or fully aerated and / or may be hydrogenated with one to three of the following groups and / or benzyl groups may be provided with one to three of the following groups: cyano, C | _4 alkyl, Cb4 haloalkyl, (V4 alkoxy, C4 haloalkoxy, and C! _4 thio group; ^ and b) a dithiocarbamate selected from the group consisting of: "" Ethylbis (dithioaminoformate) manganese (zinc complex) (IIa), -Ethylbis (dithioaminoformate) manganese (lib), Ethylbis (dithio) Amine amino acid) zinc ammonium (lie) and -ethylenyl bis (dithiocarbamate) zinc (lid), and / or c) 1- (2-amino-2) -Ethyloxy group of methoxyimine) -3 -Ethyl legs (III): H3CCH2-NHCONH-C (CN) = NOCH3 (III) This paper size applies to China National Standard (CNS) A4 (210X 297 Mm)-installed ---- · --ordered ------ salty (please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 423958 Α7 Β7 Central of the Ministry of Economic Affairs Printed by the Zhunzhou Bureau Shellfish Consumer Cooperative Co., Ltd. V. Description of the Invention (2) Furthermore, the present invention relates to a method for controlling ¥ 丨 bacteria using a mixture of a compound 丨 and [〖and / or〗〖, and related compounds jj j And the use for preparing such a mixture. The compound of formula I, its preparation method and its effect against harmful pinworms have been disclosed in the literature (WO-A 95 / 21,153, WO-A 95 / 21,154, DE 195 28 651.0). Dithioaminogallate II, its preparation method and its anti-harmful fungi function have also been revealed (Ila: common name: zinc manganese napu (mancozeb), US-A 3,379,610; lib: common name: manabi napu (maneb ), US-A 2,504,404; lie: previous common name: metiram, US-A 3,248,400; IId: common name: zinc naim (2 丨 1 ^), -US-A 2,457,674). Compound III, its preparation method, and its antibacterial effect on tadpoles have also been revealed (us_A 3,957,847; common name: simoxanin ((^ 111〇 ^^ 1 ^ 1)). 0 An object of the present invention is to provide an improved anti-harm 眞Bactericidal mixtures, which reduce the total amount of active ingredient combinations (synergistic mixtures) applied, can reduce the application rate and improve the bacterial spectrum of known compound effects. It has been found that this purpose can be achieved by the previously defined mixtures. In addition, it has also been found that compound I, π & / or III, or sequential application of compounds I, II, and III can be used to obtain better control of harmful fungi than when individual compounds are used. The present invention relates to Mixtures of compounds I and π or I and] [u and mixtures including compound I, compound 11 and compound π 丨. Formula 1 especially represents a B ether in which X is oxygen and Υ or CH or amine and Υ is The oxime ether of Ν ^ Furthermore, it is preferably a compound in which ζ is oxygen. (Please read the notes on the back before filling this page.) 23 95 〇A7 B7 V. Description of the invention (the same Preferably, the compound I in which R1 is a tombstone or a fluorenyl group is used according to its use in the synergistic mixture of the present invention. 'The best compounds are listed in the following table: Table 1 wherein each compound ZR' is equivalent to Table A —The compound of formula IA

(IA) 表2 其中各化合物Z R’相當於表A —欄之式IB化合物 CHa 1表A. CH30(IA) Table 2 wherein each compound Z R ′ is equivalent to the compound of the formula IB in Table A—Column CHa 1 Table A. CH30

〇BJ 經濟部中央標率局員工消費合作社印笨编號 , ZRr 1.1 t O-CH2CH2CH3 /1.2 〇-CH(CH3)2 1.3 0-CH2CH2CH2CH3 t 1.4 〇-CH(CH3)CH2CH3 1,5 0~CH2CH(CH3)2 1.6 〇-c(ch3)3 1:7 S-C(CH3)3 1.8 0™CHiCH3)CH2CH2CH3 、 1,9 0-CB2C(CH3)3 1.10 〇-CH2C(Cl)-CCl2 1,11 o-ch2ch=ch-ci (·反式） 1.12 Q-CH2C(CH3)=CH2 1.13 o-ch2-(環丙基卜 1.14 o-ch2-c6h5 1.15 ' 0~CH2-[4~F-C6H4] 1,16 0'CEi2CH3 1.17 0-CH(CH2CH3)2〇BJ Indian Consumer Code of the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, ZRr 1.1 t O-CH2CH2CH3 /1.2 〇-CH (CH3) 2 1.3 0-CH2CH2CH2CH3 t 1.4 〇-CH (CH3) CH2CH3 1,5 0 ~ CH2CH (CH3) 2 1.6 〇-c (ch3) 3 1: 7 SC (CH3) 3 1.8 0 ™ CHiCH3) CH2CH2CH3, 1,9 0-CB2C (CH3) 3 1.10 〇-CH2C (Cl) -CCl2 1,11 o -ch2ch = ch-ci (· trans) 1.12 Q-CH2C (CH3) = CH2 1.13 o-ch2- (cyclopropylbenzene 1.14 o-ch2-c6h5 1.15 '0 ~ CH2- [4 ~ F-C6H4] 1 , 16 0'CEi2CH3 1.17 0-CH (CH2CH3) 2

J---„------裝----.--訂-----旅 (請先閱讀背面之注意事項再填寫本頁)__I 本紙張尺度適用中國國家標準（CNS〉Μ規格（210X297公瘦） 423958 A7 B7 五、發明説明（4 ) 與〇 Υ雙鍵有關聯者，式I化合物可存有幾酸官能基）。據此仔組態（關於J --- „------ install ----.-- order ----- brigade (please read the precautions on the back before filling out this page) __I This paper size applies to Chinese national standards (CNS> M specifications (210X297 male thin) 423958 A7 B7 V. Description of the invention (4) Where there is a double bond with 〇Υ, the compound of formula I may have several acid functional groups. According to this configuration (about

m人其㈣或2異構物態之一或以E/Z (請先閲讀背面之注意事項再填寫本頁-- 異構物混合物態用於本萨明，·θ入贫月狀* s物中。較好使用Ε/Ζ異構物混&物或E異構物，以E異構物爲特佳。化^物！側鏈中之㈣之C = N雙鍵可呈現純£或2異構物 =或主E/Z異構物混合物態。化合物！可以異構物混合物態或以純異構物態使用於本發明遇合物中。由其用途來看，特佳足化合物ί爲其中侧鏈之㈣端基呈順式基對ZR|)。 3 由於其驗性特性，化合物^⑴可與無機或有機酸或與金屬離予形成加成物或鹽類。無機酸（實例爲氫由酸如氫氟酸、氫氣酸、氫溪酸及氯碘酸、硫酸 '磷酸及硝酸。經濟部中央樣準局貝工消费合作社印裝適：ϋ之有機酸爲例如甲酸、碳酸及烷酸，如乙酸 '三氟乙酸'三氣乙酸及丙酸，亦爲乙醇酸、硫氰酸'丙醇酸' 丁一酸檸檬酸、苯甲酸、肉桂酸、草酸，院確酸（含1至 20個碳原子之直鏈或分枝烷基之磺酸），芳磺酸或芳基二磺酸（其上連接有一或兩個磺酸基之芳烷基如苯基及莕基），烷膦酸（含1至20個碳原子之直鏈或分枝烷基之膦酸），芳膦酸或芳基二膦酸（其上連接有一或兩個膦酸基之芳族基，如苯基及蓁基），對烷基及芳基而言又可具有取代基，例如對-甲苯確酸，水楊酸，對-胺基水楊酸，2_苯氧基苯甲酸，2_乙醯氧基苯甲酸等。適宜之金屬離子爲（尤其是）第二主族之元素，特別是辦及本紙張尺度逋用中國國家標準（CNS ) Α4規格（210X297公嫠）經濟部中央標準局貝工消費合作杜印裝 A7 B7 五、發明説明（5 ) 鎂，第三及第四主族元素，特別是鋁、錫及鉛，第一至八亞族元素，特別是m m鋅及其他《特佳者爲第四週期亞族之元素之金屬離子。金屬可呈現其可假設之多種價數。當製備此混合物時，較好使用純活性成分以叫川：若需要亦可混合其他抗有害眞菌或其他害蟲(如昆蟲' 蟎及線蟲）之活性成分，或除草或生長調節活性成分或肥料。化合物I、11及I π之混合物或同時或分別使用化合物I， 11及111係以顯著之抗廣泛菌譜之植物致病性眞菌之活性加以區別，特別是子囊菌綱（Ascomycetes)，半知菌綱 (Deuteromycetes)，藥菌（Phyeomycetes)及擔子菌綱 (Basidiomycetes)類。其某些係以組織性作用且因此可使用作爲作用於葉及土壤之殺眞菌劑。該混合物於各種農作物如棉花、蔬菜物種（如胡瓜、大豆及葫蘆）、大麥、草地、橡樹、咖啡、玉米、果樹、稻 '裸麥、大豆、葡萄樹、小麥、裝飾性植物、甘蔗及各種種子中控制大量眞菌爲特別重要。其特別適用於控制下列植物致病性眞菌：於穀類中之禾白粉菌（Erysiphe graminis)(粉霉），於葫蘆中之二孢白粉菌 (Erysiphe cichoracearum)及蒼耳單絲殼（Sphaerotheca fuliginea)，蘋果中之白叉絲單囊殼（Podosphaera leucotricha)，於榖類中之柄銹菌屬（puccinia)，於棉花、稻及蔴中之絲殼菌屬（Rhizoctonia)，於殼類及甘蔗中之黑粉菌屬（Ustilago)，於蘋果中之蘋果黑星菌（Venturia inaequalis) 本紙張尺度適用中國國家橾準（CNS > A4規格（210X297公釐） ----„------•裝-------訂-----—i ^ {請先閱讀背面之注意事項再填寫本頁) 423958 A7 B7 五、發明説明（6 ) (scab)，於穀類中之長螺孢屬（Helminthosporium)，於小麥中之穎枯殼針抱（Septoria nodorum)，於草莓 '蔬菜 '裝飾性植物及葡萄中之灰葡萄抱（Botrytis cinerea)(灰霉），於落花生中之落花生尾抱（Cercospora arachidicola)，於小麥及大麥中之假尾孢（Pseudocercosporella herpotrichoides)，於稻米中之稻痕菌（Pyricularia oryzae)，於馬鈴薯及蕃茄中之致病疫霉（Phytophthora infestans)，於葫蘆及蛇麻草中之假霜霉屬 (Pseudoperonospora)，於葡萄中之葡萄生單轴霉 (Plasmopara viticola)，於蔬菜水果中之鏈格孢屬 (Alternaria)，及鐮抱屬（Fusarium)及輪枝抱屬 (Verticillium)。再者，其可用以保護物質（如保護木料）抗擬青霉 (Paecilomyces variotii) ° 化合物ί ' II及/或III可同時一起施用或分別或依續施用，在分別施用時，施用順序通常對控制測量結果不見任何影響。化合物I與11用量比例一般爲2 0 〇 : 1至〇 1 : 1，較好爲 1 〇 0 : 1至1 : 1，特別是5 0 : 1至5 : 1 (11: 1)之重量比。經濟部中央標準局貝工消費合作社印裝化合物I與III用量比例一般爲1〇:1至〇1:1，較好5:1至 0 _ 2 : 1，特別是3 : 1至1 : 3 (111: 1)之重量比。本發明混合物之施用率，視所需效果之性質而定，在化合物I之例中，通常自0.005至0.5公斤/公畝，較好〇〇1至〇 . 5公斤/公畝，特別是〇 . 〇〗至〇 · 3公斤/公畝。化合物II之施用率，通常自0.1至1〇公斤/公畝，較好〇 5 本紙張尺度適用令國國家標準（CNS ) A4祕（210 X 297公瘦）經濟部中央標準局貝工消費合作社印裝 423958 A7 -------- , ____________B7 五'發明説明（7 ) ~ 至5公斤/公畝，特別是1至4公斤/公畝。化合物III之施用率一般自〇〇〇5至〇8公斤/公畝，較好 0.01至0,5公斤/公畝’特別是0 0 5至〇 3公斤/公畝。對種子處理而言，混合物之施用率通常自〇〇〇1至1〇〇克 /公斤種子，較好0.01至5〇克/公斤種子，特別是〇〇1至1〇克/公斤種子。若欲控制植物致病性有害眞菌，可在植物播種之前或之後’或在植物萌芽之前或之後，對種子、植物或土壤噴霧或撒佈分別或組合施用之化合物4ΠΙ或化合物I、π 及111之混合物。m is one of the two isomers or E / Z (please read the notes on the back before filling out this page-the mixture of isomers is used for Bensamin, θ into a poor moon shape * s It is better to use E / Z isomers or E isomers, and E isomers are particularly preferred. Chemical compounds! The C = N double bond in the side chain can be pure. Or 2 isomers = or the main E / Z isomer mixture state. Compounds! It can be used in the mixture of the present invention as a mixture of isomers or as a pure isomer. From the point of view of its use, a particularly good compound ί It is the cis-group pair ZR |) in which the fluorene end group of the side chain is. 3 Due to its experimental properties, compounds can form adducts or salts with inorganic or organic acids or metals. Inorganic acids (examples are hydrogen from acids such as hydrofluoric acid, hydrogen acid, hydrogen brook acid and chloroiodic acid, sulfuric acid 'phosphoric acid, and nitric acid. The Central Samples Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, Printing Applicable: Organic acids of tritium are for example Formic acid, carbonic acid and alkanoic acid, such as acetic acid 'trifluoroacetic acid' triacetic acid and propionic acid, also glycolic acid, thiocyanic acid 'propanolic acid' succinic acid citric acid, benzoic acid, cinnamic acid, oxalic acid. Acids (sulfonic acids having linear or branched alkyl groups of 1 to 20 carbon atoms), aromatic sulfonic acids or aryl disulfonic acids (aralkyl groups having one or two sulfonic groups such as phenyl and Fluorenyl), alkylphosphonic acid (phosphonic acid of linear or branched alkyl group containing 1 to 20 carbon atoms), arylphosphonic acid or arylbisphosphonic acid (aromatic acid having one or two phosphonic acid groups attached thereto) Groups, such as phenyl and fluorenyl), may have substituents for alkyl and aryl groups, such as p-toluene acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzene Formic acid, 2_ethoxybenzoic acid, etc. Suitable metal ions are (especially) elements of the second main group, especially the Chinese national standard (CN S) Α4 size (210X297 cm) Duo Packing A7 B7, Shellfish Consumer Cooperation, Central Standards Bureau, Ministry of Economic Affairs 5. Description of the invention (5) Magnesium, the third and fourth main group elements, especially aluminum, tin and lead, Metal elements of the one to eight subgroups, especially mm zinc and other elements of the fourth cycle subgroup. Metals can exhibit various valences that can be assumed. When preparing this mixture, it is preferred to use pure The active ingredient is called Chuan: if necessary, it can also be mixed with other active ingredients that are resistant to harmful maggots or other pests (such as insects, mites and nematodes), or weeding or growth-regulating active ingredients or fertilizers. Mixtures of compounds I, 11 and I π Compounds I, 11 and 111 are used simultaneously or separately to distinguish their activity against a broad range of phytopathogenic Pseudomonas, especially Ascomycetes, Deuteromycetes, and medicinal bacteria (Phyeomycetes) and Basidiomycetes. Some of them are organized and therefore can be used as fungicides on leaves and soil. This mixture is used in various crops such as cotton, vegetable species ( Such as courgettes, soybeans and gourds), barley, grassland, oak, coffee, corn, fruit trees, rice, rye, soybeans, grape vines, wheat, decorative plants, sugarcane and various seeds are particularly important for controlling large numbers of fungi. Particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (mildew) in cereals, Erysiphe cichoracearum in gourds and Sphaerotheca fuliginea , Podsphaera leucotricha in apples, Puccinia in genus Puccinia, Rhizoctonia in cotton, rice and hemp, in shells and sugarcane Ustilago, Venturia inaequalis in apple This paper size is applicable to China National Standard (CNS > A4 size (210X297 mm) ---- „----- -• Install ------- Order ------- i ^ {Please read the notes on the back before filling out this page) 423958 A7 B7 V. Description of Invention (6) (scab) Helminthosporium (Helminthosporium) eptoria nodorum), Botrytis cinerea (Botrytis cinerea) in strawberry 'vegetable' decorative plants and grapes, Cercospora arachidicola in groundnut, and pseudocosporium in wheat and barley ( Pseudocercosporella herpotrichoides), Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Pseudoperonospora in gourds and hops, among grapes Plasmopara viticola, Alternaria, Fusarium and Verticillium in vegetables and fruits. Furthermore, it can be used to protect substances (such as wood) against Paecilomyces variotii ° Compounds II and / or III can be applied simultaneously or separately or sequentially. When applied separately, the order of application is usually The control measurement results have no effect. The ratio of the amount of compound I to 11 is generally 200: 1 to 1: 1: 1, preferably 100: 1 to 1: 1, especially 50: 1 to 5: 1 (11: 1) by weight . The dosage ratio of printed compounds I to III in the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs is generally 10: 1 to 1: 1, preferably 5: 1 to 0 _ 2: 1, especially 3: 1 to 1: 3 (111: 1) weight ratio. The application rate of the mixture of the present invention depends on the nature of the desired effect. In the case of Compound I, it is usually from 0.005 to 0.5 kg / area, preferably from 0.001 to 0.5 kg / area, especially. . 〇〗 to 0.3 kg / area. The application rate of Compound II is usually from 0.1 to 10 kg / acre, preferably 0. This paper size is applicable to the national standard (CNS) A4 secret (210 X 297 male thin). Printing 423958 A7 --------, ____________ B7 Five 'invention description (7) ~ to 5 kg / area, especially 1 to 4 kg / area. The application rate of Compound III is generally from 0.05 to 0.8 kg / area, preferably from 0.01 to 0.5 kg / area ', especially from 0.05 to 0.3 kg / area. For seed treatment, the application rate of the mixture is usually from 0.001 to 100 g / kg of seed, preferably from 0.01 to 50 g / kg of seed, especially from 0.01 to 10 g / kg of seed. If it is desired to control plant pathogenic harmful fungi, before or after planting, or before or after plant germination, spray or spread compound 4III or compounds I, π and 111 mixture.

本發明之殺眞菌協同混合物，或化合物I可調配成例如立即可噴霧之溶液、粉劑及懸浮液態或呈高濃縮水性 '油性或其他懸浮液、分散液、乳液、油分散液、糊膏、粉劑、散佈物質或顆粒，且藉喷霧、霧化、撒粉、撒佈或傾倒方式施用。使用狀態視所欲目的而定；於任何例中，較好以儘可能使本發明混合物分佈之細微且均勻態使用D 調配物可依本身已知方法製備，例如添加溶劑及/或載體。一般於調配物中混合惰性添加劑如乳化劑或分散劑。適宜之界面活性劑爲芳族續酸如木質-、驗-、萬-及二丁基莕-磺酸及脂肪酸之鹼金屬鹽、鹼土金屬鹽及銨鹽，烷基_ 及烷芳基磺酸鹽'烷基月桂基瞇及脂肪醇磺酸鹽，及硫酸化十六烷醇'十七烷眸及十八烷醇之鹽，或脂肪醇二醇謎之鹽，磺酸化萘及其衍生物與甲醛之縮合物，莕或茶續酸與齡·及甲搭之縮合物’聚氧乙締辛基酴酿，乙氧化異辛基_ -10- 本紙張从適财關家料（(：剛44祕（2獻297公釐)一' -- 1.1 — ^------裝------,訂-----^--魂 (請先闖讀背面之注意事項再填寫本頁) 經濟部中央橾準局負工消費合作社印褽 423 958 A7 _______B7 五、發明説明（8 ) 、辛基-或壬基-酚，烷基酚聚二醇醚、三丁基苯基聚二醇醚，烷基芳基聚醚醇，異十三烷醇，脂肪醇/環氧乙烷縮合物，乙氧化蓖麻油，聚氧乙烯烷醚或聚氧丙基烷醚，月桂醇聚二醇醚乙酸酯，山梨糖醇酯，木質亞硫酸鹽廢液或甲基纖維素。撒佈用粉劑材料及粉劑可藉使化合物[、π及/或〗丨〗，或化合物I、II及III之混合物與固體載體混合或—起研磨而製備。顆粒（如包衣顆粒，浸液顆粒或均勻顆粒）一般藉使活性成分結合至固體載體中而製得。填料或固體固體載體爲例如礦土如砂石、梦膠、砂酸鹽、滑石、高嶺土、石灰石、石灰 '白堊、紅玄武土、黃土、黏土、白雲石、矽藻土、硫酸鈣、硫酸鎂'氧化鎂、研磨合成料’及肥料如硫酸銨、磷酸銨、硝酸銨、尿素，及植物來源之產品如穀粉、樹皮粉、木粉及核殼粉、纖維素粉末或其他固體載體。調配物通常包括自0.1至95重量。/。，較好〇.5至90重量％之化合物I、II及/或III，或化合物I、Π&ΙΠ之混合物。活性成分使用純度自90%至100%，較好95%至100。/〇(依據 NMR或HPLC圖譜）。化合物I ' II及/或I π，或混合物，或對應之調配物，係以殺眞菌活性量之混合物、或在分別使用時爲殺眞菌活性量之化合物I，Π及/或III處理有害眞菌或植物、種子、土壤、區域、材料或空間而施用，使其維持無眞菌。受有害本紙張^^:適財關家網L (⑽丨Α4· ( 2!()><297公赛） ----^------餐-------.訂------^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印聚 A7 _____87 ___ 五、發明説明（9 ) 眞菌感染前後均可施用。本發明混合物抗有害眞菌之協同作用實例以下列實驗証明化合物及混合物之殺眞菌作用：活性成分分別或一起調配成含7 〇重量％環己酮、2 〇重量 %Nekanil® LN(Lutensol® AP6,具乳化及分散作用之溼潤劑 ’以乙氧化烷基酚爲主）及丨〇重量。AEmulphor® EL (Emulan® EL，以乙氧化脂肪醇爲主之乳化劑）之混合物之丨〇 %乳液，並以水稀釋得所需濃度。藉測定受感染葉面積百分比而評估。該等百分比轉化成作用程度，使用柯比（Colby,s)程式[R S, Colby，Weeds IX，20-22 (1967)]決定活性成分混合物之預期作用程度並與所觀察之作用程度比較。柯比程式： e = x十y + z X y . z/100 E預期之活性程度，以使用濃度a，b及c之活性成分A ’ B及C之混合物時，與未處理對照组之％表示， x作用程度’以使用濃度a之活性成分A時與未處理對照组之％表示 y作用程度，以使用濃度b之活性成分b時與未處理對照组之％表示 2作用程度，以使用濃度c之活性成分C時與未處理對照組之％表示 ’“、使用如下阿伯特（Abbot's)程式計算效率（E): E = ( 1 - ) 10 0//? α相對於經處理植物受眞菌感染之％，及 --^------，裝-------.訂------威 (請先聞讀背面之注意事項再填寫本頁) -12-The fungicidal synergistic mixture of the present invention, or Compound I can be formulated into, for example, ready-to-spray solutions, powders and suspended liquids or highly concentrated aqueous' oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, Powders, spreading materials or granules, and applied by spraying, atomizing, dusting, spreading or pouring. The state of use depends on the intended purpose; in any case, it is preferred to use the D formulation in as fine and uniform a distribution as possible of the mixture of the invention, which can be prepared according to methods known per se, such as adding a solvent and / or a carrier. Generally, inert additives such as emulsifiers or dispersants are mixed in the formulation. Suitable surfactants are aromatic continuous acids such as the alkali metal salts, alkaline earth metal salts and ammonium salts of wood-, di-, ten-, and dibutylphosphonium-sulfonic acids and fatty acids, alkyl and alkylarylsulfonic acids. Salts 'alkyl lauryl sulfonium and fatty alcohol sulfonates, and sulfated cetyl alcohol' heptadecyl and stearyl alcohol salts, or fatty alcohol diol mystery salts, sulfonated naphthalene and its derivatives Condensate with formaldehyde, 荇 or the condensate of tea acid and aging · and the condensate of phytoethene, polyoxyethylated octyl, ethoxylated isooctyl_ -10- This paper is from Shicaiguan family materials ((: Just 44 Secrets (2 offering 297 mm) a '-1.1 — ^ ------ install ------, order ----- ^-soul (please read the precautions on the back first) (Fill in this page again.) Seal of Consumers' Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs 423 958 A7 _______B7 V. Description of the Invention (8), Octyl- or Nonyl-phenol, Alkylphenol Polyglycol Ether, Tributylbenzene Polyglycol ether, alkylaryl polyether alcohol, isotridecanol, fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropyl alkyl ether, lauryl alcohol Polyglycol ether acetate, sorbitol ester, lignosulfite Acid salt waste liquid or methyl cellulose. Powder materials and powders for spreading can be prepared by compound [, π and / or], or a mixture of compounds I, II and III with a solid carrier or-grinding Granules (such as coated granules, infusion granules, or uniform granules) are generally prepared by incorporating the active ingredients into a solid carrier. Fillers or solid solid carriers are, for example, minerals such as sandstone, dream gum, oxalate, talc , Kaolin, limestone, lime 'chalk, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, abrasive composites, and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea And plant-derived products such as cereal flour, bark flour, wood flour and core-shell flour, cellulose powder, or other solid carriers. Formulations usually include from 0.1 to 95% by weight, preferably 0.5 to 90% by weight. Compounds I, II and / or III, or mixtures of compounds I, II & II. The active ingredient uses a purity from 90% to 100%, preferably 95% to 100% (based on NMR or HPLC spectra). Compound I ' II and / or I π, or mixed , Or the corresponding formulation, is a mixture of bactericidal active amounts, or compounds I, Π, and / or III, which are bactericidal active amounts when used separately, to treat harmful bacillus or plants, seeds, soil, areas, Material or space to keep it free of fungi. Harmful paper ^^: Shicai Guanjia Network L (⑽ 丨 Α4 · (2! () &Gt; < 297 public race) ---- ^- ----- Meal -------. Order ------ ^ (Please read the precautions on the back before filling out this page) Printed by APC Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs, A7 _____87 ___ 5 2. Description of the invention (9) Pleurotus can be applied before and after infection. Examples of the synergistic effect of the mixture of the present invention against harmful bacillus bacteria The bactericidal effect of compounds and mixtures is demonstrated by the following experiments: The active ingredients are formulated separately or together to contain 70% by weight of cyclohexanone and 20% by weight of Nekanil® LN AP6, wetting agent with emulsifying and dispersing effect (mainly ethoxylated alkylphenol) and weight. A mixture of AEmulphor® EL (Emulan® EL, an ethoxylated fatty alcohol-based emulsifier), and diluted with water to the required concentration. Estimated by determining the percentage of infected leaf area. These percentages are converted into the degree of action, using the Colby, s formula [RS, Colby, Weeds IX, 20-22 (1967)] to determine the expected degree of action of the active ingredient mixture and to compare with the observed degree of action. Kirby formula: e = x ten y + z X y. Z / 100 E Expected degree of activity, when using a mixture of active ingredients A 'B and C in concentrations a, b, and c,% of untreated control Indicates that the degree of action x is the degree of action of y when the active ingredient A in the concentration a is used and the untreated control group, and the degree of action is 2 when the concentration of the active ingredient b in the concentration b is used and the untreated control group. The concentration of the active ingredient C in the concentration c and the untreated control group indicates' ", and the efficiency (E) is calculated using the following Abbot's formula: E = (1-) 10 0 //? Α relative to the treated plant % Infected with Pseudomonas spp., And-^ ------, install -------. Order ------ Wei (please read the precautions on the back before filling this page)- 12-

423958 經濟部中央標準局貝工消费合作社印¾ A7 B7 五、發明説明（10 ) 点相對於未處理植物（對照組）受眞菌感染之％〇之作用程度表示經處理植物之感染程度相當於未處理對照組植物之感染程度：100之作用程度表示經處理植物未受感染貫例1 -1 4 抗葡萄生單軸霉（Plasmopara viticola)之活性多種"Milller^Thurgau"之盆載葡萄樹葉子噴佈活性化合物水性製劑，由1 〇 %活性化合物、6 3。/。環己酮及2 7 %乳化劑之原料溶液所製得，噴佈-直至滴溼。爲了可評估物質之長期，噴佈塗膜乾燥後使植物於溫室中放置7天。然後僅對葉子接種葡萄生單軸霉之游走孢子水性懸浮液，葡萄樹先於以水蒸氣飽和之室中在2 4。(：放置4 8小時，接著於2 〇 - 3 0 Ό 溫室中放置5天。接著植物再於高溼度之室中放置16小時，以刺激眞菌長孢子=接著以視覺評估葉底侧受感染程度。表3·· 實例活性化谷物活性化合物' 於嗔体液中之濃度(ppm) 禾處理對照組之作用程度％ : IV 對照组 (99% 〇 (未處理）感染t 2V A=表 1A1 25 74 、，编號1.2 10 5 0 0 3V 表 1A 5 - ------ ，編號1.4 / 4 4V Π 组乃蒲 100 η 50、 η 25 \J 0 5V Hc=iL得湖 100 74 50 —--48 -13- 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐） -----Ml It-I— I I I--11-'訂--u-ll·— I 旅 (請先聞讀背面之注意事項再填寫本頁) 423958 A7423958 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ¾ A7 B7 V. Description of the invention (10) The effect of the point (10) relative to the infection of P. infestans in the untreated plant (control group) 〇 The degree of infection indicates that the treated plant ’s infection is equivalent to Infection degree of untreated control plants: A degree of action of 100 indicates that the treated plants are uninfected. Examples 1 -1 4 Anti-Plasmopara viticola activity Multiple " Milller ^ Thurgau " The leaves are sprayed with an aqueous active compound preparation, consisting of 10% active compound, 63%. /. It is made of cyclohexanone and 27% emulsifier as raw material solution, spraying-until dripping. In order to evaluate the long term of the substance, the spray coating film was dried and the plants were left in the greenhouse for 7 days. The leaves were then inoculated only with an aqueous suspension of the zoospores of the genus Uniaxially grapes, and the vines were placed in a chamber saturated with water vapour at a temperature of 24. (: Let stand for 48 hours, and then put it in a greenhouse of 20-30 Ό for 5 days. Then the plants are placed in a high-humidity room for 16 hours to stimulate the fungus spores = Then visually evaluate the infection of the underside of the leaves Table 3. · Example concentration of activated cereal active compounds in carcass fluid (ppm) Degree of action of the treated control group%: IV control group (99% 〇 (untreated) infection 2V A = Table 1A1 25 74 ， No. 1.2 10 5 0 0 3V Table 1A 5------- ， No. 1.4 / 4 4V Π Group Napu 100 η 50, η 25 \ J 0 5V Hc = iL Dehu 100 74 50 — --48 -13- This paper uses Chinese National Standard (CNS) A4 (210X297 mm) ----- Ml It-I— II I--11-'Order --u-ll · — I Brigade (Please read the notes on the back before filling out this page) 423958 A7

7 B 五、發明説明（11 ) 表4: 經濟部中央標率局員工消贽合作社印製實例 '活性化合物於噴佈液中之濃度(ppm) 觀察之作用程度計算之作用程度η : 6 10A + 100 lib , 100 0 ΐ 7 5A + 50 lib 100 0 3 10A + 50 lib 92 0 9 5Λ + 25 lib 92 0 10 25A + 25 lib 95 74 11 10A r + 100 lie 100 74 12 10A 十 50 lie 100 48 13 ^ 5B + 50 lib .92 74 1Λ 5B 4 50 lie 95 86 ν *以柯比方法計算者本紙張尺度適用中國國家標隼（CNS) A4規格（210X 297公釐） (请先閲讀背面之注意事項再填寫本頁) /! 9 ^ ° 5 〇 ’必42395b A7 B7 五、發明説明（丨2 ) 實例15-33 於蕃莊中抗致病疫霉（Phytophthora infe stans) 之活性各種” GroBe Fleischtomate)之盆栽棱物葉子喷佈水性懸浮液，其係由含1 0 %活性化合物' 6 3 %環己酮及2 7 %乳化劑之原料溶液所製備，喷佈直至滴，澄。隔天，葉子以致病疫霉之游走孢子水性懸浮液感染。接著植物置於1 6 - 1 8 °C之以水蒸氣飽和之室中，6天後，於受感染未處理對照組植物發展出蕃茄枯萎病至可以視覺評估百分比之感染程度。 (請先閲讀背面之注意事項再填寫本頁) 經濟I中央標準局員工消費合作社印装表5: 實例活性化合物活性化合物於噴佈液中之濃度(PPm) 未處理對照組之作用程度％ 15V 對照組 (99% 0 (未處理）感染 16V Β=表 1Α， 20 ' 88 编號1.2「 ,1〇 0 5 0 17V 表 1Α， 100 74 編號1.4 ! 20 1 Π 65 X U 5 65 0 18V Π b=錳乃蒲 100 50 0 〇 25 0 19V nc=免得爛 500 93 本紙張尺度適用中國國家標準（CNS ) Μ規格（210X297公釐） 8593 247 B V. Description of the invention (11) Table 4: Example printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs of the Consumers 'Cooperative Cooperative Society' Concentration of active compound in spray solution (ppm) Observed degree of action Calculated action degree η: 6 10A + 100 lib, 100 0 ΐ 7 5A + 50 lib 100 0 3 10A + 50 lib 92 0 9 5Λ + 25 lib 92 0 10 25A + 25 lib 95 74 11 10A r + 100 lie 100 74 12 10A ten 50 lie 100 48 13 ^ 5B + 50 lib .92 74 1Λ 5B 4 50 lie 95 86 ν * Calculated by Kirby method This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) (Please read the note on the back first Please fill out this page again) /! 9 ^ ° 5 〇'42395b A7 B7 V. Description of the invention (丨 2) Example 15-33 Various activities against Phytophthora infe stans in Fanzhuang "GroBe Fleischtomate ) 'S potted prism leaf spraying aqueous suspension, which is prepared from a raw material solution containing 10% active compound '63% cyclohexanone and 27% emulsifier, spraying until dripping, clear. The next day, The leaves were infected with an aqueous suspension of zoospores of the pathogenic Phytophthora infestans. The plants were then placed at 16-18 ° C In a steam-saturated room, 6 days later, tomato blight developed in infected untreated control plants to a level where the percentage of infection can be visually assessed. (Please read the precautions on the back before filling out this page) Economic I Central Standard Bureau Cooperative Consumer Co-operative Printing Table 5: Example Active Compound Concentration of Active Compounds in Spray Solution (PPm) Degree of Action of Untreated Control Group 15V Control Group (99% 0 (Untreated) Infection 16V Β = Table 1A, 20 '88 No. 1.2 ", 1 0 0 5 0 17V Table 1A, 100 74 No. 1.4! 20 1 Π 65 XU 5 65 0 18V Π b = Manganese 100 50 0 〇 25 0 19V nc = Avoid rotten 500 93 This paper size applies to China National Standard (CNS) M specifications (210X297 mm) 8593 24

7 7 A B 五、發明説明（〗3) 表6 ：經濟部中央標準局貝工消費合作杜印袈實例活性化合物於噴佈液中之濃度(ppnj 觀察之作用笋度 1計算之作用程度(-) 20 10Λ + 100 lib 100 0 21 5A + 50 lib 100 , 0 22 20A + 100 lib 100 \ 86 23 10A + 50 lib 77 0 24 5A -+ 25 lib 77 0 25 5A + 50 lib 100 93 26 10A + 50 lie 100 93 27 10B f + 100 lib 100 65 28 5B + , 50 lib 100 0 29 2 OB + 100 lib 100 65 30 10B + 50 lib 100 65 ' 31 5B + 25 lib 77 0 32 100B + 100 lib 100 β 74 33 5B + 50 lie 100 93 • 16- --7 - - ....... I—1 」ί - - -s I k I n (請先閲讀背面之注意事項再填寫本頁) .1訂丨年本紙張尺度適用中國國家標準（CNS ) Μ規格（210X297公釐） 4 3 9 5 8 A7 B7 五、發明説明（14 實例3 4 _ 4 0 抗葡萄生單軸霉之治癒活性多種"批Uer-Thurgan ”之盆栽葡萄樹葉子接種葡萄生霉之游走孢子水性懸浮液，葡萄樹接著在以水蒸室中在22-24X：放置48小時，接著自該室中移開，且乾^ 後以活性化合物水性製劑喷佈直至滴溼，該製劑係由ι〇% 活性化合物、63%環己酮及27%乳化劑之原料溶液製備。° 喷佈塗膜乾燥後，植物再於20-3(TC溫室中培育5天，植物再於高溼度之氣候式室中-放置16小時以刺激眞菌孢子生成。接著以視覺評估葉子底侧之感染程度。 (請先閲讀背面之注意事項再填寫本頁) 經濟部中夬標準局負工消費合作社印製表7 實例活性化合物活性化合物於噴佈液中之泼度(ppm) ^處理對照組之浩冰租度％ 34V 對照組 (未-處理） (99% 感染） ---------------------- 0 35V 表 1A 25 ----------——-- 19 0 ，编號1.2 12.5 36V B=表 1A ，编號1,4 12.5 · 0 37V ΙΙΙ=Φ私零 25 「90 / 12.5 60 i本 -17- 2IQX297公董 423958 A7 B7 五、發明説明（15 表8 ：實例 38 ' _____ 1 ’活性化合物於-*貪佈峰.肀之濃度(ppm) —-- " - 觀察之作用程度計算之^用_程度〇·*) 25A + 25 III 100 92 39 12,5A + 80 , 60 12.5 III 40 12.5B 80 60 12.5 III \ *以柯比方法計算者。由實例結果証明在所有混合比例下，所觀察之作用程度高於以柯比程式計算得之作用.程度。 . IV. —裝 ^ ^訂 ---旅 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央揉準局員工消費合作社印製 -18 私紙張尺度適用中國固家標準（CNS > A4規格（210X297公着）7 7 AB V. Description of the invention (〖3) Table 6: Concentration of active compounds in the spraying solution of Du Yinyu, an example of shellfish consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs (ppnj observed effect, calculated by the degree of action 1) (- ) 20 10Λ + 100 lib 100 0 21 5A + 50 lib 100, 0 22 20A + 100 lib 100 \ 86 23 10A + 50 lib 77 0 24 5A-+ 25 lib 77 0 25 5A + 50 lib 100 93 26 10A + 50 lie 100 93 27 10B f + 100 lib 100 65 28 5B +, 50 lib 100 0 29 2 OB + 100 lib 100 65 30 10B + 50 lib 100 65 '31 5B + 25 lib 77 0 32 100B + 100 lib 100 β 74 33 5B + 50 lie 100 93 • 16- --7--....... I—1 ”ί---s I k I n (Please read the notes on the back before filling this page) .1 The paper size applies to the Chinese National Standard (CNS) M specification (210X297 mm) 4 3 9 5 8 A7 B7 V. Description of the invention (14 Example 3 4 _ 4 0 Various curative activities against phytohormones) Batch of Uer-Thurgan "potted grape vine leaves were inoculated with an aqueous suspension of the spores of the fungal spores of the grape mold, and the vine was then placed in a steaming room at 22-24X for 48 hours, then Remove from the chamber, and spray with an active compound aqueous formulation until it dries. The formulation is prepared from a raw material solution of 10% active compound, 63% cyclohexanone, and 27% emulsifier. ° Spray After the coating film was dried, the plants were cultivated in a 20-3 ° C greenhouse for 5 days, and the plants were placed in a high-humidity climatic chamber-left for 16 hours to stimulate the fungus spore formation. Then, the degree of infection on the underside of the leaves was visually evaluated (Please read the precautions on the back before filling out this page) Printed by the Ministry of Economic Affairs, Standards Bureau, Consumer Cooperatives, Table 7 Example of the active compound active compound in the spray liquid (ppm) ^ Ice rent% 34V control group (un-treated) (99% infection) ---------------------- 0 35V Table 1A 25 ------ ---------- 19 0, No. 1.2 12.5 36V B = Table 1A, No. 1,4 12.5 · 0 37V ΙΙΙ = ΦPrivate Zero 25 "90 / 12.5 60 i this -17-2 IQX297 public director 423958 A7 B7 V. Description of the invention (15 Table 8: Example 38 '_____ 1' Active compound at-* Greaves peak. Concentration (ppm) --- "-Observation of the degree of action to calculate the _ degree 〇 · *) 25A + 25 III 100 92 39 12,5A + 80, 60 12.5 III 40 12.5B 80 60 12.5 III \ * Calculated by Kirby method. The results of the examples prove that the observed effects are higher than the effects calculated by the Kirby formula at all mixing ratios. IV. —Equipment ^ ^ Order --- Brigade (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs -18 Private paper standards are subject to the Chinese solid standard (CNS > A4 specifications (210X297)

Claims

S 8 8 8 ABCD 8¾. Patent Application Fanyuan 1. A fungicidal mixture, including synergistically active amounts: a) Ether of formula I: ch3 N〇CH3

ZR '(I) The policy of the male workers' consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, where the substituents have the following meanings: X is amine (NH); Y is N; Z is oxygen or sulfur; alkyl; and b) Dithiocarbamates from: • Ethylbis (dithiocarbamate) manganese (zinc complex) (IIa), -Ethylbis (dithiocarbamate) ) Manganese (lib), ethylene bis (dithiocarbamate) zinc ammonium complex (VII) and-ethylene bis (dithiocarbamate) zinc (IId), or c) 1- (2-cyano-2-methoxyimine ethylamido) -3-ethylurea (III): H3CCH2-NHCONH-C (CN) = NOCH3 (III) 〇 2. According to the scope of patent application The fungicidal mixture of item 1 comprising ethylene dibis (dithiocarbamate) manganese (zinc complex) (IIa). 3. The fungicidal mixture according to item 1 of the patent application, including manganese (zinc complex) (IIb) of bis (dithioaminoformate). 4. According to the fungicidal mixture of item 1 of the scope of the patent application, including secondary ethyl bis ------------- (please read "Note on the back side ^ > before filling out this page) Paper size applies to China National Standards (CNS) A4 scale (2 丨〇 X 2M mm) 423958 A8 B8 C8 DS

Printed by the Central Standards Bureau of the Ministry of Economic Affairs and the Industrial Cooperative Cooperative. 6. Scope of Patent Application (Dithioamino Formate) Zinc Sulfate (IIC) ^ 5. The fungicidal mixture according to item 1 of the scope of patent application, including ethylene Zinc bis (dithiocarbamate) (11 d). 6. The fungicidal mixture according to item 1 of the scope of the patent application, including compound u or compound II »7. The fungicidal mixture according to claim 1 of the patent application, wherein the weight ratio of compound u to compound I is 2 0 0 : 1 to 0.1: 1 8. — A method for controlling harmful fungi, comprising treating harmful fungi with a compound of formula I according to item ^ of the scope of the patent application and a compound of formula n or formula III according to item 1 of the scope of the patent application 'Its environment, or treated plants, soil' areas, materials or spaces to keep them fungus-free; wherein the compound of formula I is an oxime ether of the formula: ch3 n〇ch3 z ~ η. '(丨). Wherein the substituent has The following meanings: X is amine (NH); Y is N; Z is oxygen or sulfur; IV is Cu alkyl; the compound of formula II is a dithiocarbamate selected from the group consisting of: Bis (dithiocarbamate) manganese (zinc complex) (IIa), -ethylene bis (dithiocarbamate) manganese (lib), -2- n ^ i -tf-1 in I r [) ^ (Please read the precautions on the back before filling in this page> i Paper Λ New Choi Guan Family Materials (CNS) (2ωχ 297 male thin) 423 95 8 as Β8 C8 DS 6. Scope of patent application-Ethyl bis (dithioaminocarboxylic acid) zinc amino complex (π) and-Ethyl bis (dithioaminocarboxylic acid) Zinc (lid) The compound of formula III is 1- (2-cyano-2-methoxyimine of ethylamidine) -3-ethylurea or H3CCH2-NHCONH-C (CN) = NOCH3. 9. According to the application The method according to item 8 of the patent includes the use of Compound I from 0.005 to 0.5 kg / public enemy. 10. The method according to item 8 of the patent application includes the use of Compound II from 0 "to 10 kg / are. -1 J. I ^^ 1 0---. U ^^^ 1 ^^^ 1 ^^^ 1 an HI — ^ i》 ai (please read the precautions on the back before writing this page) Printed by the Bureau ’s Consumer Cooperatives ^ This paper is a Chinese standard (CNS) M specification (210X297 mm) No. 86105284 patent + Chinese specification page, please order Ml. 4. Abstract of Chinese invention (name of invention) k hi Yuexin Correction Supplement I A fungicidal mixture comprising a synergistically active amount of a) fatty ether of formula I:

(f) where the substituents have the following meanings: X is amine (NH); Y is N; Z is oxygen or sulfur; R 'is Cu alkyl; and (Please read the weeping matters on the back before filling in each page襕) Abstract of the invention in English (Name of the invention: FUNGICIDAL MIXTURES A fungicidal mixture comprising a) an oxime ether of the formula I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs x

where the formulas have the following meaning: {〇is amino (NH); Y is N; Z is oxygen or sulfur; R 'is Ci-Cs-alkvl; and -2-This paper applies the Chinese National Standard (CNS) A4 specification (2) χ 297 mm 4 2 3 yb 〇 86105284 IV. Abstract of Chinese invention < Name of preparation b) Dithioamino formate selected from the following groups:-ethyl bis ( Dithioaminocarboxylic acid) (Zinc complex) (IIa) '-Ethylbis (dithioamino T acid) Photo (11b)'-Ethylbis (dithioamino acid) ) Zinc gas complex (Π) and-ethylene bis (dithiocarbamate) zinc (11 d) 'or c) 1- (2-cyano-2-methoxyimine) of the formula Ethyl) -3-ethylurea (Η1): h3cch2-nhconh-C (cn) = noch3 (ηι) ° (Please read the notes on the back before filling in the columns on this page) ---- * — J Order I -r English Abstract of Invention (Name of the invention: Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs b) a dithiocarbamate (II) selected from the group consisting of -manganese ethylenebis (dithiocarbamate) (zinc complex) (Ha),- m anganese ethylenebis (dithiocarbamate) -zinc ainmoniate ethylenebis (dithiocarbamate) (lie) and -2inc ethylenebis (dithiocarbamate) (lid) 〇rc) 1 ~ (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (工工 I) H3CCH2- NHCONH'C (CN) = NOCH3 (III) in a synergistically active amount. -2b-This paper size is applicable to the national standard (CNS) M specification (210 X 297 cm) Line I

ZR '(I) The policy of the male workers' consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, where the substituents have the following meanings: X is amine (NH); Y is N; Z is oxygen or sulfur; alkyl; and b) Dithiocarbamates from: • Ethylbis (dithiocarbamate) manganese (zinc complex) (IIa), -Ethylbis (dithiocarbamate) ) Manganese (lib), ethylene bis (dithiocarbamate) zinc ammonium complex (VII) and-ethylene bis (dithiocarbamate) zinc (IId), or c) 1- (2-cyano-2-methoxyimine ethylamido) -3-ethylurea (III): H3CCH2-NHCONH-C (CN) = NOCH3 (III) 〇 2. According to the scope of patent application The fungicidal mixture of item 1 comprising ethylene dibis (dithiocarbamate) manganese (zinc complex) (IIa). 3. The fungicidal mixture according to item 1 of the patent application, including manganese (zinc complex) (IIb) of bis (dithioaminoformate). 4. According to the fungicidal mixture of item 1 of the scope of the patent application, including secondary ethyl bis ------------- (please read "Note on the back side ^ > before filling out this page) Paper size applies to China National Standards (CNS) A4 scale (2 丨〇 X 2M mm)