CN101431892B - 液体组合物、液体组合物的制造方法以及哺乳动物及鸟类的外部寄生虫防除剂 - Google Patents
液体组合物、液体组合物的制造方法以及哺乳动物及鸟类的外部寄生虫防除剂 Download PDFInfo
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- CN101431892B CN101431892B CN200680054431XA CN200680054431A CN101431892B CN 101431892 B CN101431892 B CN 101431892B CN 200680054431X A CN200680054431X A CN 200680054431XA CN 200680054431 A CN200680054431 A CN 200680054431A CN 101431892 B CN101431892 B CN 101431892B
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Abstract
本发明提供一种液体组合物,含有(a)分子中不含氮原子、且具有羰基或磺酰基的溶剂:21~70重量份;(b)选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯和二元醇单烷基醚中的至少一种:30~78.9重量份;(c)生理活性成分:0.001~30重量份;(d)水:0.001~49重量份。
Description
技术领域
本发明涉及染料对光和/或热的稳定性优异的液体组合物,此组合物的制造方法以及哺乳动物和鸟类的外部寄生虫防除剂。
背景技术
在农药制剂(药物组合物)等中,从使制剂容易识别、防止误饮等的观点出发,有时要在制剂中添加染料。
这样的染料是有机色素,一般对光、热是不稳定的。
在粉状或粒状的制剂中,由于制剂中的固体成分遮蔽了光线,所以染料对光的稳定性的问题不大。
但是,在不含固体成分的液体制剂中,即使在使用遮光容器等的情况下,也经常会由于透过的少许光而使染料分解。此外,在将含有染料的液体制剂在高温下长时间放置的情况下,有时染料会受热而分解。因此,在这样的情况下,不能得到具有初期色调的液体组合物,而且染料的分解物有时对药效有恶劣的影响。
在与本发明有关的专利文献1中,记载了以规定比例含有a:昆虫烟碱性乙酰胆碱受体的作用物质或拮抗物质、b:水、c:非环式醇类、d:着色剂等的制剂。
但是,在此文献中没有记载关于为了提高着色剂对光和/或热的稳定性而选择使用的溶剂这一方面。
另外,在专利文献2中,记载了用于对人的寄生性昆虫类和蜱类进行经皮防除的制剂,其含有如下组成:(i)相对于制剂总重量浓度为0.0001~20重量%的昆虫类烟碱性乙酰胆碱受体激动剂或拮抗剂;(ii)相对于制剂总重量浓度为2.5~99.9999重量%的选自环状碳酸酯(cycliccarbonate)的溶剂;(iii)根据不同情况而选择含有的、相对于制剂总重量浓度为0~95重量%的选自醇的其它溶剂;(iv)根据不同情况而选择含有的、相对于制剂总重量浓度为0~30重量%的选自增粘剂、展开剂、着色剂、抗氧化剂、发泡剂、保存剂、胶粘剂或乳化剂中的其它助剂。
但是,在此文献中记载的制剂(组合物)不含水。此外,在此文献中,虽然记载了制剂中可以含有着色剂,但没有具体公开在制剂中的添加着色剂的例子。
专利文献1:特表2002-503682号公报
专利文献2:特表2000-509023号公报
发明内容
本发明的课题是,提供染料对光和/或热的稳定性优异的液体组合物、该液体组合物的制造方法以及含有该液体组合物的哺乳动物和鸟类的外部寄生虫防除剂。
本发明人等为了解决上述课题进行了锐意研究,结果发现,在以规定比例含有(a)分子中不含氮原子、且具有羰基或磺酰基的溶剂;(b)选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯和二元醇单烷基醚中的至少一种;(c)生理活性成分以及(d)水的液体组合物中,染料对光和/或热实现了稳定化。还发现,在此液体组合物中,含有类新烟碱(ネオニコチノイド)系杀虫活性成分作为(c)生理活性成分的组合物,作为哺乳动物和鸟类的外部寄生虫防除剂是有用的,至此完成了本发明。
因此,根据本发明的第一方面,提供下述(1)~(11)的液体组合物。
(1)一种液体组合物,其特征在于,含有下述(a)~(d)成分:
(a)分子中不含氮原子、且具有羰基或磺酰基的溶剂:21~70重量份;
(b)选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯和二元醇单烷基醚中的至少一种:30~78.9重量份;
(c)生理活性成分:0.001~30重量份;
(d)水:0.001~49重量份。
(2)一种液体组合物,其特征在于,含有下述(a)~(d)成分:
(a)分子中不含氮原子、且具有羰基或磺酰基的溶剂:50~80重量份;
(b)选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯和二元醇单烷基醚中的至少一种:20~49.9重量份;
(c)生理活性成分:0.001~30重量份;
(d)水:0.001~19重量份。
(3)如(1)或(2)所述的液体组合物,其特征在于,还含有染料作为(e)成分。
(4)如(1)或(2)所述的液体组合物,其特征在于,还含有相对于全部组合物为0.001~1重量份的染料作为(e)成分。
(5)如(1)~(4)中任一项所述的液体组合物,其中,上述在分子中不含氮原子、且具有羰基或磺酰基的溶剂是选自内酯类、亚砜类、环酮类以及环式碳酸酯类中的至少一种。
(6)如(1)~(5)中任一项所述的液体组合物,其中,上述生理活性成分是农药活性成分。
(7)如(6)所述的液体组合物,其中,上述农药活性成分是类新烟碱系杀虫活性成分。
(8)如(6)所述液体组合物,其中,上述农药活性成分是选自啶虫脒、噻虫胺、噻虫嗪、噻虫啉、吡虫啉、呋虫胺和烯啶虫胺中的至少一种。
(9)如(3)~(8)中任一项所述的液体组合物,其中,上述染料是选自酸性染料、碱性染料、媒染染料、酸性媒染染料、直接染料、分散染料、硫化染料、还原染料、冰染染料、氧化染料、活性染料、油溶染料、食用色素、天然色素和荧光增白剂中的至少一种。
(10)如在(3)~(8)中任一项所述的液体组合物,其中,上述染料是选自食用色素、天然色素、茜素绿G、醌茜绿SS、亮绿、亚甲蓝、酸性黄和苏丹黄GG中的至少一种。
(11)如(9)或(10)所述的液体组合物,其中,上述天然色素是选自类胡萝卜素系色素、类黄酮系色素、卟啉系色素、姜黄色素、红曲黄色素、红曲色素、栀子色素、甜菜红、叶绿酸铜钠、栀子蓝色素、蓝藻色素、植物碳末色素和焦糖色素中的至少一种。
根据本发明的第二方面,提供下述(12)~(14)的液体组合物的制造方法。
(12)一种液体组合物的制造方法,其特征在于,在分子中不合氮原子、且具有羰基或磺酰基的溶剂中添加含有染料的水溶液,进行混合。
(13)如(3)或(4)所述液体组合物的制造方法,其特征在于,在(1)所述的液体组合物中添加含有染料的水溶液,进行混合。
(14)如(3)或(4)所述液体组合物的制造方法,其特征在于,在(2)所述的液体组合物中添加含有染料的水溶液,进行混合。
根据本发明的第三方面,提供下述(15)所述的哺乳动物和鸟类的外部寄生虫防除剂。
(15)一种哺乳动物和鸟类的外部寄生虫防除剂,含有上述(7)~(11)中任一项所述的液体组合物。
本发明的液体组合物,其染料对光和/或热的稳定性优异。
通过在本发明的液体组合物中溶解对光、热容易分解的染料,能够经过长的时间仍获得染料的均匀显色。
根据本发明的制造方法,即使在使用在有机溶剂中的溶解度低的染料的情况下,通过预先将染料溶解于少量水中,也能够得到染料均匀溶解而成的液体组合物。
根据本发明,能够得到使用了对皮肤几乎没有刺激的溶剂、对人和动物的安全性高、液体不会分离、有效成分不会析出的外部寄生虫防除用液体组合物。
附图说明
图1是表示液体组合物(C)的制造方法的流程图。
图2是表示液体组合物(C)的其它制造方法的流程图。
具体实施方式
下面,分成1)液体组合物、2)液体组合物的制造方法、3)哺乳动物和鸟类的外部寄生虫防除剂这几项详细说明本发明。
1)液体组合物
本发明的液体组合物是下述组合物(A)~(D)中的任一种。
组合物(A)
(a)分子中不含氮原子、且具有羰基或磺酰基的溶剂:21~70重量份;
(b)选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯和二元醇单烷基醚中的至少一种:30~78.9重量份;
(c)生理活性成分:0.001~30重量份;
(d)水:0.001~49重量份。
组合物(B)
(a)分子中不含氮原子、且具有羰基或磺酰基的溶剂:50~80重量份;
(b)选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯和二元醇单烷基醚中的至少一种:20~49.9重量份;
(c)生理活性成分:0.001~30重量份;
(d)水:0.001~19重量份。
组合物(C)
(a)分子中不含氮原子、且具有羰基或磺酰基的溶剂:21~70重量份;
(b)选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯和二元醇单烷基醚中的至少一种:30~78.9重量份;
(c)生理活性成分:0.001~30重量份;
(d)水:0.001~49重量份;
(e)染料。
组合物(D)
(a)分子中不含氮原子、且具有羰基或磺酰基的溶剂:50~80重量份;
(b)选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯和二元醇单烷基醚中的至少一种:20~49.9重量份;
(c)生理活性成分:0.001~30重量份;
(d)水:0.001~19重量份;
(e)染料。
(a)分子中不含氮原子、且具有羰基或磺酰基的溶剂
本发明的液体组合物,含有分子中不含氮原子、且具有羰基或磺酰基的溶剂(下面有时称为(a)成分)作为(a)成分。
作为在本发明中使用的分子中不含氮原子、且具有羰基或磺酰基的溶剂,只要在分子中不含氮原子且具有羰基或磺酰基,就没有特别的限制。
作为优选的具体例子,可以举出选自内酯类、亚砜类、环酮类和环式碳酸酯类中的至少一种。
作为内酯类并没有特别的限制,可以是γ-内酯、δ-内酯、ε-内酯和大环内酯等中的任何一种。
作为内酯化合物的具体例子,可以举出β-丁内酯、β-丙内酯、γ-丁内酯、γ-戊内酯、δ-戊内酯、ε-十二内酯等。
作为亚砜类,可以举出二甲基亚砜、二乙基亚砜、甲基乙基亚砜、二丙基亚砜、二苯基亚砜、甲基苯基亚砜等。
作为环酮类,可以举出环戊酮、甲基环戊酮、环己酮、甲基环己酮、环庚酮、4,4-二甲氧基-2-丁酮、(3,4-二甲氧基苯基)丙酮、2-(1-环己烯基)环己酮、甲基环己酮、4-羟基-2-丁酮、异佛尔酮、环辛酮、环己酮二甲基乙缩醛等。
作为环式碳酸酯,可以举出碳酸乙二醇酯、碳酸丙二醇酯、碳酸丁二醇酯等。
相对于100重量份的组合物(A)或组合物(C),上述(a)成分的含量为21~70重量份,相对于100重量份的组合物(B)或组合物(D),上述(a)成分的含量为50~80重量份。通过在此范围内使用(a)成分,能够得到染料对光和/或热的稳定性优异的液体组合物。
(b)选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯和二元醇单烷基醚中的至少一种。
本发明的液体组合物,含有选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯、二元醇单烷基醚中的至少一种(下面有时称为(b)成分)作为(b)成分。
作为在本发明中使用的非环式醇,可以举出可以具有取代基的碳原子数1~20的脂肪族烷醇类。可以举出例如乙醇、丙醇、异丙醇、丁醇、异丁醇、叔丁醇、戊醇、异戊醇、己醇、庚醇、辛醇、壬醇、2-乙基-1-己醇、癸醇、十三烷醇、2-辛基-1-十二烷醇、四氢糠醇、3-甲氧基-1-丁醇、环己醇、3-甲基-3-甲氧基-1-丁醇、糠醇、3,5-二甲基-1-己炔-3-醇、2-苯氧基乙醇、缩水甘油等。
作为烷撑二醇,可以举出乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、3-丁二醇、丁基二乙二醇、己二醇、异丙二醇、1,3-丁二醇、1,5-戊二醇、三乙二醇、1,4-丁二醇、2-甲基-1,5-戊二醇、2-甲基-2,4-戊二醇、辛二醇、二乙二醇、丁基二乙二醇等。
作为聚烷撑二醇,可以举出聚乙二醇、聚丙二醇、聚丁二醇等。
作为三元醇,可以举出1,2,6-己三醇、甘油等。
作为二元醇单乙酸酯,可以举出乙二醇单乙酸酯、二乙二醇单乙基醚乙酸酯、3-甲基-3-甲氧基-1-丁基乙酸酯、乙二醇单乙酸酯等。
作为二元醇单烷基醚,可以举出乙二醇单甲基醚、乙二醇单乙基醚、乙二醇异丙基醚、乙二醇单丁基醚、乙二醇异戊基醚、乙二醇单苯基醚、乙二醇苄基醚、乙二醇单己基醚、二乙二醇单甲基醚、二乙二醇单乙基醚、二乙二醇单丁基醚、二乙二醇甲基乙基醚、三乙二醇单甲基醚、丙二醇单甲基醚、丙二醇单乙基醚、丙二醇单丁基醚、二丙二醇单甲基醚、二丙二醇单乙基醚等。
它们可以单独使用一种或者两种以上组合使用。
相对于100重量份的组合物(A)或组合物(C),上述(b)成分的含量为30~78.9重量份,相对于100重量份的组合物(B)或组合物(D),上述(b)成分的含量为20~49.9重量份。通过在此范围内使用(b)成分,能够得到染料对光和/热的稳定性优异的液体组合物。
(c)生理活性成分
本发明的液体组合物含有生理活性成分(下面有时称为(c)成分)作为(c)成分。
作为在本发明中使用的生理活性成分,没有特别的制约。可以举出例如农药活性成分、医药活性成分等,其中优选是农药活性成分。生理活性成分可以单独使用一种,或者两种以上混合使用。
作为农药活性成分,可以举出如下所示的杀菌剂、杀虫剂、杀螨剂、植物生长调节剂、除草剂、杀鼠剂、防菌剂、防霉剂、防藻剂等。
作为杀菌剂,可以举出CNA、DPC、EDDP、IBP、PCNB、TPN、土壤杆菌、稻瘟灵、种菌唑、异菌脲、双胍辛烷苯基磺酸盐、双胍辛乙酸盐、酰胺唑、氯唑灵(Echlomezole)、霜灵、氧化萎锈灵、土霉素、羟基喹啉铜、喹酸、春雷霉素、多菌灵、喹喔啉、克菌丹、地茂散、乙霉威、哒嗪酮、二噻农、代森辛、苯醚甲环唑、环唑醇、二甲嘧酚、福美锌、链霉素、次磺酸系(抑菌灵)、棉隆、噻二嗪、噻菌灵、甲基硫菌灵、三嗪、叶枯酞、戊唑醇、对苯二甲酸铜、三唑酮、三嗪、水杨菌胺、三环唑、氟菌唑、嗪氨灵、甲基立枯磷、壬基酚磺酸铜、井岗霉素、双苯三唑醇、羟基异唑、吡菌磷、啶斑肟、咯喹酮、乙烯菌核利、氯苯嘧啶醇、嘧菌腙、四氟苯酞、灭瘟素、氟啶胺、氟氯菌核利、磺菌胺、氟酰胺、咪鲜胺、腐霉利、双霉威盐酸盐、丙环唑、丙森锌、烯丙苯噻唑、己唑醇、稻瘟酯、戊菌隆、苯噻菌清、乙磷铝、多抗霉素、代森福美锌、腈菌唑、米多霉素、磺菌威、甲霜灵、嘧菌胺、灭锈胺、硫酸铜烯丙苯噻唑等。
作为杀虫剂,可以举出BPMC、BPPS、BRP、CPCBS、CVMP、CVP、CYAP、DCIP、DEP、ECP、EPN、ESP、MIPC、MPMC、MPP、MTMC、PAP、PHC、PMP、XMC、氟丙菊酯、啶虫脒、乙酰甲胺磷、双甲脒、棉铃威、丙烯菊酯、唑磷、异柳磷、吡虫啉、乙硫苯威、乙硫磷、乙基二甲硫吸磷、醚菊酯、丙线磷MC、乙嘧硫磷、杀线威、油酸钠、杀螟丹、丁硫克百威、喹硫磷、四螨嗪、毒死蜱、甲基毒死蜱、氟啶脲、克氯苯、开乐散、蔬果磷、除螨灵、乙氰菊酯、氯氟氰菊酯、氟氯氰菊酯、除虫脲、氯氰菊酯、甲基毒虫畏、乐果、灭蝇胺、硫丙磷、二嗪磷、硫双威、甲基乙拌磷、三氯杀螨砜、吡螨胺、七氟菊酯、伏虫隆、四溴菊酯、烯啶虫胺、蚜灭多、苄螨醚、联苯菊酯、吡唑硫磷、哒嗪硫磷、达螨灵、抗蚜威、嘧螨醚、甲基嘧啶磷、氟虫腈、溴螨酯、苯氧威、苯硫威、氰戊菊酯、唑螨酯、甲氰菊酯、噻嗪酮、呋线威、氟氰戊菊酯、丙硫磷、丙虫磷、丙溴磷、噻螨酮、氯菊酯、杀虫磺、硫丹、杀螨特、恶虫威、丙硫克百威、伏杀硫磷、噻唑硫磷、浏阳霉素复合物、聚丁烯、安果、马拉松、线虫灵(Mesulfenfos)、灭多威、四聚乙醛、久效磷、苄呋菊酯、盐酸左旋咪唑、苯丁锡、酒石酸甲噻嘧啶等。
作为除草剂,可以举出2,4-PA、ACN、CNP、DAP、DBN、DCBN、DCMU、DCPA、DPA、DSMA、IPC、MBPMC、MCC、MCP、MCPB、MCPP、MDBA、PAC、SAP、TCA、TCTP、碘苯腈、磺草灵、莠去津、甲基胺草磷、莠灭净、甲草胺、禾草灭、异隆、异酰草胺、灭草烟、唑吡嘧磺隆、戊草丹、磺噻隆、草灵、旱草丹、特胺灵、禾草克、二氯喹啉酸、草甘膦、库洛美特辛尼(chlormetoxinyl)、稗草胺、氯酞亚胺(chlorphthalim)、氰草津、氰酸钠、敌草快、氟硫草定、环草隆、醚磺隆、草乃敌、西玛津、异戊乙净、西草净、哌草丹、特草定、杀草隆、噻氟隆、噻吩磺隆、四氟丙酸钠、噻吩草胺、丁噻隆、绿草定、氟乐灵、双丙氨磷、表萘丙酰草胺、百草枯、毒莠定、毒莠定、甲羧除草醚、哌草磷、苄草唑、吡嘧黄隆、吡唑特、稗草畏、唑禾草灵、酚硫杀、甜菜宁、丁草胺、抑草磷、啶嘧磺隆、吡氟禾草灵、丙草胺、氨基丙氟灵、戊炔草胺、除草定、扑草净、溴丁酰草胺、环嗪酮、氟草胺、苄嘧磺隆、吡草酮、灭草松、禾草丹、二甲戊乐灵、调节膦、甲基杀草隆、甲磺隆、异丙甲草胺、嗪草酮、苯噻草胺、草达灭、利谷隆、环草定等。
作为杀鼠剂,可以举出香豆素系、氯鼠酮、硫酸铊、一氟乙酸钠、磷化锌等。
作为防菌剂、防霉剂、防藻剂,可以举出三烷基三胺、乙醇、异丙醇、丙醇、三硝基甲烷、氯丁醇、溴硝醇、戊二醛、甲醛、α-溴代肉桂醛、SKANE M-8、凯松CG(KATHON CG)、NS-500W、BIT、正丁基BIT、异硫氰酸烯丙酯、噻菌灵、2-苯并咪唑氨基甲酸甲酯、Lauricidin、BIOBAN、三氯卡班、卤卡班、古拉西卡鲁(glasisicar)、苯甲酸、山梨酸、癸酸、丙酸、10-十一烯酸、山梨酸钾、丙酸钾、苯甲酸钾、邻苯二甲酸一镁、十一烯酸锌、8-羟基喹啉、喹啉铜、TMTD、三氯沙、二氯和拉尼立德(dichlohelanilide)、甲苯氟磺胺、鱼精蛋白、蛋白溶菌酶、苯噻菌清、威百亩、三嗪、戊唑醇、桧木醇、四氯邻苯二甲腈、TEKTAMER38、葡糖酸洗必泰、洗必泰盐酸盐、聚六亚甲基双胍、聚双胍盐酸盐、旦特普洛姆(danthoprom)、库利旦特(clidant)、吡硫钠、吡硫锌、DENSIL、吡硫铜、麝香草酚、异丙基甲酚、OPP、苯酚、对羟基苯甲酸丁酯、对羟基苯甲酸乙酯、对羟基苯甲酸甲酯、对羟基苯甲酸丙酯、间甲酚、邻甲酚、对甲酚、邻苯基苯酚钠、苄氯酚、对氯苯酚、对氯间二甲苯酚、对氯甲酚、氟灭菌丹、聚赖氨酸、BIOBAN P-1487、二碘代甲基对甲苯基砜、聚乙烯基吡咯烷酮对氯异氰酸酯、过氧化氢、稳定化二氧化氯、过乙酸、萘酸铜、novalonAG300、氯化银、氧化钛、银、磷酸锌钙、Silver Ace、银锌铝硅酸盐、银锌沸石、novalon AGZ330、HOLONKILLER、Dimer 136、洁尔灭、二癸基二甲基氯化铵、Bardac 2250/80、苯佐特氯铵(Benzotonium chloride)、Hyamine 3500J、十六烷基基溴化铵、西曲溴胺、CTAB、十六烷基三甲基溴化铵、Dimer 38、洁尔灭、Hyamine 3500J、Bardac 170P、DC-5700、十六烷基氯化吡啶壳聚糖、敌草隆、DCMU、PREVENTOLA6、CMI、2Cl-OIT、BCM、ZPT、BNP、OIT、IPBC、TCMSP等。
作为植物生长调节剂,可以举出脱落酸、抗倒胺、吲哚丁酸、烯效唑、吲熟酯、乙烯利、氧亚乙基二十二烷醇、8-羟基喹啉硫酸盐、氯化钙、硫酸钙、过氧化钙、喹喔啉、DEP、座果酸、矮壮素、小球藻抽提液、氯化胆碱、氨基氰、滴丙酸、赤霉素、丁酰肼、癸醇、抗倒酯、多效唑、石蜡、胡椒基丁醚、吡草醚、呋嘧醇、茉莉酸诱导体、调环酸钙盐、苄基氨基嘌呤、二甲戊乐灵、丙硫克百威、抗倒胺、氯吡脲、马来酰肼钾、缩节胺、1-萘基乙酰胺、4-CPA、MCPA乙硫酯、MCPB等。
其中,在本发明中,作为生理活性成分,更优选是类新烟碱系农药活性成分,特别优选是选自啶虫脒、噻虫胺、噻虫嗪、噻虫啉、吡虫啉、呋虫胺、烯啶虫胺中的至少一种。
上述(c)成分的含量,可根据所用的生理活性成分的种类和液体组合物的用途等适当选择,但相对于100重量份的组合物(A)~(D),通常为0.001~30重量份,优选为1~20重量份。
(d)水
本发明的液体组合物含有水作为(d)成分。
作为使用的水,优选杂质含量少的水。例如可以使用井水、饮用或防火灌溉等用水、自来水、蒸馏水、离子交换水等。
相对于100重量份的组合物(A)或组合物(C),水的含量为0.001~49重量份,相对于100重量份的组合物(B)或组合物(D),水的含量为0.001~19重量份。通过在此范围内使用作为(d)成分的水,能够得到染料对光和/或热的稳定性优异的液体组合物。
(e)染料
上述组合物(C)和(D)含有染料(下面有时称为(e)成分)作为成分(e)。
在本发明中使用的染料,是色素中对纤维等材料具有亲和性,溶解于水、有机溶剂,具有从此溶剂中选择性地被吸收而染色的能力的物质。此外,色素是指选择性地吸收可见光而显示固有色相的有色物质。
在本发明的液体组合物中使用的染料,没有特别的限制。可以举出例如酸性染料、碱性染料、媒染染料、酸性媒染染料、直接染料、分散染料、硫化染料、还原染料、冰染染料、氧化染料、活性染料、油溶染料、食用色素、天然色素和荧光增白剂等。这些染料可以单独使用一种,或者两种以上组合使用。
酸性染料是具有磺酸基、羧基等酸性亲水性基团的水溶性染料。作为代表可以举出酸性橙7(OrangeII)、甲基红等。
碱性染料是以无色阴离子与含有氨基、取代氨基或含氮杂环基等碱性基团的阳离子形成盐的染料。作为代表可以举出结晶紫、俾士麦棕G、碱性蓝9(亚甲基蓝)等。
媒染染料是预先用水溶性金属盐(媒染剂)处理纤维,加热水解为金属氧化物后,通过染色在纤维上生成不溶性金属盐配合物而染色的染料。作为代表可以举出茜素、媒染红11等。
酸性媒染染料是具有酸性染料和媒染染料两者的性质的染料。作为代表可以举出酸性媒介黑T、媒染黑3等。
直接染料是能够直接对棉花、尼龙等纤维素纤维染色的水溶性染料。作为代表可以举出刚果红、直接红2等。
分散染料是将水不溶性的染料从分散浴中对疏水性纤维进行染色的染料。作为代表可以举出分散红73、分散橙3、分散红17、分散紫1等。
硫化染料是将氨基苯酚、靛酚、硝基苯酚等比较简单的芳香族化合物与硫化钠或硫一起熔融(硫化)而生成的含硫染料。作为代表可以举出硫化黑B等。
还原染料也称为染缸染料,是本来不溶于水但进行如下染法的染料,即,在碱存在下还原而成为水溶性(无色化合物的碱式盐),在此状态下将纤维染色后与空气接触而氧化,使原染料在纤维上再生。作为代表可以举出还原红1、还原蓝1(靛蓝)等。
冰染染料是使水溶性的两个成分(重氮成分和偶联成分)在纤维素纤维上发生反应(偶联),成为不溶于水的偶氮染料而达到染色目的的染料,并非现成的染料。作为代表性的底染剂,可以举出色酚AS等,作为显色剂,可以举出蓝色基B等。
氧化染料是采用在纤维上将芳香族胺、二胺或氨基酚类进行氧化而生成不溶性染料的染色法的染料,作为代表可以举出将苯胺氧化而得到的苯胺黑等。
活性染料也称为反应性染料,是与纤维形成共价键而染色的染料。作为代表可以举出活性红24等。
所谓油溶染料也称为油溶性染料,是非水溶性而可溶于以矿物油、精油、油脂为代表的许多有机溶剂的染料。作为代表可以举出溶剂红24等。
荧光增白剂是通过发出从蓝到紫的荧光,成为纤维特有的淡黄色的补色而显示出纯白的染料。作为代表可以举出荧光增白剂B等。
在这些当中,在本发明的液体组合物中,上述染料更优选为选自食用色素、天然色素、茜素绿G、醌茜绿SS、亮绿、亚甲蓝、酸性黄和苏丹黄GG中的至少一种。这些染料安全性高,环境污染的危险比较小。
食用色素是可以作为食品添加剂使用的色素。作为代表可以举出食用红2号(Amaranth:苋菜红)、食用红3号(Erythrosine:赤藓红)、食用红102号(New Coccine:胭脂红)、食用红104号(Phloxine:荧光桃红)、食用红105号(Rose Bengal:孟加拉玫瑰红)、食用106号(AcidRed:酸性红)、食用黄4号(Tartrazine:柠檬黄)、食用黄5号(SunsetYellow FCF:日落黄FCF)、食用绿3号(Fast Green FCF:固绿FCF)、食用蓝1号(Brilliant Blue FCF:亮蓝FCF)、食用蓝2号(Indigo Carmine:靛蓝胭脂)、食用红40号(诱惑红AC)等。
天然色素是习惯上作为食品使用的从天然物中提取的染料。作为天然色素的优选例子,可以举出类胡萝卜素系色素、类黄酮系色素、卟啉系色素、姜黄系色素、红曲黄色素、红曲色素、栀子色素、甜菜红、叶绿酸铜钠、栀子蓝色素、蓝藻色素、植物碳末色素和焦糖色素中的至少一种。
作为这些天然色素更具体的例子,可以举出栀子黄色素(藏化素、藏红花酸)、胭脂树橙色素(红木素、降红木素)、红辣椒抽提色素(辣椒红色素)、胡萝卜色素(β-胡萝卜素)、番茄色素(菌脂色素)、金盏草色素(类胡萝卜色素、类黄酮)、β-阿朴-8-胡萝卜醛、角黄素、辣椒色素等类胡萝卜素系天然色素;洋葱色素、牛油果色素、核桃外皮天然色素、菊苣色素等类黄酮系天然色素;红花黄色素(红花黄(safflomin))、红花红色素(红花素(carthamin))等查尔酮系天然色素;紫苏色素(紫苏素、丙二酰基紫苏素)、红甘蓝色素(花青素酰基葡萄糖苷)、红萝卜色素(花葵素酰基葡萄糖苷)、紫薯色素(花青素酰基葡萄糖苷、芍药素酰基葡萄糖苷)、紫玉米色素、葡萄果皮色素(葡萄酒色素(oenocyanine))、接骨木色素(花青素葡萄糖苷、翠雀素葡萄糖苷)、葡萄果汁色素、蓝莓色素、木槿色素等花青苷系天然色素;可可色素、柿色素(类黄酮)、罗望子色素、高粱红色素(芹菜啶、木犀草啶)等黄酮系天然色素;角豆(Carob)色素、甘草抽提色素等黄酮醇系天然色素;叶绿素等卟啉系天然色素;胭脂红色素(胭脂红酸)、虫胶色素(虫胶红酸类)、茜草色素(茜草红、茜草根苷)等蒽醌系天然色素;
姜黄色素(黄色素)、红曲黄色素(Xanthomonasin类)、红曲色素(红曲玉红素、红曲黄素)、栀子色素、甜菜红(甜菜碱系的甜菜红、异甜菜红)、叶绿酸铜钠、栀子蓝色素、蓝藻色素(蓝藻蛋白)、植物碳末色素、焦糖色素等。
(e)成分的配合量没有特别的限制,可根据液体组合物的用途、配合染料的目的适当进行选择,但相对于100重量份的组合物(C)或(D),优选为0.001~1重量份,更优选为0.005~0.5重量份。
(f)其它添加剂
本发明的液体组合物,根据需要、在不超出本发明主旨的范围内可含有其他添加剂作为(f)成分。作为此其他添加剂,可以举出表面活性剂、分子内具有氮原子的溶剂、胶粘剂、增粘剂等。
作为表面活性剂,可以举出非离子性表面活性剂、阴离子性表面活性剂、阳离子性表面活性剂和两性表面活性剂等。
作为非离子性表面活性剂,可以举出聚氧烯烷基醚、聚氧烯烷基苯基醚、聚氧烯苯乙烯基苯基醚、聚氧烯烷基酯、聚氧烯脱水山梨糖醇脂肪酸酯、蓖麻油聚氧烯醚、聚氧乙烯聚氧丙烯嵌段聚合物、聚氧烯烷基胺等聚氧烯非离子性表面活性剂,但并不限于这些化合物。上述所谓聚氧烯,表示聚氧乙烯、聚氧丙烯、聚氧乙烯聚氧丙烯的嵌段聚合物及其混合物。
作为阴离子性表面活性剂,可以举出高级脂肪酸(C10~22)的碱金属盐、碱土类金属盐或铵盐,例如从椰子油或动物脂得到的天然脂肪酸混合物的金属盐,或者特别是脂肪族磺酸、脂肪族硫酸、脂肪族磺基琥珀酸、烷基芳基磺酸或烷芳基硫酸酯等。磺酸、硫酸或磺基琥珀酸的酯通常以碱金属盐、碱土类金属盐、胺盐或铵盐的形态提供。此外,通常是含有碳原子数8~22的烷基,例如烷基硫酸酯、从天然脂肪酸得到的脂肪族醇硫酸酯的混合物或二烷基磺基琥珀酸酯的钠、钾、钙或镁盐。作为烷芳基磺酸酯的例子,是十二烷基苯磺酸、萘磺酸及其甲醛缩合物或者三苯乙烯基苯酚硫酸酯的钠、钙、铵或三乙醇胺盐。可以举出适当的磷酸盐,例如含有4~14mol环氧乙烷的烷基酚、以及三苯乙烯基酚加成物的磷酸酯的钠、钙、铵或三乙醇胺盐。
作为阳离子性表面活性剂,可以举出例如脂肪族胺及其季胺盐、脂肪酸酰胺胺盐、烷基三烷撑二醇铵盐、酰基胍衍生物、单-N-长链酰基碱性氨基酸低级烷基酯盐等氨基酸系阳离子性表面活性剂、烷基苄烷铵盐、烷基吡啶盐、咪唑盐等。
这些表面活性剂可以单独使用一种,或两种以上组合使用。
作为使用的分子内含有氮原子的溶剂,可以举出N-甲基-2-吡咯烷酮、甲酰胺、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等酰胺系溶剂;
3-乙氧基丙胺、3-甲氧基丙胺、N,N-二乙基乙醇胺、N,N-二甲基乙醇胺、n-己胺、N-甲基-3,3’-亚氨基二(丙胺)、异丙胺、乙醇胺、乙胺、N-甲基二乙醇胺、仲丁胺、二乙胺、环己胺、苯乙胺、丙胺、苄胺、正丁胺、二异丙胺、三乙胺、二正丁胺、三正丁胺、二环己基胺、二苄基胺、三正辛基胺、二烯丙基胺、三烯丙基胺、叔丁胺、二-2-乙基己胺、2-乙基己胺、3-(2-乙基己氧基)丙胺、烯丙胺、异丙醇胺、N,N-二丁基乙醇胺、N-(2-氨基乙基)乙醇胺、N,N-二异丙基乙胺等胺系溶剂;
乙二胺、1,2-二氨基丙烷、1,3-二氨基丙烷、1,4-二氨基丁烷、3-(二乙基氨基)丙胺、3-(二甲基氨基)丙胺、3-(甲基氨基)丙胺、3,3-亚氨基二(丙胺)、四甲基-1,3-二氨基丙烷、N,N,N,N-四甲基-1,6-六亚甲基二胺、3-(二丁基氨基)丙胺、N-甲基乙醇胺、2-羟基乙基氨基丙胺、四甲基乙二胺等二胺系溶剂;
吡啶甲醇、2-氰基吡嗪、2-乙烯基吡啶、2-甲基吡嗪、3-醛基吡啶、N-(3-氨丙基)吗啉、N-甲基哌啶、丙烯酰吗啉、喹啉、哌啶、吡啶、吡咯烷、2,5-二甲基吡嗪、二氨丙基哌嗪、喹哪啶、吗啉、N-甲基哌嗪、1-氨基-4-甲基哌嗪、2-氯吡啶、2-哌可啉、4-哌可啉、3-哌可啉、(羟乙基)哌嗪、1-(2-氨乙基)哌嗪、聚乙烯基吡咯烷酮、吖丙啶等环状胺系溶剂;
N,N-二甲基丙烯酰胺、丙烯酸二甲基氨基乙酯、3-二甲基氨基丙烯酸乙酯、甲基丙烯酸二甲基氨基乙酯等氨基丙烯酸系溶剂;
丙烯腈、乙腈、3,3-二甲氧基丙腈、3,3-亚氨基二丙腈、丙酮氰醇、3-羟基丙腈、苯甲腈、丙腈等腈系溶剂;
二甲基肼、单甲基肼等肼系溶剂;
硝基甲烷、2-硝基丙烷、硝基甲苯、1-硝基丙烷、硝基乙烷等硝基化合物系溶剂;
α-甲基吡啶、β-甲基吡啶、γ-甲基吡啶、苯胺、N,N-二乙基苯胺、邻硝基苯甲醚、甲基苯胺、对氨基苯甲醚、2-丙基吡啶、2,4,6-三甲基吡啶、N,N-二甲基苯胺、N-乙基苯胺、二甲基苯胺、N,N-二缩水甘油基苯胺、N,N-二缩水甘油基-邻甲基苯胺、苄基乙基苯胺、2,4,6-三(二甲氨基甲基)苯酚、间三氟甲基苯胺、对乙氧基苯胺、间苯二甲基二胺、均三甲苯胺等苯胺系溶剂;
三烯丙基异氰脲酸酯、邻联甲苯胺异氰酸酯、二烯丙基二甲基氯化铵、巯基乙酸铵、甲苯二异氰酸酯、六亚甲基二异氰酸酯、甲基乙基酮肟等其它含氮化合物溶剂等。
这些溶剂可以单独使用一种,或两种以上组合使用。
作为胶粘剂并没有特别的限制,可以举出例如淀粉、糊精、纤维素、甲基纤维素、乙基纤维素、羧甲基纤维素、羟乙基纤维素、羟丙基纤维素、羧甲基淀粉、普鲁蓝多糖、藻酸钠、藻酸铵、藻酸丙二醇酯、瓜尔胶、刺槐豆胶、阿拉伯胶、黄原胶、明胶、酪素、聚乙烯醇、聚环氧乙烷、聚乙二醇、乙烯-丙烯嵌段聚合物、聚丙烯酸钠、聚乙烯基吡咯烷酮、卡拉胶等。
这些胶粘剂可以单独使用一种,或两种以上组合使用。
作为增粘剂,可以举出羟基烷基纤维素、羧甲基纤维素及其金属盐等纤维素衍生物、聚乙烯醇衍生物、聚乙烯基吡咯烷酮、天然橡胶类、膨润土等。
本发明的液体组合物还可以含有稳定剂之类的固体或液体助剂,例如环氧化或未环氧化的植物油(例如环氧化的椰子油、菜子油或大豆油)、消泡剂(例如硅酮油)、粘度调节剂、粘合剂和/或胶粘剂以及其它有效成分,例如杀细菌剂、杀霉菌剂、杀菌剂或杀螨剂。
本发明的液体组合物可以直接使用,也可以与适当的助剂制成粉剂、粒剂、片剂、可湿性粉剂、水分散粒剂、胶囊剂、液剂、乳剂、乳浊剂、乳化悬浮剂、水悬浮剂、油性悬浮剂等各种形式使用。除了上述制剂形式以外,在适合本发明目的的限度内,可以制成在通常该领域中使用的一切制剂形式。
将农药活性成分作为上述(c)成分来含有的本发明液体组合物,可直接或者用水等稀释后施用在种子、植物体、水面或土壤中。还可以与其它杀菌剂、杀虫剂、除草剂、展开剂、肥料、土壤改良剂等一起使用。
特别是在本发明的液体组合物含有作为上述(c)成分的杀虫活性成分、优选类新烟碱系杀虫活性成分的情况下,如下所述,作为哺乳动物和鸟类的外部寄生虫防除剂是有用的。
此外,本发明的液体组合物除了农业用途以外,还可以作为土壤病虫害防除剂、白蚁防除剂、衣料用剂、害虫防除剂、木材害虫防除剂、毒饵剂、动物外部寄生虫防除剂、卫生害虫防除剂、家庭防疫剂、喷墨打印机用墨、涂料、船底涂料、渔网等的防藻剂、木材的防霉剂等。
2)液体组合物的制造方法
在本发明的液体组合物中,组合物(A)和(B)可以通过按规定比例混合(a)成分、(b)成分、(c)成分、(d)水和根据需要的(f)表面活性剂(下面有时称为(f)成分),使之均匀溶解而得到。
作为将上述(a)成分、(b)成分、(c)成分、(d)水以及根据需要的(f)成分混合并使之均匀溶解的方法,没有特别的限制。可以举出例如使用在槽内设置有搅拌装置的搅拌槽、喷流混合机、静力混合机、阀式均化器、超声波均化器、挤塑机的方法。
组合物(C)和(D)可以例如在图1中所示,将上述(a)成分、(b)成分、(c)成分、(d)水和根据需要的(f)成分以及(e)染料按规定比例混合并均匀溶解而得到。作为将上述(a)成分、(b)成分、(c)成分、(d)水以及根据需要的(f)成分和(e)染料混合并均匀溶解的方法,可以举出与配制上述组合物(A)和(B)的方法同样的方法。
此外,在此情况下,如在图2中所示,当使用的染料在有机溶剂中的溶解度低或者为不溶性的情况下,可预先将染料溶解于水而制成染料的水溶液,将此染料的水溶液添加到有机溶剂中,从而得到使染料均匀溶解并显色的液体组合物。另外,在本发明中,将染料的水溶液添加到有机溶剂中、或者将有机溶剂添加到染料的水溶液中皆可。此外,生理活性成分、任意成分在什么时候加入都可以。
3)哺乳动物和鸟类的外部寄生虫防除剂
本发明的哺乳动物和鸟类的外部寄生虫防除剂,其特征在于,含有本发明的液体组合物,所述本发明的液体组合物中,作为上述(c)成分,含有杀虫活性成分,优选含有类新烟碱系杀虫活性成分。
作为本发明哺乳动物和鸟类的外部寄生虫防除剂的对象的哺乳动物和鸟类,可以举出狗、猫、鼷鼠、鼠、田鼠、豚鼠、松鼠、兔、雪貂、鸟(例如鸽、鹦鹉、鹩哥、文鸟、鹦哥、白腰文鸟、金丝雀)等玩赏动物类;牛、马、猪、绵羊、山羊等家畜类;鸭、鸡、鹅等家禽类等。
作为外部寄生虫,可以举出加害哺乳动物和鸟类的跳蚤、蜱、虱子、蝇、虻、蠓、羽虱等。其中本发明的哺乳动物和鸟类的外部寄生虫防除剂,特别可用作动物寄生性蜱、跳蚤的防除剂。
作为动物寄生性蜱类,可以举出例如微小牛蜱(Boophilusmicroplus)、血红扇头蜱(Rhipicephalus sanguineus)、长角血蜱(Haemaphysalis longicornis)、褐黄血蜱(Haemaphysalis flava)、铃头血蜱(Haemaphysalis campanulata)、嗜群血蜱(Haemaphysalisconcinna)、日本血蜱(Haemaphysalis j aponica)、北岗血蜱(Haemaphysalis kitaokai)、衣亚斯血蜱(Haemaphysalis ias)、卵形硬蜱(Ixodes ovatus)、日本硬蜱(Ixodes nipponensis)、全沟硬蜱(Ixodespersulcatus)、奥特盖血蜱(Haemaphysalis megaspinosa)、网状革蜱(Dermacentor reticulatus)、台湾革蜱(Dermacentor taiwanesis)等硬蜱类;
鸡皮刺螨(Dermanyssus gallinae)、林禽刺螨(Ornithonyssussylviarum)、囊禽刺螨(Ornithonyssus bursa)等叮咬鸟类的蜱类;
威氏真恙螨(Eutrombicula wichmanni)、红纤恙螨(Leptotrombidium akamushi)、苍白纤恙螨(Leptotrombidiumpallidum)、富士纤恙螨(Leptotrobidium fuji)、(Leptotrombidiumtosa)、秋收恙螨(Neotrombicula autumnalis)、北美恙螨(Eutrombiculaalfreddugesi)、宫川恙螨(Helenicula miyagawai)等恙虫类;
犬姬螯螨(Cheyletiella yasguri)、兔姬螯螨(Cheyletiellaparasitivorax)、猫姬螯螨(Cheyletiella blakei)等肉食螨类;
兔痒螨(Psoroptes cuniculi)、牛足螨(Chorioptes bovis)、犬猫耳螨(Otodectes cynotis)、疥螨(Sarcoptes scabiei)、猫背肛螨(Notoedrescati)等疥螨科类;
犬蠕形螨(Demodex canis)之类的蠕形螨类等。
作为蚤类可以举出属于蚤目(Siphonaptera)的外部寄生性无翅昆虫,具体可以举出属于蚤科(Pulicidae)、角叶蚤科(Ceratephyllus)等蚤类的例子。
作为属于蚤科蚤类,可以举出例如犬栉头蚤(Ctenocephalidescanis)、猫栉头蚤(Ctenocephalides felis)、人蚤(Pulex irritans)、禽冠蚤(Echidnophaga gallinacea)、印鼠客蚤(Xenopsylla cheopis)、缓慢细蚤(Leptopsylla segnis)、欧洲鼠蚤(Nosopsyllus fasciatus)、不等单蚤(Monopsyllus anisus)等。
向哺乳动物和鸟类给予本发明组合物,可以通过口服或非口服的方式进行。
作为口服给药的方法,可以举出给予片剂、液体剂、胶囊剂、威化饼干、饼干、肉末、其它饲料等的方法等。
作为非口服给药的方法,可以举出例如将本发明的液体组合物经静脉注射、肌内给药、皮内给药、皮下给药等进行处理的方法;将本发明的液体组合物通过滴注(spot-on)处理、灌注(pour-on)处理、喷涂处理等给药于体表面的方法;使树脂中含有本发明的液体组合物,然后将该树脂埋入哺乳动物和鸟类的皮下的方法等。
向哺乳动物和鸟类给予本发明的液体组合物的量,因给药方法、给药目的、疾病症状等的不同而异,但通常相对于1kg体重的哺乳动物和鸟类,以0.01mg~100g、优选0.1mg~10g的比例给药是适当的。
实施例
下面通过实施例和比较例更具体地说明本发明,但本发明并不受以下实施例的任何限制。
(实施例1~12,比较例1~12)
通过如下方法B中所示的方法配制实施例1~12和比较例1~12的液体组合物。在实施例1~12和比较例1、2、4~12中,得到了各成分均匀溶解的液体组合物。但是在比较例3的液体组合物的情况下,(a)成分没有完全溶解,得到了不均匀的溶液。
方法A:如图1所示,向(a)成分中依次添加规定量的(c)成分、(b)成分、(f)成分、(e)成分和(d)水,进行混合,配制成液体组合物。
方法B:如图2所示,向(a)成分中依次添加规定量的(c)成分、(b)成分和(f)成分,进行混合,再向其中添加将作为(e)成分的染料溶解于蒸馏水而得的水溶液,进行混合,配制成液体组合物。
在配制实施例1~12、比较例1~12的液体组合物时,(a)成分~(f)成分的种类、其使用量(重量份)和配制方法汇总示于表1。
[表1]
表1
表1中,作为(a)成分~(e)成分,使用了如下的化合物。
(a)分子中不含氮原子且具有羰基或磺酰基的溶剂
a-1:γ-丁内酯
a-2:碳酸丙二醇酯
(b)选自非环式醇、烷撑二醇、聚烷撑二醇、三元醇、二元醇单乙酸酯和二元醇单烷基醚中的至少一种;
b-1:二丙二醇
(c)生理活性成分
c-1:啶虫脒(日本曹达公司制造)
(d)水
使用蒸馏水。
(e)染料
e-1:以食用黄4号78%、食用蓝1号2%和食用红40号20%的比例混合而成的混合色素
e-2:食用蓝1号
(f)其他成分
f-1:Pluronic PE6400(BASF公司制造)
NMP:N-甲基吡咯烷酮
(试验例1)对光和热的稳定性试验
将实施例2和比较例1的液体组合物装入透光性高的聚乙烯单层瓶中,在黑暗处于室温下和在黑暗处于54℃的高温下放置2周。另外,将实施例2和比较例1的液体组合物装入透光性高的聚乙烯单层瓶中,曝露在阳光下。从开始曝露于阳光下之后12天或两周之后,目视观察药液的颜色。按照Munsell色度法评价药液的颜色。评价结果示于表2。
表2
表2
从表2可以看出,实施例2的液体组合物,与在实施例2的液体组合物中用32.26重量份的N-甲基吡咯烷酮代替32.26重量份的碳酸丙二醇酯得到的比较例1的液体组合物相比,染料的热稳定性(在暗处54℃放置2周)、光稳定性(在日光下曝露12天)都特别优异。
(试验例2)制剂的稳定性(冷却试验)
将实施例3~12和比较例2~12的液体组合物在-5℃下冷却,观察有无分离、原有成分的析出等。将没有产生相分离的情况评价为○,产生了相分离的情况评价为×。此外,投入少量原有成分晶核,研究有无原有成分晶体生长。目视观察的结果,将没有结晶生长的情况评价为◎;将虽然观察到微细的结晶生长,但恢复到室温之后再次变成均匀溶液的情况评价为○;将观察到有结晶生长,但恢复到室温之后再次成为基本均匀的溶液的情况评价为△;将观察到结晶生长,恢复到室温后也不能成为均匀溶液的情况评价为×。评价结果示于表3。
表3
表3
从表3可以看出,实施例3~7、9、10的液体组合物,即使在冷却到-5℃的情况下也没有引起相分离,在投入原有成分晶核的情况下也没有原有成分结晶生长。
实施例8、11、12的液体组合物,即使在冷却到-5℃的情况下也没有引起相分离,在投入原有成分晶核的情况下,虽然观察到有微细的结晶生长,但经恢复到室温又变成均匀的溶液。
比较例4~7、10的液体组合物,虽然在冷却到-5℃时没有引起相分离,但在投入原有成分晶核的情况下观察到结晶生长。比较例7、9的液体组合物,即使恢复到室温也没有成为均匀的溶液。
比较例2、8、9、11、12的液体组合物,在冷却到-5℃的情况下引起了相分离。
(试验例3)染料的溶解试验
(比较实验1)
试着采用方法A配制与实施例1中配制的液体组合物具有同样成分构成的液体组合物。即,在32.26重量份γ-丁内酯、57.66重量份二丙二醇中添加0.94重量份Pluronic PE6400(BASF公司制造)、8.64重量份啶虫脒、0.0078重量份食用黄4号、0.0002重量份食用蓝1号、0.002重量份食用红40号,结果得到不均匀的溶液。添加0.49重量份蒸馏水以使不溶的染料溶解,用搅拌机(THREEONE moter)混合,但均匀性没有改善,仍然是不均匀的溶液。
目视观察实施例1的液体组合物以及比较实验1中得到的液体组合物中染料的溶解状态、颜色。结果示于表4。
表4
表4
从表4可以看出,即使是同样组成的液体组合物,在向(a)成分中依次添加(c)成分、(b)成分、(f)成分和(e)成分的情况下,得到不均匀的液体组合物,与此相对,在将预先将(e)成分溶解于蒸馏水而得到的水溶液添加到(a)成分、(c)成分、(b)成分和(f)成分的混合液中的情况下,能够得到均匀的液体组合物。
(试验例4)使用犬的对跳蚤的药效试验
(1)配制液体组合物
(实施例13)
在32.26份γ-丁内酯和57.66重量份二丙二醇的混合溶剂中加入8.64重量份啶虫脒并使其溶解,在得到的溶液中加入0.94重量份表面活性剂(Pluronic PE6400,BASF公司制造)和0.49重量份的水,用搅拌机混合溶解,得到均匀的溶液(液体组合物)。
(比较例13)
在35.31重量份γ-丁内酯和63.12重量份二丙二醇的混合溶剂中,加入1.03重量份表面活性剂(Pluronic PE6400,BASF公司制造)和0.54重量份的水,用搅拌机混合溶解,得到均匀的溶液(液体组合物)。
(2)药效试验
对6只各种体重的犬滴注给予规定的药液,在检查日(给药后经过2天、9天、16天、23天和30天之后)的前一天,对6只犬接种规定个数的跳蚤(Ctenocephalidis felis)。
检查在给药(处理)后经过规定的天数之后寄生在犬上的跳蚤数,基于下述计算式求出杀虫率。
杀虫率(%)={(X-Y)/X}×100
上式中,X表示在用比较例13的液体组合物处理过的犬上寄生的跳蚤数,Y表示在用实施例13的液体组合物处理过的犬上的跳蚤数。评价结果示于表5。
表5
表5
从表5可以看出,实施例13的外部寄生虫防除用液体组合物,对防除跳蚤具有优异的效果。
本发明的液体组合物,其染料对光和/或热的稳定性优异。
通过在本发明的液体组合物中溶解对光和/热容易分解的染料,经长期仍能够得到染料的均匀显色。
根据本发明的制造方法,即使在使用在有机溶剂中的溶解度低的染料的情况下,通过预先将染料溶解于少量水中,也能够得到染料均匀溶解的液体组合物。
通过本发明,能够得到使用了对皮肤几乎没有刺激的溶剂、对人和动物的安全性高、液体不会分离、有效成分不会析出的外部寄生虫防除用液体组合物。
Claims (9)
1.一种液体组合物,其特征在于,含有下述(a)~(e)成分:
(a)选自内酯类和环式碳酸酯类中的至少一种:在液体组合物100重量份中为21~70重量份;
(b)选自烷撑二醇和聚烷撑二醇中的至少一种:在液体组合物100重量份中为30~78.9重量份;
(c)类新烟碱系杀虫活性成分:在液体组合物100重量份中为0.001~30重量份;
(d)水:在液体组合物100重量份中为0.001~49重量份;
(e)染料:在液体组合物100重量份中为0.001~1重量份。
2.一种液体组合物,其特征在于,含有下述(a)~(e)成分:
(a)选自内酯类和环式碳酸酯类中的至少一种:在液体组合物100重量份中为50~80重量份;
(b)选自烷撑二醇和聚烷撑二醇中的至少一种:在液体组合物100重量份中为20~49.9重量份;
(c)类新烟碱系杀虫活性成分:在液体组合物100重量份中为0.001~30重量份;
(d)水:在液体组合物100重量份中为0.001~19重量份;
(e)染料:在液体组合物100重量份中为0.001~1重量份。
3.根据权利要求1或2所述的液体组合物,其中,所述类新烟碱系杀虫活性成分是选自啶虫脒、噻虫胺、噻虫嗪、噻虫啉、吡虫啉、呋虫胺和烯啶虫胺中的至少一种。
4.根据权利要求1或2所述的液体组合物,其中所述染料是选自酸性染料、碱性染料、媒染染料、直接染料、分散染料、硫化染料、还原染料、冰染染料、氧化染料、活性染料、油溶染料、食用色素、天然色素和荧光增白剂中的至少一种。
5.根据权利要求1或2所述的液体组合物,其中所述染料是选自食用色素、天然色素、茜素绿G、醌茜绿SS、亮绿、亚甲蓝、酸性黄和苏丹黄GG中的至少一种。
6.根据权利要求4所述的液体组合物,其中所述天然色素是选自类胡萝卜素系色素、类黄酮系色素、卟啉系色素、姜黄色素、红曲黄色素、红曲色素、栀子色素、甜菜红、叶绿酸铜钠、栀子蓝色素、蓝藻色素、植物碳末色素和焦糖色素中的至少一种。
7.进一步含有在液体组合物100重量份中为0.001~1重量份的染料作为(e)成分的液体组合物的制造方法,其特征在于,在含有下述(a)~(d)成分的液体组合物中,添加含有染料的水溶液,进行混合,
(a)选自内酯类和环式碳酸酯类中的至少一种:在液体组合物100重量份中为21~70重量份;
(b)选自烷撑二醇和聚烷撑二醇中的至少一种:在液体组合物100重量份中为30~78.9重量份;
(c)类新烟碱系杀虫活性成分:在液体组合物100重量份中为0.001~30重量份;
(d)水:在液体组合物100重量份中为0.001~49重量份。
8.进一步含有在液体组合物100重量份中为0.001~1重量份的染料作为(e)成分的液体组合物的制造方法,其特征在于,在含有下述(a)~(d)成分的液体组合物中,添加含有染料的水溶液,进行混合,
(a)选自内酯类和环式碳酸酯类中的至少一种:在液体组合物100重量份中为50~80重量份;
(b)选自烷撑二醇和聚烷撑二醇中的至少一种:在液体组合物100重量份中为20~49.9重量份;
(c)类新烟碱系杀虫活性成分:在液体组合物100重量份中为0.001~30重量份;
(d)水:在液体组合物100重量份中为0.001~19重量份。
9.一种哺乳动物和鸟类的外部寄生虫防除剂,含有权利要求1或2所述的液体组合物。
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2006
- 2006-05-02 PL PL06746017T patent/PL2014163T4/pl unknown
- 2006-05-02 US US12/226,339 patent/US9277746B2/en active Active
- 2006-05-02 CN CN200680054431XA patent/CN101431892B/zh active Active
- 2006-05-02 WO PCT/JP2006/309167 patent/WO2007129395A1/ja active Application Filing
- 2006-05-02 KR KR1020087026612A patent/KR101026092B1/ko active Active
- 2006-05-02 JP JP2008514339A patent/JP4956532B2/ja active Active
- 2006-05-02 RU RU2008142926/15A patent/RU2409391C2/ru active
- 2006-05-02 EP EP06746017.0A patent/EP2014163B1/en active Active
- 2006-05-02 ES ES06746017.0T patent/ES2612274T3/es active Active
- 2006-05-02 BR BRPI0621641-2A patent/BRPI0621641B1/pt active IP Right Grant
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2016
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WO1997037544A1 (de) * | 1996-04-03 | 1997-10-16 | Bayer Aktiengesellschaft | Mittel zur bekämpfung parasitierender insekten und milben an menschen |
WO1999041986A1 (de) * | 1998-02-23 | 1999-08-26 | Bayer Aktiengesellschaft | Dermal applizierbare wasserhaltige formulierungen von parasitiziden |
WO1999041987A1 (de) * | 1998-02-23 | 1999-08-26 | Bayer Aktiengesellschaft | Wasserhaltige mittel zur bekämpfung parasitierender insekten und milben an menschen |
CN1389113A (zh) * | 2002-07-22 | 2003-01-08 | 张淑静 | 一种啶虫脒杀虫剂 |
WO2004100662A1 (ja) * | 2003-05-19 | 2004-11-25 | Nippon Soda Co., Ltd. | 殺虫剤組成物 |
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US20090069386A1 (en) | 2009-03-12 |
US20160129114A1 (en) | 2016-05-12 |
EP2014163A4 (en) | 2012-08-08 |
US9277746B2 (en) | 2016-03-08 |
KR101026092B1 (ko) | 2011-03-31 |
PL2014163T3 (pl) | 2017-03-31 |
JP4956532B2 (ja) | 2012-06-20 |
EP2014163A1 (en) | 2009-01-14 |
KR20080108148A (ko) | 2008-12-11 |
BRPI0621641A2 (pt) | 2011-12-20 |
WO2007129395A1 (ja) | 2007-11-15 |
RU2008142926A (ru) | 2010-05-10 |
ES2612274T3 (es) | 2017-05-16 |
CN101431892A (zh) | 2009-05-13 |
PL2014163T4 (pl) | 2017-06-30 |
RU2409391C2 (ru) | 2011-01-20 |
BRPI0621641B1 (pt) | 2020-03-24 |
EP2014163B1 (en) | 2016-09-28 |
JPWO2007129395A1 (ja) | 2009-09-17 |
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