TW200845902A - Composition for controlling external parasites and method therefor - Google Patents
Composition for controlling external parasites and method therefor Download PDFInfo
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200845902 / 九、發明說明: 【發明所屬之技術領域】 本發明乃有關外部寄生蟲驅除劑組成物及外部寄生蟲 驅除方法。更詳言之,本發明乃關於增強光安定性之動2 用外部寄生蟲驅除劑組成物及使用該組成物之外部寄生蟲 驅除方法。 【先前技術】 长乙蟎唑((RS)-5·第三丁基-2-[2-(2,6-二氟苯基)_4,5_二 _虱-1,3-喔唾_4_基]苯乙⑽)已知可供殺蟲·殺蜗劑用途(表昭 。日本專利第3刪u號;專利文獻」及日本專利第Μ747” 唬,專利文獻2),另外,提供動物之外部寄生蟲及單食性 蟎之防除劑用途(參照日本專利特表2〇〇〇_5〇丨695號公報; 專利文獻3)的噁唑啉化合物。然而,σ惡唑啉化合物在戶外 使用時’因其光安定性不足’故光安定劑的選擇成為重要 事項。 § 曰本專利特開平9_59115號公報(專利文獻4)中,雖提 f賦:噪㈣化合物光安定性,並記載有將氛基丙稀酸醋 系、本亚二峻系或二苯曱酮系紫外光吸收劑單獨使用或併 用而亦热法充分獲得光安定性乃屬實情。 一另外,也有併用2,2’,4,4’-四羥基二苯曱酮及2,6_二第 二丁基-4_(4,6-雙(辛硫*H,3,5_三哄_2_基胺基)紛之光安 疋化之方法(麥照日本專利特開2002」146〇4號公報;專利 文獻5),^,此係有關抑制除蟲菊精劑之分解者,並未 述及有關。惡唾琳系化合物。另外,併用該系統之紫外光吸 319273 5 200845902 :d及抗氧化劑遇是無法充分抑制農藥有效成分之光分 解^夕半僅可仔加成效果,據說有時還發生枯抗作用而降 低其效果。 曰本專利第3189011號說明書。 曰本專利第3574785號說明書。 曰本專利特表2000-501695號公報。 曰本專利特開平9-59115號公報。 曰本專利特開2002-114604號公報。 專利文獻1 專利文獻2 專利文獻3 專利文獻4 專利文獻5 【發明内容】 (發明擬解決之課題) 本發明之目的在提供光安定優異之動物之 ^生 驅除劑組成物及使用該組成物 * 了 * (解決課題之方法) M可生蟲驅除方法。 本發明研究者就乙端哇之光安定性專心致结 果,發現乙蟎唑以紫外光吸收劑尸' 九、口 之組成物可顯亍弁容1 “⑽糸抗乳化劑組合而成 丨 J頌不先文疋性之相乘作用效果。更咩丄夕7 蟎唑併用1種以上之紫外光吸收劑及i種以丨…之’ _時顯示較分別單獨使用時所沒有之對 :之:,安定化效果, 解。又,發現並無損及對於外部寄 之光刀 高殘效性而完成本發明。蛛之效果,且顯示其 即,本發明係下述外部寄生蟲驅除此 組成物之外部寄生蟲驅除方法之發明/、、成使用該 319273 6 200845902 '乙料:=之:卜部寄生蟲驅除劑組秦 2成分,並含有紫外光吸收細系抗氧, 2.丽述1所却番 f 丁、机乳化劑0 紫外光吸收劑係選生蟲驅除劑組成物,其中, 上為特徵·· ”擇自下列化合物並使用其1種或2種以 般式(1)所子-乂 ^ / 下一本甲酮系化合物, R3200845902 / IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to an external parasite repellent composition and an external parasite repelling method. More specifically, the present invention relates to an external parasite repellent composition for enhancing light stability and an external parasite repelling method using the same. [Prior Art] Long-ethyloxazole ((RS)-5·t-butyl-2-[2-(2,6-difluorophenyl)_4,5_di-虱-1,3-喔Sal] 4_yl]phenethyl (10)) is known to be useful for insecticidal and smoldering agents (Table Illustrated. Japanese Patent No. 3, No. 5; Patent Document) and Japanese Patent No. Μ 747 唬, Patent Document 2), in addition, Use of an external parasite of an animal and a control agent for a single-feeding cockroach (refer to Japanese Patent Publication No. 2〇〇〇5〇丨695; Patent Document 3). However, the σ oxazoline compound is outdoors. In the case of use, the selection of the light stabilizer is important because of the lack of light stability. § In the patent publication No. 9_59115 (Patent Document 4), the optical stability of the compound is described. It is true that the ultraviolet acrylate vinegar, the benzoic acid sulfonate or the benzophenone ketone ultraviolet light absorber can be used alone or in combination, and the light stability is also fully obtained by thermal method. In addition, there are also 2, 2 in combination. ',4,4'-Tetrahydroxydiphenyl fluorenone and 2,6_di-second butyl-4_(4,6-bis(octyl sulphide*H,3,5-trioxan-2-ylamino) The method of smashing the light Japanese Patent Laid-Open Publication No. 2002-146/4; Patent Document 5), which relates to the inhibition of the decomposition of pyrethroid extract, is not related to the sputum-based compound. In addition, the system is used in combination. UV light absorption 319273 5 200845902 :d and anti-oxidant can not fully inhibit the photolysis of the active ingredients of pesticides. The half-only effect can be added. It is said that sometimes the anti-effect is also reduced to reduce the effect. 曰本专利第389011 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Patent Document 3 Patent Document 4 Patent Document 5 [Problem to be Solved by the Invention] An object of the present invention is to provide a composition of an animal repellent excellent in light stability and use of the composition* (Solution of the problem) Method) M can be used for insect repellent method. The researcher of the present invention focused on the stability of the light of B-side wow, and found that the carbazole was absorbed by the ultraviolet light absorber. "(10) 糸 糸 糸 糸 组合 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 颂 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 Compared with the single use: the stability effect, the solution, and the discovery and non-destructive and the high residual effect of the external light knife to complete the invention. The effect of the spider, and it is shown that the present invention is The invention of the external parasite repelling method for repelling the composition by the following external parasites, and the use of the 319273 6 200845902 'b material:=: the parasite parasitic repellent group Qin 2 component, and containing ultraviolet light absorption fine system Antioxidant, 2. Lishen 1 is not only, machine emulsifier 0 ultraviolet light absorber is selected from the insect repellent composition, wherein, the above is characterized by "selected from the following compounds and used one or two The general formula (1) - 乂 ^ / the next ketone compound, R3
(I) (式中,R1示氫原子、碳數為丨至12之具直鏈或分 键之烷基、苯m式⑴所示之基, •(CH2)4-Ο(I) (wherein R1 represents a hydrogen atom, a linear or branched alkyl group having a carbon number of 丨 to 12, a benzene group (1), and (CH2)4-Ο
⑴ R2示氫原基、續酸基或式(2)所示之基, H3C0(1) R2 represents a hydrogen primordium, a repeating acid group or a group represented by the formula (2), H3C0
(2) R3不氫原子或羥基,R4示氫原子、羥基或曱氧基, 一般式(II)所示氰基丙烯酸酯系化合物, 7 319273 200845902 σ' 、COORe (Π) 我分枝鏈之烷基。) (式中’ R1 2示碳數為1至8之具直鍵 一般式(ΙΠ)所示苯並三唑系化合物, HO R3(2) R3 is not a hydrogen atom or a hydroxyl group, R4 is a hydrogen atom, a hydroxyl group or a decyloxy group, and a cyanoacrylate compound represented by the general formula (II), 7 319273 200845902 σ', COORe (Π) I branch chain alkyl. (wherein R 1 2 represents a straight bond having a carbon number of 1 to 8; a benzotriazole compound represented by the general formula (ΙΠ), HO R3
(III) R9 (式中,R3示氫原子、碳數為、至 鏈之烧基、α,α,··^甲基苯甲基,或式(3)=具直鏈或分枝 〇 W -C-N H2、C II 〇 示之基 (3) 或式(4)所示之基,(III) R9 (wherein R3 represents a hydrogen atom, a carbon number, a burnt group to a chain, an α,α,··^methylbenzyl group, or a formula (3)=having a straight chain or a branching group W -CN H2, C II shows the base shown by (3) or (4),
319273 8 1 2 R4示氫原子或辛驗,R8錢原K數為 3 具直鏈或分枝鏈之烧基、甲氧基、α,α,_二甲 4 曱基丙烯醯氧基,R9示氫原子或氯原子), 土 200845902 :般式Μ所示水揚酸系化合物,319273 8 1 2 R4 represents a hydrogen atom or a succinct test. R8 is a linear or branched chain alkyl, methoxy, α,α, dimethyl dimethyl decyl propylene oxy group, R9 Hydrogen atom or chlorine atom), soil 200845902: a salicylic acid compound represented by the general formula
(IV) C-0 II 0 氧原子,或碳數為1至8之具直鏈或分 (式中,R10 枝鏈之烷基)。 3上述丨項所記载之外部寄 南且成 中,酚系抗氧化劑係潠摆ήπ+、 丨示y組成物,其 物以及下列⑴至(13) έ 幻種* 2種以卜乂或多酚系化合物中,使用 八禋^種从上之化合物為特徵··(IV) C-0 II 0 Oxygen atom, or a linear or branched carbon number of 1 to 8 (wherein the alkyl group of the R10 chain). (3) The phenolic antioxidants contained in the above-mentioned items are ή + ή 、 、 、 、 、 、 、 、 、 , , , , y y y y y y y y y y y y y y y y y y y y y y y y y y y y y In the polyphenol-based compound, the compound from the top is used as a feature.
(V) (式中,R11示氫原子、異丙基、氯甲基、第三丁基、 _苯甲基、4-曱基苯曱基或甲基丙烯酸酯基,Rl2示氫原子或 第二丁基,R13示氫原子、曱基、乙基、甲氧基、異辛基 丙酸酯基或硬脂基丙酸酯基,R14示氫原子或曱基,Rl5示 氫原子或碳數為1至5之具直鏈或分枝鏈之烧基), (1) 2,2’_亞曱基雙(4-曱基-6-第三丁基酚), (2) 2,2、亞曱基雙(4_乙基-6-第三丁基酚), (3) 4,4’-硫基雙(3-曱基-6-第三丁基酚), (4) 4,4,·亞丁基雙(3-曱基-6-第三丁基酚), 9 319273 200845902 " (5)3,9-雙[1,1·二甲基 -(3-第三丁基-4-羥基-5-甲 本基)丙氧基]乙基]_2,4,8,四σ惡螺[5,5]十一烧, (6) 2,2-硫基二乙烯基雙[3-(3,5-二第三丁基_4_羥基苯 基)丙酸酯], (7) 三乙二醇雙[3-(3-第三丁基-4-羥基-5-甲苯基)丙酸 酯], (8) 1,6-己二醇雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸 酯], ♦ (9)1,1,3·三(2_曱基羥基_5_第三丁基苯基)丁烷, (10)1,3,5-三甲基-2,4,6-三(3,5-二第三丁基_4·羥基苯 甲基)苯, (U)四[亞曱基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯] 曱烷, (12) 二(3,5-二第二丁基-4-羥基苯甲基)異氰尿酸酯,或 (13) 雙[3,3^雙·(4’_羥基_3,_第三丁基苯基)丁酸]乙二 醇酯。 4·上述1至3中任一項所記載之外部寄生蟲驅除劑組 成物,其中,乙螨唑、紫外光吸收劑及酚系抗氧化劑之間 之調配比率,以質量比計,係i : 〇 〇5至5 : 〇.〇5 : 5。 5·—種外部寄生蟲驅除方法,其特徵為使用上述丨至 4中任一項之外部寄生蟲驅除劑組成物。 (發明之效果) 本發明之動物之外部寄生蟲驅除劑組成物,藉由 成分之紫外光吸收劑㈣系抗氧化劑間之相乘性光安定化 319273 10 200845902 效果,可頒著抑制有效成分之乙蟎唑之·光分解。又,併用 糸外光吸收劑及酚系抗氧化劑,對於外部寄生蟲之驅除效 果也不受影響。目此,該組成物併用於動物,可使有效成 部寄生蟲驅除效果得以長期間持續,且殘效性也顯 著提,扣別疋在戶外等陽光下使用時,其效果更為顯著, 做為動物之外部寄生蟲驅除劑極為有用。 、、 【實施方式】 (實施發明之最佳形態) •本發明之外部寄生蟲驅除劑組成物m坐為有效 成分,且含有紫外光吸收劑及i系抗氧化劑做為光安定劑。 、該紫外光吸收劑宜使用選自下列化合物之^重或^種 一般式(I)所示二苯甲酮系化合物;(V) (wherein R11 represents a hydrogen atom, an isopropyl group, a chloromethyl group, a tert-butyl group, a benzyl group, a 4-mercaptophenyl fluorenyl group or a methacrylate group, and R12 represents a hydrogen atom or a Dibutyl, R13 represents a hydrogen atom, a mercapto group, an ethyl group, a methoxy group, an isooctylpropionate group or a stearyl propionate group, R14 represents a hydrogen atom or a fluorenyl group, and Rl5 represents a hydrogen atom or a carbon number. a linear or branched chain of 1 to 5, (1) 2,2'-arylene di(4-mercapto-6-tert-butylphenol), (2) 2,2 , anthracenyl bis(4_ethyl-6-tert-butylphenol), (3) 4,4'-thiobis(3-mercapto-6-tert-butylphenol), (4) 4 ,4,·Butylene bis(3-indolyl-6-t-butylphenol), 9 319273 200845902 " (5) 3,9-bis[1,1·dimethyl-(3-third 4--4-hydroxy-5-methylphenyl)propoxy]ethyl]_2,4,8, tetrasigmine snail [5,5] eleven, (6) 2,2-thiodivinyl Bis[3-(3,5-di-t-butyl-4-yl-hydroxyphenyl)propionate], (7) triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5) -tolyl)propionate], (8) 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], ♦ (9)1 ,1 3·3(2_fluorenylhydroxy_5_t-butylphenyl)butane, (10) 1,3,5-trimethyl-2,4,6-tris (3,5-di third Butyl-4(hydroxybenzyl)benzene, (U)tetrakis[-indenyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] decane, (12) Bis(3,5-di-dibutyl-4-hydroxybenzyl)isocyanurate, or (13)bis[3,3^bis·(4'-hydroxy-3,_t-butyl) Phenyl) butyrate] ethylene glycol ester. 4. The composition of the external parasite repellent according to any one of the above 1 to 3, wherein the ratio of the ratio of the oxazole, the ultraviolet light absorber, and the phenolic antioxidant is expressed by mass ratio: 〇〇5 to 5: 〇.〇5: 5. An external parasite repelling method characterized by using the external parasite repellent composition according to any one of the above items. (Effect of the Invention) The composition of the external parasite repellent of the animal of the present invention can be inhibited by the effect of the synergistic light stabilization of 319273 10 200845902 by the ultraviolet light absorber (IV) of the component. The decomposition of acetylcarbazole. Further, the external light absorber and the phenolic antioxidant are used together, and the effect of external parasites is not affected. Therefore, the composition is used in an animal, and the effective parasitic repellency effect can be sustained for a long period of time, and the residual effect is also remarkably improved, and the effect is more remarkable when the shackle is used outdoors in sunlight or the like. Animal external parasite repellents are extremely useful. (Embodiment) (Best Mode for Carrying Out the Invention) The external parasite repellent composition m of the present invention is an active ingredient and contains an ultraviolet light absorber and an i-type antioxidant as a photostabilizer. Preferably, the ultraviolet light absorbing agent is selected from the following compounds: a benzophenone compound represented by the general formula (I);
一般式(II)所示氰基丙烯酸酯系化合物;a cyanoacrylate compound of the general formula (II);
一般式(III)所示苯並三唾系化合物; 319273 11 200845902 HO r6a benzotrisal compound represented by the general formula (III); 319273 11 200845902 HO r6
(HI)(HI)
或一般式(IV)所示水揚酸系化合物 OHOr the general formula (IV) of the salicylic acid compound OH
(IV) r°O-Rl 該驗系抗氧化劑宜使用選自一般式(干單备 合物及雙驗系化合物或多I系化合物 二:早齡糸化 之化合物。 必1種或2種以上 13 .(IV) r°O-Rl The antioxidant of the test system is preferably selected from the general formula (dry single compound and double test compound or multi-type compound 2: early age chemical compound. 1 or 2 Above 13 .
(V) 本發明中,宜併用:ι種或2種以上自上述 k酮系化合物(I)、萄其石π * ►π人此/ Λ基丙烯酸酯系化合物(II)、苯並二唑 化合物(III)及水楊酿备 種或2種以上、璧白 (IV)之紫外光吸收劑,以及 1 ^舱糸介入4 ^上述單酚系化合物(V)及雙酚系化合 紫外光吸收劑中, 令,示氫原子、、户f二又式(1)所示二苯"同系化心 A , ^ ^ A A數為1至12之具直鏈或分枝鏈之;) 基本甲基或式(υ所示之基 319273 12 200845902 (CH2)4—Ο(V) In the present invention, it is preferred to use one or more kinds of the above-mentioned k-ketone compound (I), the stone π* ►π human/mercapto acrylate compound (II), benzobisazole Compound (III) and water-sucking seed or two or more kinds of white light (IV) ultraviolet light absorber, and 1 ^ cabin intervening 4 ^ the above monophenolic compound (V) and bisphenol-based ultraviolet light absorption In the agent, the hydrogen atom, the diphenyl group represented by the formula (1), and the homologous heart A, ^ ^ AA number of 1 to 12 have a straight or branched chain; Base or formula (υ 319 319273 12 200845902 (CH2) 4—Ο
R2示氫原子、磺酸基,或式(2)所示之基,R2 represents a hydrogen atom, a sulfonic acid group, or a group represented by the formula (2),
R3示氫原子或羥基, 又’ R4示氫原子、羥基或曱氧基。 上述一般式(II)所示氰基丙烯酸酯系化合物中,R5示 厌數為1至8之具直鏈或分枝鏈之烧基。 上述一般式(III)所示苯並三唑系化合物中,R6示氫原 子、灰數為1至5之具直鏈或分枝鏈之烷基、α,α,-二曱 基笨甲基,式(3)所示之基,R3 represents a hydrogen atom or a hydroxyl group, and R4 represents a hydrogen atom, a hydroxyl group or a decyloxy group. In the above cyanoacrylate compound represented by the general formula (II), R5 represents a linear or branched chain alkyl group having an anisotropy of from 1 to 8. In the benzotriazole compound represented by the above formula (III), R6 represents a hydrogen atom, a linear or branched alkyl group having a ash number of 1 to 5, and an α,α,-dimercaptomethyl group. , the base shown in formula (3),
13 319273 (4) 20084590213 319273 (4) 200845902
OHOH
ch3 R7不氫原子或辛氧基,R8示氫原子,炉 具直鏈或分枝鏈之料、甲氧基、 :^至8之 •甲基丙婦酿氧基,R9示氯原子或氯原子。’Ch3 R7 is not a hydrogen atom or an octyloxy group, R8 represents a hydrogen atom, a linear or branched chain material of a stove, a methoxy group, a methyl methoxy group of: - 8 to 8, a chlorine atom or a chlorine atom atom. ’
上述-般式(iv)所示水揚酸系化合物中,r1〇 或碳㈣1至8之具直鏈或分枝鏈H 由^系抗氧化劑中,上述一般式(v)所示單紛系化合物 中不氫原子、異丙基、氯甲基、第三丁基、苯曱基、 4-曱基,甲,、或甲基丙稀酸酯基,Rl2示氫原子或第三丁 基’R13示氫原子、甲基、乙基、ψ氧基、異辛基丙酸酿 基或硬脂基丙酸酯基,Ri4示氫原子或曱基,r]5示氫原子 或碳數為1至5之具直鏈或分枝鏈之烷基。 上述雙驗系化合物或多盼系化合物之具體例如下: (1) 2,2’_亞甲基雙(4_曱基-6_第三丁基酚), (2) 2,2’·亞甲基雙(4-乙基-6-第三丁基酚), (3) 4,4’_硫基雙(3-甲基_6-第三丁基酚), (4) 4,4’_亞丁基雙(3_曱基-6-第三丁基酚), (5)3,9-雙[1,1_一 曱基_2-[/5 -(3-第三丁基-4-經基-5 -甲 苯基)丙醯氧基]乙基]-2,4,8,10-四喔螺[5,5]十一烷, 14 319273 200845902 - (6)2,2-硫基二乙烯基雙[3_(3,5_二第三丁基-4·羥基苯 基)丙酸酯], (7) 三乙二醇雙[3-(3-第三丁基-4-羥基-5-甲苯基)丙酸 酯], (8) 1,6-己二醇雙[3_(3,5_二第三丁基·4_羥基苯基)丙酸 酯], (9) 1,1,3-二(2 -曱基-4-¾ 基-5-弟二丁 基苯基)丁燒’ (10) 1,3,5-三曱基-2,4,6-三(3,5-二第三丁基-4-羥基苯 •曱基)苯, (11) 四-[亞曱基-3-(3,5-二第三丁基-4_羥基苯基)丙酸 酯]曱燒, (12) 三(3,5-二第三丁基-4-羥基苯甲基)異氰尿酸酯,或 (13) 雙[3,3’_雙-(4,-羥基-3’-第三丁基苯基)丁酸]乙二 醇酯等' 紫外光吸收劑之具體化合物如下: 二苯甲酮系化合物: 化合物1 : 2,4-二羥基二苯甲酮, 化合物2 : 2-羥基·4-曱氧基二苯曱酮, 化合物3 : 2-羥基-4-辛氧基二苯曱酮, 化合物4 : 2-羥基胃4-十二烷氧基二苯甲酮, 化合物5 : 2,2、二羥基-4-曱氧基二苯甲酮, 化合物6 : 2,2,-二羥基-4,4’-二曱氧基二苯曱酮, 化合物7 : 2-羥基-4-曱氧基二苯曱酮-5-磺酸· 3水合物, 化合物8 : 4-苯甲氧基-2-羥基二苯曱酮, 15 319273 200845902 , 化合物9 : 2,2’4,4、四羥基二苯曱酮,· 化合物10 : 1,4-雙(4-苯曱醯基-3-羥基苯氧基)丁烷, 化合物11 :雙(2-甲氧基-4-羥基-5-苯甲醯基苯基)曱烷。 氰基丙烯酸酯系化合物: 化合物12 : 2-乙基己基-2-氰基-3,3,-二苯基丙烯酸酯, 化合物13 ·乙基-2-氧基-3,3’-二苯基丙稀酸醋, 苯並三嗤系化合物: 化合物14 ·· 2_(2_羥基-5-曱苯基)-2H-苯並三唑, _化合物15 : 2-(2-經基-5-第三丁基苯基)-2H-苯並三。坐, 化合物16:2-(2-羥基-3,5-二第三丁基苯基pH-苯並三唑, 化合物17 : 5-氯-2-(2•羥基-3-第三丁基_5_甲苯基)-2H-苯並 σ坐, 化合物18 : 5-氯-2-(2-羥基-3,5-二第三丁基苯基)-2Η-苯並 —一 , 化合物19 : 2-(2-羥基-3,5-二第三戊基苯基)_2H-苯並三唑, •化合物20 · 2-(2H-苯並三嗤_2'基)_4_曱基冬(ίο四氫 敌酸亞胺基甲基)紛, 化合物21 · 2,2’-亞甲基雙-[4_(ΐ,ι,3,3·四甲基丁基)-6_(2U-本並二嗤-2 -基)驗], 化合物22 : 2-(2-羥基-4-辛氧基苯基)_2H-苯並三唑, 化合物23 : 2-(2-羥基-5-第三辛基苯基)-2Η-苯並三唑, 化合物24 · 2-(2·羥基-5-曱基丙烯醯氧基苯基)-2Η_苯並三 tr坐 5 319273 16 200845902 :化合物25.2-[2-羥基-3,5-雙(〇:,“_二曱基苯甲基)苯 基]_2H-苯並三唑。 水揚酸系化合物·· 化合物26:苯基水揚酸酯, 化合物27 :對-第三丁基苯基水揚酸酯, 化合物28 :對-辛基苯基水楊酸酯。 其中,以化合物2之2-羥基-4-曱氧基二苯甲酮為較佳。 酚系抗氧化劑之例如下列化合物: _化合物A : 2-異丙基_5_甲基酚(另名為百里香酚), 化合物B : 2,6-二異丙基-4-曱基酚, 化合物C · 2-本曱基-4,6-二曱基驗, 化合物D : 2-氯曱基-4,6-二曱基紛, 化合物E : 2-(4-曱基苯曱基)-4,6-二曱基酚, 化合物F:甲基-3-(2-羥基_5_曱氧基苯基)丙烯酸酯, 化合物G ·甲基- 3-(2-經基-3,5-二曱基苯基)丙稀酸酯, _化合物H:甲基·3-(2-羥基-3-第三丁基-5-曱氧基苯基)丙烯 ,酸酯, 化合物I : 2,6_二第三丁基-4-曱基酚, 化合物J : 2,6-二第三丁基-4-乙基酚, 化合物Κ: 2-第三丁基-4-曱氧基酚及3-第三丁基-4-曱氧基 紛之混合物, 化合物L:硬脂基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯, 化合物Μ·兴辛基-3-(3,5-二第三丁基-4-备基苯基)丙酸酯, 化合物N : 亞曱基雙(4-甲基-6-第三丁基酚), 17 319273 200845902 化合物Ο · 2,2 -亞曱基雙(4-乙基-6-第三丁基盼)、, 化合物Ρ : 4,4,_硫基雙(3-曱基-6-第三丁基酚), 化合物Q : 4、4、亞丁基雙(3-曱基-6-第三丁基酚), 化合物R: 3,9-雙[1,1_二曱基_2-[召-(3-第三丁基-4-羥基-5-甲苯基)丙醯氧基]乙基]-2,4,8,10-四噁螺[5,5]十一烷, 化合物S : 2,2-硫基二乙烯基雙[3-(3,5_二第三丁基經基 苯基)丙酸酯], 化合物τ : 1,1,3-三(2-甲基-4-羥基_5_第三丁基苯基)丁烷, _化合物U: 1,3,5-三曱基-2,4,6-三(3,5-二第三丁基_4_羥基苯 曱基)苯, 化合物V:四_[亞曱基-3_(3,5_二第三丁基·4•羥基苯基)丙酸 酯]甲烷, 化合物W:三乙二醇雙[3-(3_第三丁基羥基甲苯基) 丙酸酯], 化合物X.二(3,5-二第三丁基-4-羥基苯曱基)異氰尿酸酯, φ化合物Y: 1,6-己二醇雙[3_(3,5_二第三丁基冬羥基笨基) 丙酸酯], 化合物Ζ:雙[^…經基仏第王丁基苯基仃酸化二 醇酯。 其中,以化合物I之2,6 -二第三丁基_ 4 甲基驗為較佳。 纟發明中,㈣哇、紫外光吸收劑及❹抗氧化. 調配比率以質量比率計,一般為1: 〇〇5至5: 〇〇5至5, 其中,以1 : 0.1至1 : (U至i為較佳,以1 : 〇a至Β . 0.1至0.5為更佳。當紫外光吸收劑或㈣抗氧化劑之任意 319273 18 200845902 :之調配比率過小,就難以得到經由併用而產生之光安定化 之相乘效果,當二者之調配量皆少時,則無法獲得充分之 光安定化效果。相反地,當紫外光吸收劑及/或驗系抗氧化 劑過多時,則無經濟性。 又,·紫外光吸收劑及酚系抗氧化劑之調配比率以質量 比計,宜為广㈣至⑽,其中,以1:〇.〇5至2〇較佳, 以1 : 0.1至10更佳,最佳為1:〇2至5。 本發明之外部寄生蟲驅除劑組成物含有乙蟠唑及化人 物(1)至(28)之i種以上為佳,以及含有化合物(八)至 ^ 種以上為佳。 外部寄生蟲驅除劑組成物之適用對象之動物,呈體例 如牛、絲羊、山羊、雞等之家畜,狗、猫等之小動物等。 外部寄生蟲驅除劑組成物之投與方法,例如直接投 與,或製成適當製劑形態以經皮投與於動物身上,以= 型製品投與,或施用在環境中。經皮投與藉由例如浸潰、 L霧:洗!;灌注(ρ·°η)、塗佈、點滴或撒粉而 丁 ’、 以灌,主、點滴為較佳。藉成型f厂口;^ I在‘ 藉由細片、板片、帶、耳標―)等而進 =境=由撒粉、撒粒、散佈、噴霧、壤蒸或塗:等 進仃,其中,以散佈、喷霧為較佳。 *適當製劑形態,就成型製品而言,例如細片 標等。另外,添加液體載劑、固體载劑或輔劑等, 油劑、軟貧劑、凝膠劑、乳劑、懸浮 、 ^ 水中油型乳化 319273 19 200845902 厂ί制=中水型乳化劑、水合齊卜顆粒水合齊卜粉劍或粒劑In the salicylic acid-based compound represented by the above formula (iv), the linear or branched chain H of the r1〇 or carbon (4) 1 to 8 is a compound of the above formula (v). The compound is not a hydrogen atom, an isopropyl group, a chloromethyl group, a tert-butyl group, a benzoinyl group, a 4-fluorenyl group, a methyl group, or a methyl acrylate group, and R12 represents a hydrogen atom or a tert-butyl group. R13 represents a hydrogen atom, a methyl group, an ethyl group, a decyloxy group, an isooctylpropionic acid aryl group or a stearyl propionate group, and Ri4 represents a hydrogen atom or a fluorenyl group, and r]5 represents a hydrogen atom or a carbon number of 1 A linear or branched alkyl group of up to 5. Specific examples of the above-mentioned double-test compound or poly-try compound are as follows: (1) 2,2'-methylenebis(4-fluorenyl-6_t-butylphenol), (2) 2,2'· Methylene bis(4-ethyl-6-tert-butylphenol), (3) 4,4'-thiobis(3-methyl-6-t-butylphenol), (4) 4, 4'-butylidene bis(3_mercapto-6-tert-butylphenol), (5)3,9-bis[1,1_-indenyl_2-[/5-(3-t-butyl) 4--4-yl-5-tolyl)propanooxy]ethyl]-2,4,8,10-tetraspiro[5,5]undecane, 14 319273 200845902 - (6)2, 2-thiodivinylbis[3_(3,5-di-t-butyl-4-hydroxyphenyl)propionate], (7) triethylene glycol bis[3-(3-t-butyl) -4-hydroxy-5-tolylpropionate], (8) 1,6-hexanediol bis[3_(3,5-di-t-butyl-4-ylhydroxyphenyl)propionate], (9) 1,1,3-bis(2-indolyl-4-ylyl-5-dibutylphenyl)butane-(10) 1,3,5-trimethyl-2,4, 6-tris(3,5-di-t-butyl-4-hydroxyphenylindenyl)benzene, (11) tetra-[indenyl-3-(3,5-di-t-butyl-4-hydroxyl) Phenyl)propionate]曱, (12) Tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanuric acid , or (13) bis [3,3'-bis-(4,-hydroxy-3'-t-butylphenyl)butanoic acid] ethylene glycol ester, etc. The specific compounds of the ultraviolet light absorber are as follows: Methyl ketone compound: Compound 1: 2,4-dihydroxybenzophenone, compound 2: 2-hydroxy-4-indolyldibenzophenone, compound 3: 2-hydroxy-4-octyloxydiphenyl Anthrone, Compound 4: 2-Hydroxygastrid 4-dodecyloxybenzophenone, Compound 5: 2,2, Dihydroxy-4-decyloxybenzophenone, Compound 6: 2,2,- Dihydroxy-4,4'-didecyloxybenzophenone, compound 7: 2-hydroxy-4-decyloxybenzophenone-5-sulfonic acid·3 hydrate, compound 8: 4-benzoic acid Oxy-2-hydroxybenzophenone, 15 319273 200845902 , compound 9 : 2,2'4,4, tetrahydroxydibenzophenone, · compound 10 : 1,4-bis(4-benzoinyl- 3-Hydroxyphenoxy)butane, compound 11: bis(2-methoxy-4-hydroxy-5-benzomercaptophenyl)decane. Cyanoacrylate compound: Compound 12: 2-ethylhexyl-2-cyano-3,3,-diphenylacrylate, compound 13 ·Ethyl-2-oxy-3,3'-diphenyl Acrylic acid vinegar, benzotriazine compound: compound 14 ·· 2_(2_hydroxy-5-fluorenylphenyl)-2H-benzotriazole, _compound 15 : 2-(2-amino-5 -T-butylphenyl)-2H-benzotrien. Sit, Compound 16: 2-(2-hydroxy-3,5-di-tert-butylphenyl pH-benzotriazole, Compound 17: 5-Chloro-2-(2•hydroxy-3-t-butyl) _5_tolyl)-2H-benzo sine, compound 18: 5-chloro-2-(2-hydroxy-3,5-di-t-butylphenyl)-2 fluorene-benzo-one, compound 19 : 2-(2-hydroxy-3,5-di-t-pentylphenyl)_2H-benzotriazole, •Compound 20 · 2-(2H-benzotrisin-2-yl)_4_fluorenyl winter (ίο tetrahydrofuranylidene iminomethyl), compound 21 · 2,2'-methylenebis-[4_(ΐ,ι,3,3·tetramethylbutyl)-6_(2U-ben And 嗤-2 -yl), Compound 22: 2-(2-hydroxy-4-octyloxyphenyl)_2H-benzotriazole, Compound 23: 2-(2-hydroxy-5-third Octylphenyl)-2Η-benzotriazole, compound 24 · 2-(2·hydroxy-5-mercaptopropenyloxyphenyl)-2-indole-3-benzotrizine 5 319273 16 200845902 : Compound 25.2- [2-Hydroxy-3,5-bis(indole, "-di-decylphenylmethyl)phenyl]_2H-benzotriazole. Salicylic acid-based compound · Compound 26: Phenyl salicylate, Compound 27: p-tert-butylphenyl salicylate, compound 28: p-octylphenyl Among them, 2-hydroxy-4-decyloxybenzophenone of the compound 2 is preferred. Examples of the phenolic antioxidant include the following compounds: _Compound A: 2-isopropyl-5-A Phenolic (also known as thymol), Compound B: 2,6-diisopropyl-4-nonylphenol, Compound C · 2-Benzyl-4,6-diindole, Compound D: 2 -Chloromethyl-4,6-diindenyl, Compound E: 2-(4-mercaptophenyl)-4,6-dinonylphenol, Compound F: methyl-3-(2-hydroxyl _5_decyloxyphenyl) acrylate, compound G · methyl 3-(2-transyl-3,5-dimercaptophenyl) acrylate, _ compound H: methyl · 3- (2-hydroxy-3-t-butyl-5-nonyloxyphenyl)propene, acid ester, compound I: 2,6-di-t-butyl-4-nonylphenol, compound J: 2,6 -Di-tert-butyl-4-ethylphenol, compound hydrazine: 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-decyloxy compound, compound L: hard Fatty-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, compound Μ·hin-octyl-3-(3,5-di-t-butyl-4-predyl) Phenyl) propionate, compound N: fluorenyl bis(4-methyl-6-third Phenol), 17 319273 200845902 Compound Ο · 2,2--indenyl bis(4-ethyl-6-t-butyl-p-),, compound Ρ : 4,4,-thio-bis(3-indenyl) -6-tert-butylphenol), compound Q: 4, 4, butylene bis(3-indolyl-6-tert-butylphenol), compound R: 3,9-bis[1,1_dioxin Base_2-[call-(3-tert-butyl-4-hydroxy-5-tolyl)propoxy]ethyl]-2,4,8,10-tetraoxiro[5,5] Monoalkane, compound S: 2,2-thiodivinylbis[3-(3,5-di-t-butylbutylphenyl)propionate], compound τ: 1,1,3-tri 2-methyl-4-hydroxy-5_t-butylphenyl)butane, _compound U: 1,3,5-trimethyl-2,4,6-tris (3,5-di third Butyl-4-hydroxyphenylhydrazino)benzene, compound V: tetra-[indolyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, compound W: three Ethylene glycol bis[3-(3_t-butylhydroxytolyl)propionate], compound X. bis(3,5-di-t-butyl-4-hydroxyphenyl)-isocyanurate , φ compound Y: 1,6-hexanediol bis[3_(3,5-di-t-butyl-t-butanylhydroxy)propionate], compound Ζ: double [^...仏King butyl phenyl decanoate. Among them, the 2,6-di-t-butyl-4-methyl group of the compound I is preferred. In the invention, (iv) wow, ultraviolet light absorber and antimony oxidation. The ratio of blending is usually 1: 〇〇5 to 5: 〇〇5 to 5, where 1: 0.1 to 1: (U) Preferably, i is from 1: 〇a to Β 0.1 to 0.5. When the ultraviolet light absorber or (iv) any of the antioxidants 319273 18 200845902: the blending ratio is too small, it is difficult to obtain light generated by the combination. When the synergistic effect of the stabilization is small, sufficient light stabilization effect cannot be obtained. Conversely, when the ultraviolet light absorber and/or the test system antioxidant are too much, there is no economy. Further, the ratio of the ultraviolet light absorber and the phenolic antioxidant is preferably from four (4) to (10) in terms of mass ratio, and preferably from 1:5 to 2, preferably from 1:0.1 to 10. Preferably, it is 1: 〇2 to 5. The composition of the external parasite repellent of the present invention contains etoxazole and more than one kind of the characters (1) to (28), and contains the compound (VIII) to ^ More preferably, the animal of the external parasite repellent composition is a body such as a cow, a sheep, a goat, a chicken. Livestock, small animals such as dogs and cats, etc. The method of administration of the composition of the external parasite repellent, for example, direct administration, or preparation into a suitable preparation form for transdermal administration to an animal, and administration of the type product, Or applied in the environment. Transdermal administration is by, for example, dipping, L-mist: washing!; perfusion (ρ·°η), coating, drip or dusting, and irrigation, main, drip is preferred By molding the f factory mouth; ^ I in the 'by fine pieces, plates, belts, ear tags --) etc. into the environment = by dusting, graining, spreading, spraying, soil steaming or coating: etc. Among them, it is preferred to spread and spray. * Appropriate formulation form, for molded articles, such as fine chips. In addition, add liquid carrier, solid carrier or auxiliary agent, oil agent, soft agent, gel, emulsion, suspension, oil emulsification in water 319273 19 200845902 factory 制 system = medium water emulsifier, hydration颗粒 granule hydrated Qi Bu powder sword or granule
4製劑之形態使用皆可。 J 田液體載劑之例如水;脂肪族或脂環煙,例如液狀石壤、 *鏈烷、環己烷、萘,或煙霧燈油等;芳香族烴如 二三Μ、甲基萘、二甲基萘、二異丙基萃,絲 f乙一:己苯丨乙Τ·脂肪族醇’例如甲醇、乙醇、異丙醇、 2-乙基己醇、正辛醇、異十三垸基醇、録犧醇,或油 芳香族醇,例如苯甲醇、苯乙醇 氧美、, η , 乂丰虱1乙醇等;酯類, 二:酸乙酯、乙酸丁酯、月桂酸甲酯、癸酸甲酯、I乙 基己酉文甲酯、油酸甲酯、油酸異 己_ 田 等;賴,例如甲基乙基酮,、療己J己一-丁醋 例如菜軒油、黃豆油、番紅花然植物油, 笠·人士、斗、丄此 搪/由、撖欖油或棕櫚油 寻,5成甘油知,例如辛酸三甘油酯、辛酸單.二甘 或辛酸/癸酸三甘油酯等;乙— *θ 驗、二乙二醇單丁_、丙二醇^^類’例如乙二醇單丁 歷;二甲基乙酿胺;_〇;队甲基·寺, 固體載劑之例如天然礦物質類,例如膨潤土、滑石、 ‘土、綠坡縷石、海泡石、酸性白土、高嶺土 或石炭酸㈣;或合成礦物質類,例如氧化銘、白石炭了石夕酸 f炭酸錢、硫_,或氯化又、 (cork)叙末、尿素或小麥粉等皆可採用。 、 319273 20 200845902 if..輔4之例如界面活化冑、分散劑或濕潤劑、固著气 (flXmga州、增黏劑、凌結安定劑、結合劍、崩 安定劑等。 W 朋%劑.、 界面活性劑、分散劑或濕潤劑之例如非離子系壬 = 例如聚氧化稀烴院基"、聚氧化烯烴^ 乙减趟、♦氧化乙烯蓖麻籽油、聚氧化·聚氧化 聚物、聚氧化乙烯單1.三山梨糖醇酐脂肪酸醋、Η 化乙細四油酸山梨糖醇、單脂肪酸甘油酯、單山半糖醇二 脂肪_、隸贿酸醋,或絲葡糖㈣。陰離子系χ 面活化劑之例如絲硫酸鈉、烧基苯續酸鈉,“、二 烧基石黃基琥轴酸鋼鹽、萘石黃酸鹽、木質素石黃酸鹽 卜 烯烴烧基__鹽或硫酸醋鹽、聚氧化烯烴聚苯乙二美 醚磷酸酯鹽或硫酸醋鹽、α_油基磺酸鹽、烷烴碏酸趟等二 兩性界面活化劑之例如Ν_月桂H亞胺基二丙酸 鹽,或卵磷脂等。 =劑之例如酪蛋白、明膠、阿拉伯膠、褐藻酸錢鹽 或納二兵石反酸甸之混合物、膨潤土,或聚乙稀醇等。 增黏劑之例如黃原膠、拉姆參膠(rhamsan gum)等雜多 糖類、羧甲基纖維素、?基纖維素、羥乙基澱粉等之纖維 素或殺粉衍生物、$乙烯醇、聚乙烯料朗,或曱基乙 烯基醚.馬來酸酐共聚物、蒙脫石系黏土礦物、膨潤石系 站土廣物陽離子改質蒙脫石系黏土礦物或膨潤石系黏土 礦物、煙務狀二氧化⑦,或烧基改質煙霧狀二氧化石夕等。 319273 21 200845902 黏接如乙,醇、·丙二醇,或甘油等。 粉等之纖維素或二曱=維素、甲基纖維素、羥乙基殿 鹿妒^飞焱知何生物,或聚乙烯醇等。 制之例如羧曱基纖維辛、 取石 或異謂馬來酸軒共聚物等。、…月—, 女疋劍之例如磷—田 或妥爾油脂肪酸等。夂—兴丙ΜΡΑΡ)、環氧基化黃豆油, 本發明之動物之外邱中4虫 效之有害生物之例舉如;棘驅除劑組成物所能發揮功 鱗翅目害蟲:人蚤、猫蚤, 碑瞒目害蟲:粉表皮蜗、燒表皮. 毛粉蟎、麥粉蟎箄> 、表皮端類;長 〜内战Γ 媒類;塵肉端、家肉端、直足肉蟎 f之肉蟎頦,鍬形爪蟎、肥 •家敗·二刺血真端、二 矮虫知蛛等之㈣蛛類;烏等之_類等:㈠、 ftr月之㈣之外部寄生蟲驅除劑組成物經皮投盘, 盘^由成型製品投與時,適用對象動物體重ik 之乙蠕唾為宜。施用於叫 250mg/m2施用乙蟎唑為宜。 王 (實施例) 町,本㈣之外部寄生蟲驅除劑組成物以製劑例 例舉,亚以防止乙㈣分解之功能試驗及生物效 試驗例’ Ilf _及比㈣更詳細說日林發明,惟本=明 不叉其任何侷限。X,本製劑例中之「份」乃指質量份。 319273 22 200845902 , 製劑例r:油劑 溶解1質量份之乙螨唑,0.25質量份之化合物(2),0.25 質量份之化合物I於10質量份之丙二醇單丁基醚中,再溶 解於35質量份之辛基三甘油酯及53.5質量份之液態石蠟 中,調製得油劑。 製劑例2 :油性懸浮劑 將4質量份之山梨糖醇酐單油酯,1質量份之聚氧化 乙烯山梨糖醇酐三油酯及91質量份之液態石蠟均勻溶 ⑩解,並將1質量份之乙蟎唑,0.25質量份之化合物(1),0.25 質量份之化合物L,以及陽離子改質蒙脫石系黏土礦物2.5 質量份攪拌分散之後,使用球磨機進行濕式粉碎,調製得 油性懸浮劑。 製劑例3 :乳劑 將5質量份之乙螨唑、1質量份之化合物(26),1質量 份之化合物C,10質量份之聚氧化乙烯三苯乙烯基苯基 _醚,5質量份之十二烧基苯磺酸鈣以及78質量份之二曱苯 混合溶解,調製得乳劑。 製劑例4 :水性懸浮劑 將5質量份之聚氧化乙烯三苯乙烯基苯基醚磷酸酯, 20質量份之1 %黃原膠水溶液,1質量份之蒙脫石系黏土 礦物及6 7質量份之水分散·溶解,再將5質量份之乙蜗咬, 1質量份之化合物(3),1質量份之化合物Ε攪拌分散之後, 藉球磨機進行濕式粉碎,調製得水性懸浮劑。 23 319273 200845902 ’#次’藉試驗例具體說明本發明之防止有效成分分解 的效果及生物效果: 广 达:驗例1 :防止乙果試驗 一依照製劑例r調製各種油劑做為實施例。又,調製自 製劑例1僅去除紫外光吸收劑之油劑,僅去除.系抗氧化 劑之油劑,以及去除紫外光吸收劑及驗系抗氧化劑之油劑 做為比較例。所調製之油齊Ij 200mg塗佈於直徑9cm之玻璃 培養皿之後,在陽光直射下放置2星期及i個月。然後將 2〇ml正己烷放入玻璃培養皿中溶解試料,取其2址注入 Sep-pak (商標名稱)plus siliea eanriges 中,再用 w 正己 烷沖洗’去除流出液。其次1 5ml乙酸乙酉旨沖洗,收隹 流出液於霖形燒瓶中。用旋轉蒸鶴器蒸撥去除乙酸乙醋: =中_加入2ml之乙腈予以溶解。再藉備有紫外 =光檢測器之胤以量乙—。並由下式求得乙蜗吐 螓於%光後之分解率。其結果示於表】及表2。又,分別 ^得η日後及丨個月後之照㈣、積度*於各試驗結ς之 知僅在併用紫外線吸收劑及亀氧蝴 吐之光安定性顯示相乘性增加。 刀解十(%)气曝曬陽光丽之乙蟎唑量_曝曬陽光後之乙氧噁 嗤量)χ 1007曝曬陽光前之乙蜗唾量 319273 24 200845902: 表14 The form of the preparation can be used. J field liquid carrier such as water; aliphatic or alicyclic smoke, such as liquid stone, *alkane, cyclohexane, naphthalene, or smoke lamp oil; aromatic hydrocarbons such as diterpene, methylnaphthalene, two Methylnaphthalene, diisopropyl extract, silk f, ethyl hexyl benzoate, aliphatic alcohol, such as methanol, ethanol, isopropanol, 2-ethylhexanol, n-octanol, isotridecyl alcohol , alcohol, or oil aromatic alcohols, such as benzyl alcohol, phenethyl alcohol, η, 乂 虱 虱 1 ethanol; esters, two: ethyl acetate, butyl acetate, methyl laurate, tannic acid Methyl ester, Iethylhexanyl methyl ester, methyl oleate, oleic acid disperse _ field, etc.; Lai, such as methyl ethyl ketone, and hexyl butyl vinegar, such as vegetable oil, soybean oil, Saffron vegetable oil, 笠·人,斗,丄 搪/由, 撖油油 or palm oil, 50% glycerin, such as octanoic acid triglyceride, octanoic acid monosaccharide or octanoic acid/capric acid triglyceride ; B - * θ test, diethylene glycol monobutyl _, propylene glycol ^ ^ class 'such as ethylene glycol monobutyl calendar; dimethyl ethyl amine; _ 〇; team methyl · Temple, solid carrier such as natural mineral Classes, such as bentonite, talc, 'soil, attapulgite, sepiolite, acid white clay, kaolin or carbolic acid (four); or synthetic minerals, such as oxidized Ming, white stone charcoal, sulphuric acid, charcoal, sulphur Or chlorination, (cork), urea or wheat flour can be used. , 319273 20 200845902 if.. auxiliary 4 such as interface activation 胄, dispersant or wetting agent, fixation gas (flXmga state, tackifier, Lingjie stabilizer, combined sword, collapse stabilizer, etc. W Peng% agent. , surfactants, dispersants or wetting agents such as nonionic enthalpy = for example, polyoxyalkylenes, "polyoxyalkylenes", oxime, oxidized ethylene, castor oil, polyoxygenated polyoxyl , polyoxyethylene single 1. trisorbide fatty acid vinegar, bismuth tetraacetate sorbitol, mono-fatty acid glyceride, mono-half sugar alcohol two fat _, bribe vinegar, or silk sugar (four) Anionic surfactants such as sodium sulphate, sodium benzoate, "dicalcium sulphate, sulphate, naphthalene, lignin, olefins" _ salt or sulfate vinegar, polyoxyalkylene polystyrene ether phosphate or sulfate vinegar, α oleyl sulfonate, alkane bismuth citrate and other two amphoteric interfacial activators such as Ν _ _ laurel H imine Dipropionate, or lecithin, etc. = such as casein, gelatin, gum arabic, alginic acid money salt Or a mixture of Na 2 shishi anti-sweet, bentonite, or polyethylene glycol, etc. Adhesives such as xanthan gum, rhamsan gum and other heteropolysaccharides, carboxymethyl cellulose, base Cellulose or powder-killing derivatives of cellulose, hydroxyethyl starch, etc., vinyl alcohol, polyethylene mer, or mercapto vinyl ether. maleic anhydride copolymer, montmorillonite clay mineral, bentonite station Soil cations modified montmorillonite clay minerals or bentonite clay minerals, oxidized dioxide dioxide 7, or burnt-based modified smog-like sulphur dioxide, etc. 319273 21 200845902 Bonding such as B, alcohol, · Propylene glycol, or glycerin, etc. Cellulose or diterpenoids such as powder, vitamins, methylcellulose, hydroxyethyl sulphate, scorpion scorpion, or polyvinyl alcohol, etc. , stone or a different type of maleic acid copolymer, etc., ... month -, female scorpion sword such as phosphorus - field or tall oil fatty acid, etc., 夂 兴 ΜΡΑΡ ΜΡΑΡ, epoxidized soybean oil, the present invention An example of a pest in which 4 insects are effective in animals, such as a spine repellent composition. Hymenoptera pests: human cockroaches, cat mites, sturgeon pests: powder epidermis, burned epidermis. edulis, wheat flour 螨箄 >, epidermis end; long ~ civil war 媒 media; dusty meat, home meat End, straight meat, f, meat, scorpion, scorpion, fat, home, two thorns, two worms, etc. (four) spiders; (4) The composition of the external parasite repellent is percutaneously cast, and when the disc is administered by the molded product, it is suitable for the animal to weigh the weight of the animal ik. It is suitable to apply the ethazole at 250 mg/m2. Example) The external parasite repellent composition of the town (4) is exemplified by the preparation example, and the functional test and the biological test example 'Ilf _ and the ratio (4) for preventing the decomposition of B (4) are described in more detail. = clearly does not fork any of its limitations. X, "Parts" in the present preparation examples means parts by mass. 319273 22 200845902 , Formulation Example r: an oil agent dissolves 1 part by mass of oxazole, 0.25 parts by mass of the compound (2), 0.25 parts by mass of the compound I in 10 parts by mass of propylene glycol monobutyl ether, and is dissolved in 35 An oil agent is prepared in an amount of octyl triglyceride and 53.5 parts by mass of liquid paraffin. Formulation Example 2: Oily Suspending Agent: 4 parts by mass of sorbitan monooleate, 1 part by mass of polyoxyethylene sorbitan trioleate, and 91 parts by mass of liquid paraffin are uniformly dissolved, and 1 mass is obtained. Ethyl oxazole, 0.25 parts by mass of the compound (1), 0.25 parts by mass of the compound L, and 2.5 parts by mass of the cationically modified smectite-based clay mineral are stirred and dispersed, and then subjected to wet pulverization using a ball mill to prepare an oily suspension. Agent. Formulation Example 3: 5 parts by mass of ethiazole, 1 part by mass of the compound (26), 1 part by mass of the compound C, 10 parts by mass of polyoxyethylene tristyrylphenyl ether, 5 parts by mass of the emulsion The calcium dodecylbenzenesulfonate and 78 parts by mass of dinonylbenzene were mixed and dissolved to prepare an emulsion. Formulation Example 4: aqueous suspension agent 5 parts by mass of polyoxyethylene tristyrylphenyl ether phosphate, 20 parts by mass of 1% aqueous solution of xanthan gum, 1 part by mass of montmorillonite clay mineral and 67 mass The water is dispersed and dissolved, and 5 parts by mass of the acetylene bite, 1 part by mass of the compound (3), and 1 part by mass of the compound Ε are stirred and dispersed, and then subjected to wet pulverization by a ball mill to prepare an aqueous suspension. 23 319273 200845902 The effect of the decomposition of the active ingredient of the present invention and the biological effect are specifically described by the test example: GENERAL: Test Example 1: Prevention of the test of the fruit B. Various oil agents were prepared in accordance with the formulation example r as an example. Further, the preparation example 1 only removes the oil agent of the ultraviolet light absorber, and only the oil agent which is an antioxidant is removed, and the oil agent which removes the ultraviolet light absorber and the antioxidant is used as a comparative example. The prepared oil Qi Ij 200 mg was applied to a glass culture dish having a diameter of 9 cm, and placed under direct sunlight for 2 weeks and 1 month. Then, 2 ml of n-hexane was placed in a glass petri dish to dissolve the sample, and the site was injected into Sep-pak (trade name) plus siliea eanriges, and then rinsed with w-hexane to remove the effluent. Next, 15 ml of ethyl acetate was rinsed, and the effluent was collected in a Lin-shaped flask. The acetic acid was removed by steaming with a rotary steamer: = medium _ 2 ml of acetonitrile was added to dissolve. Then borrow the UV = photodetector to measure the amount of B. And the decomposition rate of the second ray is obtained by the following formula. The results are shown in Tables and Table 2. In addition, the photos (4) and the accumulation of * after the η day and after the month were found to have an increase in the multiplicative property of the ultraviolet light absorber and the oxygen stability of the oxygen. Knife solution ten (%) gas exposure Sunshine acetazol amount _ exposure to sunlight after the ethoxy oxime amount) χ 1007 exposure to the sun before the snail volume 319273 24 200845902: Table 1
製劑例1之油劑 分解率(%) 紫外線吸收劑 抗氧化劑 添加量(份) 1 4日後 1個月後 實施例1 化合物(2) 化合物I 0.25+0,25 2 10 實施例2 化合物(2) 化合物I 0.25+0.50 1 5 實施例3 化合€ (2) 化合物I 0.10+1.00 3 6 實施例4 化合物(2 ) 化合物I 1,00+0.10 8 15 實施例5 化合物(3) 化合物K 0.25+0.25 8 9 實施例6 化合物(3) 化合物K 0.25+0.50 3 5 實施例7 化合物(3) 化合物K 0.10+1.00 4 6 實施例8 化合物(3) 化合物K 1 1.00+0.10 10 18 實施例9 化合物(4) 化合物A 0.25+0.25 8 '15 實施例1 0 化合物(8) 化合物B 0.25+0.25 1 4 實施例1 1 化合物(1 0〉 化合物D 0.25+0.25 2 6 實施例1 2 化合物(6) 化合物G 0.25+0.25 1 3 比較例1 化合物(2) 一 0.25 70 89 比較例2 化合物(2) — 1.0 60 80 比較例3 化合物(3) 一 0.25 55 84 比較例4 化合物(3) — 1.0 5¾ 79 比較例5 化合物(4) — 1.0 65 • 90 比較例6 化合物(8) 一 1.0 53 79 比較例7 化合物(1 0) — 1.0 70 91 比較例8 化合物(6) — 1.0 62 84 比較例9 — 化合物A 1.0 15 50 比較例1 0 — 化合物B 1.0 29 55 比較例1 1 一 化合物D 1.0 21 48 比較例1 2 — 化合物G 1.0 12 34 比較例1 3 一 化合物I 0.25 79 84 比較例1 4 — 化合物I 1.0 7 39 比較例1 5 — 化合物K 0.25 77 89 比較例1 6 一 化合物K 1.0 18 47 比較例1 7 一 — — 88 99 照射累積度:14日為止6050kLx · hr,1個月為止14,120kLx · hr 25 319273 200845902 / 表Formulation Example 1 Oil Decomposition Rate (%) UV Absorber Antioxidant Addition Amount (Parts) 1 month after 1 month after Example 1 Compound (2) Compound I 0.25+0, 25 2 10 Example 2 Compound (2) Compound I 0.25+0.50 1 5 Example 3 Compounding (2) Compound I 0.10+1.00 3 6 Example 4 Compound (2) Compound I 1,00+0.10 8 15 Example 5 Compound (3) Compound K 0.25+ 0.25 8 9 Example 6 Compound (3) Compound K 0.25+0.50 3 5 Example 7 Compound (3) Compound K 0.10+1.00 4 6 Example 8 Compound (3) Compound K 1 1.00+0.10 10 18 Example 9 Compound (4) Compound A 0.25 + 0.25 8 '15 Example 1 0 Compound (8) Compound B 0.25 + 0.25 1 4 Example 1 1 Compound (1 0 > Compound D 0.25 + 0.25 2 6 Example 1 2 Compound (6) Compound G 0.25 + 0.25 1 3 Comparative Example 1 Compound (2) - 0.25 70 89 Comparative Example 2 Compound (2) - 1.0 60 80 Comparative Example 3 Compound (3) - 0.25 55 84 Comparative Example 4 Compound (3) - 1.0 53⁄4 79 Comparative Example 5 Compound (4) - 1.0 65 • 90 Comparative Example 6 Compound (8) A 1.0 53 79 Comparative Example 7 Compound (10) - 1.0 70 91 Comparative Example 8 Compound (6) - 1.0 62 84 Comparative Example 9 - Compound A 1.0 15 50 Comparative Example 1 0 - Compound B 1.0 29 55 Comparative Example 1 1 A compound D 1.0 21 48 Comparative Example 1 2 - Compound G 1.0 12 34 Comparative Example 1 3 A compound I 0.25 79 84 Comparative Example 1 4 - Compound I 1.0 7 39 Comparative Example 1 5 - Compound K 0.25 77 89 Comparative Example 1 6 A compound K 1.0 18 47 Comparative Example 1 7 One - 88 99 Accumulation of radiation: 6050kLx · hr up to 14th, 14,120kLx · hr 25 319273 200845902 / Table
製劑例1之油劑 分解率(%) 紫外線呢收劑 抗氧化劑 添加量(份) 1 4日後 1個月後 實施例1 3 化合物(14) 化合物N 0.25+0.25 2 7 實施例1 4 化合物(1 5) 化合物U 0.25+0.25 7 15 實施例1 5 化合物(1 6) 化合物Y 0.25+0.25 10 18 實施例1 6 化合物(1 9) 化合物I 0.25+0.25 3 5 實施例1 7 化合物(2 3) 化合物R 0.25+0.25 8 9 實施例1 8 化合物(2 5) 化合物Η 0,25+0.25 5 10 實施例1 9 化合物(1 2) 化合物I 0.25+0.25 4 6 實施例2 0 化合物(2 7) 化合物Κ 0.25+0.25 3 8 比較例1 8 化合物(1 4) — 1.0 58 78 比較例1 9 化合物(1 5) — 1.0 61 81 比較例2 0 化合物(16) — 1.0 65 82 比較例2 1 化合物(1 9) 一 1.0 66 87 比較例2 2 化合物(2 3) — 1.0 65 90 比較例2 3 化合物(2 5) — 1.0 60 85 比較例2 4 化合物(1 2) 一 1.0 55 75 比較例2 5 化合物(2 7) 一 1.0 62 84 比較例2 6 — 化合物Ν 1.0 15 50 比較例2 7 — 化合物U 1.0 21 55 比較例2 8 一 化合物Υ 1.0 21 48 比較例2 9 - 化合物I 1.0 18 43 比較例3 0 — 化合物R 1.0 25 61 比較例3 1 — 化合物Η 1,0 18 50 比較例3 2 — 化合物Κ 1.0 15 45 比較例3 3 一 一 — 84 99 照射累積度:14日為止7100kLx · hr,1個月為止13,540kLx · hr 試驗例2 防止乙蟎唑油中懸浮劑分解之效果試驗 依照製劑例2調製各種油中懸浮劑做為實施例。另調 製從製劑例2僅去除紫外光吸收劑之油中懸浮劑,僅去除 紛系抗氧化劑之油中懸浮劑,以及去除紫外光吸收劑及紛 系抗氧化劑之油中懸浮劑做為比較例。調製之油中懸浮劑 取其200mg塗佈於直徑9cm之玻璃培養jul之後,在陽光照 射下放置2星期及1個月。然後將20ml正己烷放入玻璃 26 319273 200845902 " 培養皿中溶解試料。取其2ml注入Sep-pak(商標名稱)plusFormulation Example 1 Oil Decomposition Rate (%) UV Receptor Antioxidant Addition Amount (Parts) 1 month after 1 month Example 1 3 Compound (14) Compound N 0.25+0.25 2 7 Example 1 4 Compound ( 1 5) Compound U 0.25 + 0.25 7 15 Example 1 5 Compound (1 6) Compound Y 0.25 + 0.25 10 18 Example 1 6 Compound (1 9) Compound I 0.25 + 0.25 3 5 Example 1 7 Compound (2 3 Compound R 0.25+0.25 8 9 Example 1 8 Compound (2 5) Compound Η 0,25+0.25 5 10 Example 1 9 Compound (1 2) Compound I 0.25+0.25 4 6 Example 2 0 Compound (2 7 ) Compound 0.25 0.25 + 0.25 3 8 Comparative Example 1 8 Compound (1 4) - 1.0 58 78 Comparative Example 1 9 Compound (1 5) - 1.0 61 81 Comparative Example 2 0 Compound (16) - 1.0 65 82 Comparative Example 2 1 Compound (1 9) - 1.0 66 87 Comparative Example 2 2 Compound (2 3) - 1.0 65 90 Comparative Example 2 3 Compound (2 5) - 1.0 60 85 Comparative Example 2 4 Compound (1 2) - 1.0 55 75 Comparative Example 2 5 Compound (2 7) - 1.0 62 84 Comparative Example 2 6 - Compound Ν 1.0 15 50 Comparative Example 2 7 - Compound U 1.0 21 55 ratio Comparative Example 2 8 A compound Υ 1.0 21 48 Comparative Example 2 9 - Compound I 1.0 18 43 Comparative Example 3 0 - Compound R 1.0 25 61 Comparative Example 3 1 - Compound Η 1,0 18 50 Comparative Example 3 2 - Compound Κ 1.0 15 45 Comparative Example 3 3 One-84 99 Accumulation of radiation: 7100 kLx · hr at 14 days, 13,540 kLx · hr for one month Test Example 2 Effect of preventing decomposition of suspending agent in etoxazole oil Test according to Formulation Example 2 Suspending agents in various oils are used as examples. Further, a suspension agent for removing only the ultraviolet light absorber from the preparation example 2, a suspension agent for removing only the oil of the various antioxidants, and a suspension agent for removing the ultraviolet light absorber and the various antioxidants are used as a comparative example. . The suspended oil in the prepared oil was applied to a glass culture jul having a diameter of 9 cm and placed under a sun irradiation for 2 weeks and 1 month. Then, 20 ml of n-hexane was placed in a glass 26 319273 200845902 " Petri dish to dissolve the sample. Take 2ml into Sep-pak (trade name) plus
Silicacartriges,以5ml正己烷沖洗,去除流出液。繼之, 用5ml乙酸乙酯沖洗,收集流出液於茄形燒瓶中,用旋轉 蒸餾器蒸餾去除乙酸乙酯,於殘渣中精確加入2ml之乙腈 亚予以溶解。藉備有紫外光分光檢測器之HPLC定量乙織 ^再按照試驗例1相同方法求得曝曬陽光所造“分解 ¥·,其結果示於表3中。又,μ日; 積度示於試驗结果之表…Γ後及1個月後之照射累 •同,僅在併用ΐ ί表。由結果顯示與上述表1及表2相 光安定性知千 』/、酚糸抗虱化劑時,乙蟎唑之 女疋性獲侍相乘性增強效果。Silicacartriges, rinsed with 5 ml of n-hexane to remove the effluent. Subsequently, it was washed with 5 ml of ethyl acetate, and the effluent was collected in an eggplant-shaped flask, and ethyl acetate was distilled off by a rotary distiller, and 2 ml of acetonitrile was accurately added to the residue to dissolve. The HPLC was used to quantify the woven fabric by an ultraviolet spectrophotometer. The same method as in Test Example 1 was used to obtain the "decomposition", and the results are shown in Table 3. Further, μ day; The results are shown in the following paragraphs and after 1 month, the exposure is the same, only in combination with the ΐ ί table. The results show that compared with the above Table 1 and Table 2, the light stability is known as /, phenolphthalein anti-deuteration agent The female sex of acetazole is enhanced by the multiplicative effect.
319273 27 200845902 •' 表3 製劑例2之油中懸浮劑 分解率(%) 紫外線吸收劑 抗氧化劑 添加量(份) 1 4日後 1個月後 實施例2 1 化合物(1) 化合物L 0.25+0.25 8 16 實施例2 2 化合物(7) 化合物Μ 0.25+0.25 7 12 實施例2 3 化合物(9) 化合物Ρ 0.25+0.25 5 10 實施例2 4 化合物(1 1) 化合物X 0.25+0.25 8 14 實施例2 5 化合物(2 0) 化合物Ζ 0.25+0.25 8 18 實施例2 6 化合物(2 8 ) 化合物I 0·25+0·25 3 8 實施例2 7 化合物(1 8) 化合物S 0.25+0.25 6 11 實施例2 8 化合物(2 0) 化合物W 0.25+0.25 9 17 比較例3 4 化合物(1) 一 1.0 58 .78 比較例3 5 化合物(7) 一 1.0 61 81 比較例3 6 化合物(9) 一 1.0 65 82 比較例3 7 化合物(1 1) — 1.0 66 87 比較例3 8 化合物(2 0) 一 L0 65 90 比較例3 9 化合物(2 S) — 1,0 60 85 比較例4 0 化合物(1 8) — 1.0 55 75 比較例4 1 化合物(2 0) — 1.0 62 84 比較例4 2 一 化合物L 1.0 35 ^ 70 比較例4 3 一 化合物Μ 1.0 28 64 比較例4 4 一 化合物Ρ 1.0 20 48 比較例4 5 一 化合物X 1.0 22 55 比較例4 6 一 化合物Ζ 1.0 28 60 比較例4 7 一 化合物I 1.0 20 45 比較例4 8 一 化合物S 1.0 18 50 比較例4 9 — 化合物W 1.0 21 61 比較例5 0 — — 一 87 100 照射累積度:14日為止6220kLx · hr,1個月為止12,740kLx · hr319273 27 200845902 •' Table 3 Disintegration rate of the suspension in oil of Formulation Example 2 (%) UV absorber added amount of antioxidant (parts) 1 month after 1 month Example 2 1 Compound (1) Compound L 0.25+0.25 8 16 Example 2 2 Compound (7) Compound Μ 0.25 + 0.25 7 12 Example 2 3 Compound (9) Compound Ρ 0.25 + 0.25 5 10 Example 2 4 Compound (1 1) Compound X 0.25 + 0.25 8 14 Example 2 5 Compound (2 0) Compound Ζ 0.25 + 0.25 8 18 Example 2 6 Compound (2 8 ) Compound I 0·25+0·25 3 8 Example 2 7 Compound (1 8) Compound S 0.25+0.25 6 11 Example 2 8 Compound (20) Compound W 0.25 + 0.25 9 17 Comparative Example 3 4 Compound (1) - 1.0 58 .78 Comparative Example 3 5 Compound (7) - 1.0 61 81 Comparative Example 3 6 Compound (9) 1.0 65 82 Comparative Example 3 7 Compound (1 1) - 1.0 66 87 Comparative Example 3 8 Compound (2 0) - L0 65 90 Comparative Example 3 9 Compound (2 S) - 1, 0 60 85 Comparative Example 4 0 Compound ( 1 8) — 1.0 55 75 Comparative Example 4 1 Compound (2 0) — 1.0 62 84 Comparative Example 4 2 A compound L 1.0 35 ^ 70 Comparative Example 4 3 A compound Μ 1.0 28 64 Comparative Example 4 4 A compound Ρ 1.0 20 48 Comparative Example 4 5 A compound X 1.0 22 55 Comparative Example 4 6 A compound Ζ 1.0 28 60 Comparative Example 4 7 A compound I 1.0 20 45 Comparative Example 4 8 A compound S 1.0 18 50 Comparative Example 4 9 - Compound W 1.0 21 61 Comparative Example 5 0 - - 87 100 Irradiation cumulative: 6220 kLx · hr on the 14th, 12,740 kLx · hr from 1 month
試驗例3 防止乙蟎唑乳劑分解之效果試驗 依照製劑例3調製各種乳劑做為實施例。另外,調製 自製劑例3僅去除紫外光吸收劑之乳劑,僅去除酚系抗氧 化劑之乳劑,以及去除紫外光吸收劑及酚系抗氧化劑之乳 劑做為比較例。調製之乳劑取其lg用水稀釋成全量為 100ml。將4ml之稀釋液放入直徑9cm之玻璃培養皿中, 蒸散水分之後,陽光照射下放置2星期及1個月。玻璃培 28 319273 200845902 , 養皿中放入20ml之乙腈並溶解試料,於茄形燒瓶中收集 溶解液,用旋轉式蒸散器蒸餾去除乙腈,殘渣中精確加入 2ml之乙腈並加以溶解。藉備有紫外光分光檢測器之HPLC 定量乙蟎唑。再按照試驗例1相同方法求得曝曬陽光所造 成之分解率。其結果示於表4中。又,14日後及1個月後 之照射累積度示於試驗結果之表。由結果顯示與表1、2 及3同樣,在併用紫外光吸收劑與酚系抗氧化劑時,乙螨 唑之光安定性獲得相乘性增強效果。 •表4 製劑例3之乳劑 分解率(%) 紫外線吸收劑 抗氧化劑 添加量C份) 1 4日後 1個月後 實施例2 9 化合物(2 6 ) 化合物C L0+1.0 4 7 實施例3 0 化合物(2) 化合物I 1.0+1.0 3 6 實施例3 1 化合物(5) 化合物〇 1.0+1.0 5 9 實施例3 3 化合物(1 7 ) 化合物Q 1.0+1.0 6 13 實施例3 4 化合物(1 6 ) 化合物J 1.0+1.0 6 9 比較例5 1 化合物(2 6 ) — 5.0 50 75 比較例5 2 化合物(2 > — 5.0 48 70 比較例5 3 化合物(5 ) 一 5.0 53 82 比較例5 4 化合物(1 7) — 5.0 65 86 比較例5 5 化合物(1 6 ) — 5.0 65 81 比較例5 6 — 化合物C 5.0 17 40 比較例5 7 — 化合物I 5.0 10 38 比較例5 8 一 化合物〇 5.0 15 45 比較例5 9 — 化合物Q 5.0 20 50 比較例6 0 一 化合物J 5.0 15 42 比較例6 1 一 一 一 87 99 照射累積度:14日為止7530kLx · hr,1個月為止14, ISOkLx · hrTest Example 3 Effect Test for Preventing Decomposition of Acetazole Emulsion Various emulsions were prepared in accordance with Formulation Example 3 as an example. Further, from the preparation of Example 3, only the emulsion of the ultraviolet light absorber was removed, only the emulsion of the phenolic antioxidant was removed, and the emulsion of the ultraviolet light absorber and the phenolic antioxidant was removed as a comparative example. The prepared emulsion was diluted with lg of water to a total amount of 100 ml. 4 ml of the diluted solution was placed in a glass petri dish having a diameter of 9 cm, and the water was evaporated to dryness, and then left to stand for 2 weeks and 1 month under sunlight. Glass culture 28 319273 200845902 , 20 ml of acetonitrile was placed in a dish and the sample was dissolved. The solution was collected in an eggplant-shaped flask, and the acetonitrile was distilled off by a rotary irrigator, and 2 ml of acetonitrile was accurately added to the residue and dissolved. Ethyl oxazole was quantified by HPLC with an ultraviolet spectrophotometer. Further, the decomposition rate by exposure to sunlight was determined in the same manner as in Test Example 1. The results are shown in Table 4. Further, the cumulative accumulation of radiation after 14 days and one month later is shown in the table of test results. As a result, in the same manner as in Tables 1, 2 and 3, when the ultraviolet light absorber and the phenolic antioxidant were used in combination, the light stability of the carbazole was enhanced to obtain a synergistic effect. • Table 4 Formulation Example 3 Emulsion Decomposition Rate (%) UV Absorber Antioxidant Addition C Part) 1 month after 1 month after Example 2 9 Compound (2 6 ) Compound C L0+1.0 4 7 Example 3 0 Compound (2) Compound I 1.0+1.0 3 6 Example 3 1 Compound (5) Compound 〇 1.0+1.0 5 9 Example 3 3 Compound (1 7 ) Compound Q 1.0+1.0 6 13 Example 3 4 Compound (1 6 Compound J 1.0+1.0 6 9 Comparative Example 5 1 Compound (2 6 ) - 5.0 50 75 Comparative Example 5 2 Compound (2 > - 5.0 48 70 Comparative Example 5 3 Compound (5) - 5.0 53 82 Comparative Example 5 4 Compound (17) - 5.0 65 86 Comparative Example 5 5 Compound (1 6 ) - 5.0 65 81 Comparative Example 5 6 - Compound C 5.0 17 40 Comparative Example 5 7 - Compound I 5.0 10 38 Comparative Example 5 8 A compound 〇 5.0 15 45 Comparative Example 5 9 - Compound Q 5.0 20 50 Comparative Example 6 0 A compound J 5.0 15 42 Comparative Example 6 1 One-to-one 87 99 Irradiation cumulative: 7530 kLx · hr at 14 days, 14 months, ISOkLx Hr
試驗例4 ··防止乙瞒嗤水中懸浮劑分解之效果試驗 依照製劑例4調製各種水中懸浮劑做為實施例。另 外,調製自製劑例4僅去除紫外光吸收劑之水中懸浮劑, 僅去除酚系抗氧化劑之水中懸浮劑,以及去除紫外光吸收 29 319273 200845902 , 劑及酚系抗氧化劑之水中懸浮劑做為比較例。調製之水中 懸浮劑取其lg用水稀釋成全量為100ml,放入4ml之稀釋 液於直徑9cm之玻璃培養皿中,蒸散水分之後,在陽光照 射下放置2星期及1個月。於玻璃培養皿中放入20ml乙 腈溶解試料,於茄形燒瓶中收集溶解液。用旋轉蒸散器蒸 餾去除乙腈,殘渣中精確加入2ml之乙腈予以溶解。藉備 有紫外光光度檢測器之HPLC定量乙螨唑。按照試驗例1 相同方法求得曝曬於陽光下所造成之分解率。其結果示於 善表5。又,14日後及1個月後之照射累積度示於試驗結果 之表。由結果顯示可知與表1、2、3及4相同,當併用紫 外光吸收劑及酴抗氧化劑時,乙蜗嗤之光安定性獲得相乘 性增強效果。 表5Test Example 4·Effect Test for Preventing Decomposition of Suspending Agent in Ethylhydrazine Water Various aqueous suspending agents were prepared in accordance with Formulation Example 4 as an example. In addition, it was prepared from the preparation of Example 4 to remove only the aqueous suspension of the ultraviolet light absorber, to remove only the phenolic antioxidant in the aqueous suspension, and to remove the ultraviolet light absorption 29 319273 200845902, the agent and the phenolic antioxidant in the water suspension agent as Comparative example. In the prepared water, the suspension was diluted with lg to 100 ml of the whole amount, and 4 ml of the diluted solution was placed in a glass petri dish having a diameter of 9 cm, and the water was evaporated, and then placed under sunlight for 2 weeks and 1 month. The sample was dissolved in 20 ml of acetonitrile in a glass petri dish, and the solution was collected in an eggplant-shaped flask. The acetonitrile was removed by distillation using a rotary emulsifier, and 2 ml of acetonitrile was accurately added to the residue to dissolve. Ethyl oxazole was quantified by HPLC with an ultraviolet photometric detector. The decomposition rate caused by exposure to sunlight was determined in the same manner as in Test Example 1. The results are shown in Table 5. Further, the cumulative accumulation of radiation after 14 days and one month later is shown in the table of test results. From the results, it can be seen that, similarly to Tables 1, 2, 3 and 4, when the ultraviolet light absorbing agent and the ruthenium antioxidant are used in combination, the light stability of the acetaminophen is enhanced. table 5
製劑例4之水中懸浮劑 分解率(%) 紫外線吸收劑 抗氧化劑 添加量(份) 1 4日後 1個月後 實施例3 5 化合物(3) 化合物E 1.0+1.0 5 10 實施例3 6 化合物(2 1) 化合物F 1.0+1.0 7 15 實施例3 7 化合物(2 2 ) 化合物T 1.0+1.0 10 18 實施例3 8 化合物(2 4 ) 化合物V 1.0+1.0 3 5 實施例3 9 化合物(1 3 ) 化合物Z 1.0+1.0 8 9 比較例6 2 化合物(3) 一 5.0 55 80 比較例6 3 化合物(2 1) 一 5.0 61 83 比較例6 4 化合物(2 2) — 5.0 65 85 比較例S 5 化合物(2 4 ) — 5.0 60 .87 比較例6 6 化合物(1 3 ) — 5.0 51 77 比較例6 7 — 化合物E 5.0 17 48 比較例6 8 一 化合物F 5.0 13 37 比較例6 9 一 化合物丁 5.0 15 40 比較例7 0 — 化合物V 5.0 11 42 比較例7 1 — 化合物Z 5.0 19 55 比較例7 2 — 一 一 80 97 照射累積度:14日為止7530kLx · hr,1個月為止14,180kLx · hr 30 319273 200845902 於二刺.血真蟎之生物敔要試路 已知乙蟎唑具有優異之殺印、殺幼蟎效果,然而對於 成蟲蜗卻無殺蟲效果。本試驗中,由殺即效果評估其初期 效果及其线效性。按照製劑例丨調製之油劑及按照製劑例 2調製之油中懸浮劑,以牛體^ 1〇kg計,藉供應器灌注 1ml。處理】日後,釋放雌蟎成蟲。成蟎寄生並吸血,收 集,飽血落下之雌蟎成蟲所產印,保存在25它,3星期後 觀祭卵之孵化情形,求得孵化率。另外,在戶外放飼丨個 •月後’同樣釋放_成蟲’同樣求得雌蜗成蟲所產即之解 化率。由該結果顯示,較之單獨使用紫外光吸收劑或酚抗 氧化劑者,併用紫外光吸收劑及酚抗氧化劑之乙蟎唑,有 助於其殘效性之延長。 卵孵化率(%) =(醇化卵數/產卵卵數)^⑽ 表β i 由劑及製劑例2^^中懸浮劑 卵孵化率’ 紫外光吸收劑 抗氧化劑 添加量(份) 1曰後 1個月後 貫施例1 油劑 化合物(2) 化合物I 0.25+0.25 0 0 — 貫施例5 油劑 化合物(3) 化合物K 0.25+0.25 0 0 ~ 貫施例10 油劑 化合物(8) 化合物B 0.25+0.25 0 0 比較例2 油劑 化合物(2) —— 1.0 0 87 比較例14 油劑 — 化合物I 1.0 0 52 比較例17 油劑 — —— .— 0 100 ' 貫施例21 油中懸浮劑 化合物(1) 化合物L 0.25+0.25 0 0 實施例22 油中懸浮劑 化合物(7) 化合物Μ 0.25+0.25 0 0 實施例26 油中懸浮劑 化合物(28) 化合物I 0.25+0.25 0 0 比較例34 油中懸浮劑 化合物(1) — 1.0 0 81 比較例42 油中懸浮劑 — 化合物L 1.0 0 68 ^ 比較例50 油中懸浮劑 —— — — 0 100 ' 試•驗例_..6 1^數龙猫蚤之生物效果試驗 31 319273 200845902 •-…依照製劑例3調製之乳劑及依照製劑例“周製之水 懸浮劑’以猫體|叫計,在猫背頸部處使用ι〇〇倍水稀 釋液4m卜以乙蜗唑計2mg,藉微注射針灌注。處理卫曰 後釋放雌蚤成蟲使之寄生。釋放4日後回收所產印,移至 培養皿。在25ΐ保存所收集之卵,3星期後觀察即之解^ 情形’求得畔化率。又,飼養猫於戶外1個月後,同樣釋 放雌蚤成蟲,同樣對所產卵求其孵化率。由該結果顯示, 較之單獨使用紫外光吸收劑或酚抗氧化劑者,併用紫外光 吸收劑及酚抗氧化劑者對乙蟎唑有助於殘效性之延長。 表7 i 1劑例3之季 u劑及製劑例4之水中懸洋劑 卵孵化 rri-T* » ,广\ 紫外光吸收劑 抗氧化劑 添加量(份) 1日後 1個月德 貫施例0 乳劑 化合物(2) 化合物I 1.0+1.0 0 /4 1 又 0 貫施例31 Γ乳劑 化合物(5) 化合物0 1.0+1.0 0 0 貫施例34 _乳劑 化合物(16) 化合物J 1.0+1.0 0 〇 tb較例55 _乳劑 化合物(16) 一 5.0 0 82 比車父例60 乳劑 化合物J 5.0 0 70 比較例61 __乳劑 — — 0 99 實施例36 懸浮g 化合物C21) 化合也rl 1.0+1.0 0 〇 實施例37 懸浮劑 化合物(22) 1 化合物Τ 1·0+1·0 0 一 〇 實施例39 Μ懸浮劑 化合物(13) 化合物Ζ 1.0+1.0 0 〇 比較例64 懸浮劑 化合物(22) — 5.0 0 80 比較例69 Μ懸浮劑 一 化合物Τ 5.0 0 65 比較例72 it懸浮劑 — — 0 100 319273 32Formulation Example 4 Aqueous Suspension Decomposition Rate (%) UV Absorber Antioxidant Addition Amount (Parts) 1 month after 1 month after Example 3 5 Compound (3) Compound E 1.0+1.0 5 10 Example 3 6 Compound ( 2 1) Compound F 1.0+1.0 7 15 Example 3 7 Compound (2 2 ) Compound T 1.0+1.0 10 18 Example 3 8 Compound (2 4 ) Compound V 1.0+1.0 3 5 Example 3 9 Compound (1 3 Compound Z 1.0+1.0 8 9 Comparative Example 6 2 Compound (3) - 5.0 55 80 Comparative Example 6 3 Compound (2 1) - 5.0 61 83 Comparative Example 6 4 Compound (2 2) - 5.0 65 85 Comparative Example S 5 Compound (2 4 ) - 5.0 60 .87 Comparative Example 6 6 Compound (1 3 ) - 5.0 51 77 Comparative Example 6 7 - Compound E 5.0 17 48 Comparative Example 6 8 A compound F 5.0 13 37 Comparative Example 6 9 A compound 5.0 15 40 Comparative Example 7 0 - Compound V 5.0 11 42 Comparative Example 7 1 - Compound Z 5.0 19 55 Comparative Example 7 2 - One-to-one 80 97 Irradiation cumulative: 7530 kLx · hr at 14 days, 14,180 kLx at 1 month Hr 30 319273 200845902 In the second thorn. The blood of the true cockroach is going to test the path of known carbazole It has excellent killing and killing effects, but it has no insecticidal effect on adult worms. In this test, the initial effect and its line effect were evaluated by the killing effect. According to the preparation example, the oil agent prepared in accordance with the preparation example and the suspending agent in the oil prepared according to the preparation example 2 were perfused with 1 ml in a bovine body by 1 〇kg. Treatment] In the future, the female adult is released. Into the mistletoe and blood-sucking, collecting, the blood-sucking female cockroaches produced by the insects, preserved in 25 it, after 3 weeks to observe the hatching of the eggs, to obtain the hatching rate. In addition, the release rate of the female worms is also obtained after the feeding of the cockroach. From the results, it has been shown that the use of an ultraviolet light absorber or a phenolic antioxidant in combination with an ultraviolet light absorber or a phenol antioxidant alone contributes to the prolongation of the residual effect. Egg hatching rate (%) = (alcoholized eggs / number of eggs laid) ^ (10) Table β i by the agent and preparation example 2 ^ ^ suspending agent egg hatching rate 'UV light absorber antioxidant amount (parts) 1曰After 1 month, the application of the oil compound (2) Compound I 0.25 + 0.25 0 0 - Example 5 Oil compound (3) Compound K 0.25 + 0.25 0 0 ~ Example 10 Oil compound (8 Compound B 0.25 + 0.25 0 0 Comparative Example 2 Oil Compound (2) - 1.0 0 87 Comparative Example 14 Oil Agent - Compound I 1.0 0 52 Comparative Example 17 Oil Agent - ——. - 0 100 ' Example 21 Suspension Compound in Oil (1) Compound L 0.25+0.25 0 0 Example 22 Suspension Compound in Oil (7) Compound Μ 0.25 + 0.25 0 0 Example 26 Suspension Compound in Oil (28) Compound I 0.25+0.25 0 0 Comparative Example 34 Suspension Compound in Oil (1) - 1.0 0 81 Comparative Example 42 Suspension in Oil - Compound L 1.0 0 68 ^ Comparative Example 50 Suspension in Oil—————— 0 100 ' Test • Test Case _. .6 1^Number of the biological effects test of the chinchillas 31 319273 200845902 •-...the emulsion prepared according to the preparation example 3 and according to the preparation example Weekly water suspending agent 'in cat body|calling, in the cat's back neck using ι〇〇 times water dilution 4m b with acetonitrile azole 2mg, by microinjection needle perfusion. After 4 days of release, the printed product was recovered and transferred to a Petri dish. The collected eggs were stored at 25 ,, and after 3 weeks, they were observed and resolved. The situation was 'resolved.' After that, the female adult is also released, and the hatching rate is also obtained for the eggs. The results show that the ultraviolet light absorber and the phenol antioxidant are used together with the ultraviolet light absorber or the phenol antioxidant alone. The azole contributes to the prolongation of the residual effect. Table 7 i 1 agent of the season 5 agent and preparation of the water suspension of the suspension of the sample of Example 4 rri-T* » , wide \ ultraviolet light absorber antioxidant amount (parts) 1 month later 1 month Decoction Example 0 Emulsion Compound (2) Compound I 1.0+1.0 0 /4 1 Again 0 Example 31 Oxide Emulsion Compound (5) Compound 0 1.0+1.0 0 0 Example 34 _Emulsion Compound (16) Compound J 1.0+1.0 0 〇tb Comparative Example 55 _ Emulsion Compound (16) One 5.0 0 82 than the car father Example 60 Emulsion Compound J 5.0 0 70 Comparative Example 61 __ Emulsion - 0 99 Example 36 Suspension g Compound C21) Compound rl 1.0+1.0 0 〇 Example 37 Suspending Agent Compound (22) 1 Compound Τ 1·0+ 1·0 0 〇 Example 39 Μ Suspending Agent Compound (13) Compound Ζ 1.0+1.0 0 〇Comparative Example 64 Suspending Agent Compound (22) — 5.0 0 80 Comparative Example 69 ΜSuspending Agent-Compound Τ 5.0 0 65 Comparative Example 72 it suspending agent — — 0 100 319273 32
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