CN1114525A - 非致敏杀虫剂组合物及其方法 - Google Patents
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Abstract
本发明提供了其中3-异噻唑酮用作杀生物剂的组合物,包括堵缝剂、密封剂、油漆、罩光漆、胶粘剂、粘合剂、成膜聚合物,木材浸渍剂、塑料和橡胶。用于建筑、装饰或船舶涂料组合物中的适宜的成膜聚合物是任何被用于水基涂料中的成膜聚合物,优选丙烯酸或乙酸乙烯酯乳液共聚物类型的成膜聚合物。对涂料来说,被包封的颗粒可以通过与成膜聚合物,水和选择性的颜料混合来加入。
Description
本发明涉及含有防治霉病或防止污染的杀生物剂的组合物。
如涂料、罩光漆、胶粘剂、密封剂、粘合剂、堵缝剂、金属加工液等组合物代表性地含有一种用于防治霉病或防止污染的杀生物剂。在这些应用中3—异噻唑酮类杀生物剂非常有效。例如,在易发霉的涂料和其它组合物中,2—正辛基—3—异噻唑酮是普通的杀霉剂。
在船舶漆领域中,已经证明4,5—二氯—2—正辛基—3—异噻唑酮是一种对防止航海被用物如船、码头、鱼网、帆装等上面的干燥膜污染特别有效的杀生物活性成分。对所述的异噻唑酮来说一个问题是油漆工必须小心而不与含有异噻唑酮的湿涂料相接触,因为它会引起皮肤过敏。由于这一问题限制了所述异噻唑酮的商业上可接受性(不仅在船舶漆中,而且在装饰涂料中),为此已进行了大量的研究。先有技术未提出一种解决由3—异噻唑酮类化合物(用为杀生物剂)带来的过敏问题的方法。
以前对封装异噻唑酮杀生物剂的尝试包括在活性成分存在下使甲基丙烯酸甲酯和甲基丙烯酸聚合和然后在涂料中混入包封的杀生物剂以改善其热老化稳定性。
Redlich等人在美国专利5,225,279中教导了为了控制或减少活性成分释放速率而进行的这种封装。
用聚脲包封物封装农药以控制释放速率也是已知的。
但是,到现在为止还没有人解决了由于接触了组合物中的3—异噻唑酮活性成分而过敏的重大问题。
因此本发明的一个目的是提供一种当将3—异噻唑酮杀生物剂用于组合物中时能降低其过敏可能性的方法。
另一目的是提供涂料组合物,该组合物含有3—异噻唑酮杀生物剂并且改进了引起皮肤过敏的可能性。
本发明可达到这些目的和通过下列公开变得很明显的其它目的,本发明的一个方面,涉及包括一种将3—异噻唑酮杀生物剂包封于聚脲颗粒中和将所述颗粒引入到组合物中的方法。
本发明的另一方面涉及一种含有水和杀生物有效量的一种或几种包封于聚脲颗粒中的3—异噻唑酮类化合物的组合物。
本发明也包括用这样的组合物涂覆或浸渍一结构物或基底。
聚脲包封物(或壳)是一种或几种聚异氰酸酯和一种或几种多官能胺的反应产物。优选的聚异氰酸酯是聚亚甲基聚苯基异氰酸酯(PAPI);2,6—甲苯二异氰酸酯(TDI);双(4—异氰酰环己基)甲烷;六亚甲基二异氰酸酯(HDI);对—亚苯基二异氰酸酯,间—亚苯基二异氰酸酯;萘—1,5—二异氰酸酯;二苯基甲烷—4,4—二异氰酸酯(MDI);三苯基甲烷—4,4′,4″—三异氰酸酯,异丙基苯二异氰酸酯;和异佛尔酮二异氰酸酯(IPDI)。优选的多官能胺是1,2—乙二胺;二亚乙基三胺;三亚乙基四胺;四亚乙基五胺;五亚乙基六胺;亚苯基二胺;甲苯二胺;1、3、5—苯三胺·3HCl;2,4,6—三氨基甲苯·3HCl;聚亚乙基胺;1、3、6—三氨基萘;3、4、5、8—四氨基蒽醌;六亚甲基二受;和哌嗪。
聚异氰酸酯和多胺在有3—异噻唑酮活性成分存在下聚合,优选地是通过界面缩聚,其中异氰酸酯和活性成分是在油相中,多官能胺是在水相中。优选地是将有机相加入到混合器的水相中,然后将生成的分散液转移至反应容器中并保持温度在大约30—40℃直到反应完全并形成固体颗粒,将固体颗粒分离并在空气中使之干燥。代表性的颗粒含有25—90%(重量)活性成分,其粒度大约1—100微米。
虽然任何3—异噻唑酮类化合物都是适用的,但优选的3—异噻唑酮化合物是2—正辛基—3—异噻唑酮和4,5—二氯—2—正辛基—3—异噻唑酮,后者对航海应用是优选的,二者对通常用于装饰或建筑涂料中的杀霉剂应用是优选的。
组合物是其中3—异噻唑酮类化合物可用作杀生物剂的任何组合物,包括堵缝剂;密封剂;油漆;罩光漆;胶粘剂;粘合剂;成膜聚合物;木材浸渍剂;塑料和橡胶。
对于建筑,装饰或船舶涂料组合物来说适宜的成膜聚合物是在水基油漆中所使用的那些,优选丙烯酸或乙酸乙烯酯乳液共聚物型的聚合物。
对涂料来说,包封颗粒可以通过与成膜聚合物、水和选择性地与颜料混合来加入。
可用标准方法将异噻唑酮类化合物包封于各种聚合物基质中。
当与其它包封材料相比较时,只有聚脲包封的异噻唑酮使皮肤过敏减少。这是未预见到的。
在下列实施例中除非特别指明所有份数和百分比均按重量计。
实施例1—异噻唑酮包封,A
经界面聚合包封异噻唑酮。
制备三种溶液,即,水相、有机相和交联溶液。水相通过将991.6克去离子水;0.20克二乙基己基磺基琥珀酸钠(作为MonowetMO—70E是商业上可得到的);和8.20克聚乙烯醇(88%聚乙酸乙烯酯水解,作为Airvol205是商业上可得到的)混合来制得。有机相通过将141.25克4,5—二氯—2—正辛基—3—异噻唑酮;40.0克二甲基;12.0克邻苯二甲酸二辛酯;和148.8克4,4′—二苯基甲烷二异氰酸酯(作为Mondur MRS商业上可得到的)混合来制得。交联溶液通过将17.04克1,2—乙二胺;23.64克三亚乙基四胺;和400.00克去离子水混合来制得。
将有机相加入到水相中并将混合物用Tekmar Tissumixer以15000rpm均化30秒。将生成的分散液转移至一个装有架设搅拌器、温度计和温度调节器的2升圆底烧瓶中。以400rpm的速率搅拌分散液。将交联溶液加入到搅拌着的分散液中,结果温度升高至35℃。反应在35℃下保持搅拌4小时。
4小时结束后,反应混合物的pH为7.8。经真空过滤从溶液中除去生成的固体颗粒并在空气中干燥。颗粒分析表明44.7%是4,5—二氯—2—正辛基—3—异噻唑酮。其平均粒度为18微米。
实施例2—异噻唑酮包封,B
经界面聚合包封异噻唑酮。
制备三种溶液,即水相、有机相和交联溶液、水相通过将991.6克去离子水;0.20克二乙基己基磺基琥珀酸钠(作为Monowet MO—70E是商业上可得到的);和8.20克聚乙烯醇(88%聚乙酸乙烯酯水解,作为Airvol 205是商业上可得到的)混合来制得。有机相通过将141.25克4,5—二氯—2—正辛基—3—异噻唑酮;40.0克二甲基;12.0克邻苯二甲酸二辛酯;和148.8克4,4′—二苯基甲烷二异氰酸酯(作为Mondur MRS是商业上可得到的)混合来制得。交联溶液通过将17.04克1,2—乙二胺;23.64克三亚乙基四胺;和400.00克去离子水混合来制得。
将有机相加入到水相中并用Ross Micro—Mixer Emulsifier以6000rpm将混合物均化3分钟。将生成的分散液转移至装有架设搅拌器、温度计和温度调节器的3升圆底烧瓶中。在加入交联溶液之前将分散液在40℃以400rpm的搅拌速度保持1小时。在40℃下将交联溶液加入到搅拌着的分散液中。反应在40℃下保持搅拌4小时。
4小时结束后,反应混合物的pH为9.2。经真空过滤从溶液中除去生成的固体颗粒并在空气中干燥。颗粒分析表明48%是4,5—二氯—2—正辛基—3—异噻唑酮。其平均粒度为8微米。
实施例3—包封材料和方法的比较
测定了本发明的聚脲包封的异噻唑酮和其它聚合物包封的异噻唑酮的相对速率(“RRR”)。
通过将足够提供总共26mg 4,5—二氯—2—正—辛基—3—异噻唑酮的包封的异噻唑酮加入到360克肥皂水溶液(0.2%二乙基己基磺基琥珀酸钠)中制成包封的4,5—二氯—2—正—辛基—3—异噻唑酮的分散液。每种包封的异噻唑酮的实际加入量取决于异噻唑酮在每种聚合物基质中的载荷。
将—“U”型的含有176根纤丝的空心丝渗析膜装置放入分散液中。将肥皂水溶液从含有1200克肥皂水溶液的贮液器中泵出,以2.9—3.1ml/分的流速通过空心丝返回贮液器。异噻唑酮从包封基质中渗入到分散液的水相中,然后通过空心丝膜流入到贮液器系统中。通过在不同的时间从贮液器中抽取等分试样来监测异噻唑酮在贮液器体系中的积聚。用HPLC分析等分试样中的4,5—二氯—2—正辛基—3—异噻唑酮。
对于未包封的4,5—二氯—2—正辛基—3—异噻唑来说,向肥皂水溶液中加入26毫克异噻唑酮以形成分散液并如上所述进行实验。未包封的4,5—二氯—2—正辛基—3-异噻唑酮的RRR被定义为1.0。根据该值测定了各种形成的包封的4,5—二氯—2—正辛基—3—异噻唑酮的RRR值。
如实施例1制备了本发明的聚脲包封的4,5—二氯—2—正辛基—3—异噻唑酮。用已知的方法制备了对比形式的包封的4,5—二氯—2—正辛基—3—异噻唑酮:用乙烯基聚合接种法制备用DVB延伸的苯乙烯/二乙烯基苯(“STY/DVB”);用界面聚合法制备聚酰胺;用喷雾干燥法制备聚乙烯醇;通过将溶解有异噻唑酮的二氯甲烷/PVC溶液分散于水中接着蒸发溶剂来制备聚氯乙烯(“PVC”)/分散液;用界面聚合法制备三乙酰乙酸酯/分散液;和用乙烯基聚合法制备交联的丙烯酸分散液。
结果列于表1中。
表1—本发明的颗粒和参比制品的相对释放速率
试验化合物 | %包封的同异噻唑酮 | RRR |
对照物4,5二氯—2—正辛基—3—异噻唑酮本发明聚脲(界面聚合)参比Sty/DVB,用DVB延伸(乙烯基聚合)聚酰胺(界面聚合)聚乙烯醇(喷雾干燥)聚氯乙烯(AI于聚氯乙烯的分散液)三乙酰乙酸酯分散液(界面聚合)X—交联丙烯酸分散液(乙烯基聚合) | —44.737.573.865.719.825.031.7 | 1.00.090.310.370.310.360.610.60 |
从以上数据,可以看出用聚脲包封异噻唑酮大大地降低了异噻唑酮的释放速率并且比其它包封组合物有效得多。
实施例4—包封的异噻唑酮功效的测定
制备表2中所列的一系列涂料组合物并测试异噻唑酮杀生物剂的功效(外部暴露结果)和淋巴节分析(过敏)。异噻唑酮杀生物剂即可以按照实施例1制成的颗粒形式引入也可按照参比包封方法以按照涂料组合物总量计足够引入2000ppm或1000ppm活性成份的量引入。
进行一项用以说明包封和降低释放速率不会影响长期功效的外部暴露研究。用表2所述的涂料涂刷面板,涂料中加入了适量的活性成分。空气干燥后,以正比垂直的位置将面板暴露于佛罗里达州圣玛丽峡谷的一个农场中。
表2—涂料组合物
2个月和6个月后总的霉变程度列于表3中。级别从0(完全被霉覆盖)至10(无霉菌生长)。
原料 | 功能 | 重量比率 | 体积百分率 | ||
Natrosol 250 MHR(HEc)乙二醇水Tamol 960三聚磷酸钾Triton CF-10Colloid 643丙二醇Ti—Pure R一902(TiO2)Minex 4Icecap KAttagel 50 | 增稠剂防冻剂稀释剂分散剂助分散剂表面活性剂消泡剂湿边助剂遮光剂扩充剂扩充剂抗粘结剂 | 3.025.0120.07.11.52.51.034.0225.0159.450.05.0 | 0.262.6514.400.670.070.280.133.946.577.322330.25 | ||
上述成分在cow1es Disso1ver上以3800-4500rpm研磨大约15分钟并在较低速度下加入如下成分: | |||||
Rhoplex AC-64(60.5%)Colloid 643Texanol杀霉剂氮水,28%水2.5%Natrosol 250 MHR | 乳液粘合剂消泡剂聚结剂pH控制剂粘度调节剂 | 305.93.09.32 to 72.0 | 34.100.391.170.25—1.000.27 | ||
足够达90—95KU并调节到总共100gal | |||||
总值 大约1162 100.00 | |||||
组合物常数颜料体积含量(%)含固量%(体积)起始粘度,KUpH | 45.436.290to959.5 |
表3—暴露结果,装饰涂料
总霉变程度(2个月/6个月) | |||
样品 | 0ppm | 1000ppm | 2000ppm |
空白对照物未包封的异噻唑酮聚脲(本发明)聚酰胺(参比)Sty/DVB(参比) | 5.6/0 | 6.0/6.35.6/5.69.0/7.39.0/6.7 | 9.7/9.39.6/9.19.7/9.68.7/93 |
因此,聚脲包封的异噻唑酮证明是与未包封的异噻唑酮同样有效的。
实施例5—过敏可能性的评估
小鼠淋巴节分析被用作测定皮肤激敏物的快速筛选技术。耳部直接表皮施用是评估由接触试验物质而引起过敏的可能性的一种适当的给药途径。由于接触激敏物,施用于耳部背侧和腹侧后细胞的增殖使得3H—胸苷掺入到从耳淋巴节中分离出的淋巴细胞的DNA中。测定细胞所摄取的3H—胸苷是客观的和可定量的反应。因此,掺入的3H—胸苷越多,测试化合物引起皮肤过敏的可能性就越大。
根据Gerberick等人〔Fundam.Appl. Toxicol.,19,438—445(1992)〕的方法用淋巴节分析法评价实施例4的涂料组合物,将不同浓度的实施例4的涂料组合物在1天到4天的时间里施用于4—5只小鼠的耳部(背侧和腹侧或只是背侧)。在第5天,给全部小鼠静脉注射3H—胸苷(20uci/小鼠)。注射5小时后,经二氧化碳窒息使动物死亡并切除耳部淋巴节。将淋巴节在5%三氯乙酸中均化并通过将3H—胸苷掺入到DNA部分中测定在消耗耳部淋巴节中的细胞增殖。这可通过液体闪烁计数来测量。
致敏测试的结果列于表4,其中全部样品含有4000ppm的4,5—二氯—2—辛基异噻唑酮并记载了每分钟的分解情况(DPM)。较低的DPM代表较低的致敏(掺入的3H—胸苷较少)。试验2起证实作用。
表4
包封方法 | DPM试验1 | DPM试验2 |
对照物无杀生物剂未包封的异噻唑酮本发明实施例1参比聚酰胺st/DVB | 12,87224,05213,77425,61622,543 | 10,76524,92211,013 |
从以上数据,惊人地发现本发明的聚脲包封的异噻唑酮具有比其它包封物或未包封的异噻唑酮低得多的皮肤致敏可能性。
Claims (19)
1.由颗粒组成的组合物,所述的颗粒包括包封于聚脲中的3—异噻唑酮杀生物剂。
2.根据权利要求1的组合物,其中所述的3—异噻唑酮选自4,5—二氯—2—正辛基—3—异噻唑酮和2—正辛基—3—异噻唑酮。
3.根据权利要求1的组合物,其中所述的聚脲是通过一种或几种聚异氰酸酯和一种或几种聚胺在所述的3—异噻唑酮存在下聚合而成的。
4.根据权利要求3的组合物,其中所说的聚胺选自二亚乙基、三亚乙基和四亚乙基胺。
5.根据权利要求3的组合物,其中所说的聚异氰酸酯选自聚亚甲基聚苯基异氰酸酯(PAPI);2,6—甲苯二异氰酸酯(TDI);双(4—异氰酰环己基)甲烷;1,6—亚己基二异氰酸酯(HDI);对—亚苯基二异氰酸酯,间—亚苯基二异氰酸酯;萘—1,5—二异氰酸酯;二苯基甲烷—4,4—二异氰酸酯(MDI);二苯基甲烷—4,4′,4″—三异氰酸酯,异丙基苯二异氰酸酯;和异佛尔酮二异氰酸酯(IPDI)。
6.根据权利要求1的组合物,其中所述的颗粒具有小于大约100微米的直径。
7.根据权利要求6的组合物,其中所说的颗粒具有小于大约40微米的直径。
8.降低人类由于接触含有杀生物有效量的3—异噻唑酮的组合物而过敏的方法,该方法包括将所说的3—异噻唑酮包封于聚脲颗粒中并将所说的颗粒分散于所说的组合物中。
9.根据权利要求8的方法,其中所说的组合物选自堵缝剂、密封剂、油漆、罩光漆、胶粘剂、粘合剂、成膜聚合物、木材浸渍剂、塑料和橡胶。
10.根据权利要求9的方法,其中所说的组合物是船舶涂料或鱼网涂料,所说的3—异噻唑酮是4,5—二氯—2—正辛基—3—异噻唑酮。
11.根据权利要求1的方法,其中所说的4,5—二氯—2—正辛基—3—异噻唑酮的浓度按所说的湿涂料组合物重量计为大约1—20%。
12.根据权利要求7的方法,其中所说的组合物是一种装饰涂料,所说的3—异噻唑酮选自2—正辛基—3—异噻唑酮和4,5—二氯—2—正辛基—3—异噻唑酮并以能对装饰涂料提供杀霉保护的有效剂量存在。
13.根据权利要求12的方法,其中所说的3—异噻唑酮的浓度按所说的湿涂料组合物重量计是大约300—5000ppm。
14.根据权利要求1的组合物,进一步包括一种或几种聚合物、溶剂、塑料和橡胶,所说的组合物以下列形式存在:堵缝剂、密封剂、油漆、罩光漆、胶粘剂、粘合剂、成膜聚合物、木材浸渍剂、塑料或橡胶。
15.根据权利要求14的组合物,该组合物可用作为船舶抗污染涂料并含有所说的颗粒,成膜聚合物和颜料,所说的异噻唑酮是4,5—二氯—2—正辛基—3—异噻唑酮并以能对由所说的涂料形成的膜提供抗污染性质的有效量存在。
16.包有由根据权利要求15的组合物形成具有抗污染性质的干燥的涂料膜的航海用设备。
17.根据权利要求16的物品,其中所说的航海用设备选自船舶、浮动平台、码头、帆装和鱼网。
18.根据权利要求14的组合物,该组合物可用作为装饰涂料并含有所说的颗粒、成膜聚合物和颜料,其中所说的颗粒具有小于大约20微米的直径并占所说组合物重量的大约0.03—0.5%。
19.包有由根据权利要求18的组合物干燥后形成的具有防霉性质的装饰涂料膜的被用物。
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DE19644224A1 (de) * | 1996-10-24 | 1998-04-30 | Bayer Ag | Antifoulingbeschichtung |
AU731386B2 (en) * | 1996-10-31 | 2001-03-29 | George Henry Hart | Rain water vessel |
AUPO821197A0 (en) * | 1997-07-24 | 1997-08-14 | Aquaculture Crc Limited | Antifouling of shellfish |
US7354596B1 (en) * | 1998-05-01 | 2008-04-08 | 3M Innovative Properties Company | Anti-microbial agent delivery system |
DE60005101D1 (de) | 1999-03-17 | 2003-10-16 | Api Corp | Beschichtetes bis(2-pyridinthiol 1-oxid) kupfersalz |
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DE102006030705A1 (de) * | 2006-06-30 | 2008-01-03 | Thor Gmbh | Antimikrobielle Mikropartikel |
DE102006036556A1 (de) | 2006-08-04 | 2008-02-07 | Wacker Chemie Ag | Vernetzbare Massen auf der Basis von Organosiliciumverbindungen |
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