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CN102176822A - 含杀生物剂的高固体分散体 - Google Patents

含杀生物剂的高固体分散体 Download PDF

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CN102176822A
CN102176822A CN2009801403929A CN200980140392A CN102176822A CN 102176822 A CN102176822 A CN 102176822A CN 2009801403929 A CN2009801403929 A CN 2009801403929A CN 200980140392 A CN200980140392 A CN 200980140392A CN 102176822 A CN102176822 A CN 102176822A
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M·C·巴克
D·D·P·弗黑延
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Janssen Pharmaceutica NV
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Abstract

本发明涉及含杀生物剂、聚合物表面活性剂、抗沉降剂和一种或多种载液的分散体，所述杀生物剂选自曲洛比利、吡啶硫酮锌或对甲抑菌灵或它们的组合。这些分散体具有可达80％重量的固体含量，且当用于防污涂料制剂时提供无尘释放系统。

Description

含杀生物剂的高固体分散体
本发明涉及含杀生物剂、聚合物表面活性剂、抗沉降剂和一种或多种载液的分散体，所述杀生物剂选自曲洛比利(tralopyril)、吡啶硫酮锌或对甲抑菌灵(tolylfluanid)或者它们的组合。这些分散体具有可达80％重量的固体含量，且在用于防污涂料制剂时提供无尘释放系统。
杀生物剂如曲洛比利和吡啶硫酮锌是作为抗菌剂、抗真菌剂或防污剂用于多种应用的熟知化合物。这些杀生物剂通常以干粉出售，用于油漆和涂料。这种干粉的缺点在于，其在处理过程中产生微尘，由于这些杀生物剂可通过接触导致对工人的手指或手的刺激，故此需要专门的处理设备。而且，工人在处理这些化合物的过程中不得不穿上合适的防护装备，例如防尘面具、护目镜、防护手套、防护服等。另外，通常安装局部排气系统，以便在处理这些杀生物剂时，产生的粉尘不会污染工作环境。
曲洛比利对于通过口服消化的急性口服哺乳动物毒性具有28.7mg/kg的LD50，吡啶硫酮锌对于急性吸入毒性具有1,03mg/L的LC50(4h)。基于处理干粉形式的杀生物剂时的这些问题，无尘释放系统的建立被视为有利的。
为油漆或涂料公司所用的无尘释放系统优选为这样的液体释放系统：其不释放微尘到空气中、能够容易处理、高度浓缩且也是贮藏稳定和易于倒出。
已发现用于杀生物剂曲洛比利、吡啶硫酮锌和对甲抑菌灵的这样的液体释放系统，其包括以下：
基于分散体总重量计算含量达80％重量的杀生物剂，选自曲洛比利、吡啶硫酮锌或对甲抑菌灵或者它们的组合，
聚合物表面活性剂；
抗沉降剂；
载液；及
任选的配制剂(formulation agent)如填充剂、粘合剂、树脂等。
曲洛比利在EP-0,312,723-A中公开用于控制软体动物类，其在防污组合物中的用途公开于EP-0,746,979。亦熟知所述化合物学名为4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-甲腈，由下式表示：
Figure BPA00001347364600021
吡啶硫酮锌，亦称为硫氧吡啶锌(zinc omadine)，是首次报道于二十世纪三十年代的配位络合物。其特征为通过氧和硫原子结合到锌上的两个吡啶衍生的螯合配体。它的IUPAC名是由下式表示的1，1’-二氧化双(2--吡啶硫基)合锌：
Figure BPA00001347364600022
吡啶硫酮锌最为人熟知的是其在治疗头皮屑和脂溢性皮炎中的用途。由于其在水中的溶解度低，其适合用作针对霉和藻提供保护的户外油漆和其它制品。
对甲抑菌灵具有广谱抗微生物活性，是化合物1，1-二氯-N-[(二甲氨基)磺酰基]-1-氟-N-苯基-甲烷次磺酰胺的通用名，该化合物由下式表示：
Figure BPA00001347364600023
为本发明之目的，术语“分散体”是指在液体介质中均匀分布的细颗粒系统。术语“表面活性剂”是指用于减少两边界表面的界面张力以此提高液体或固体的乳化性、铺展性、可分散性、或可湿性的制品。术语“抗沉降剂”是指用于在混悬液中保持细颗粒的制品。
适合用于本发明分散体的聚合物表面活性剂为：
-聚乙二醇醇酸树脂(alkyd polyethylene glycol)，如可购自Croda的Atlox 4914；以及
-ABA聚羟基酯-PEG-聚羟基酯共聚物，如可购自Croda的Hypermer B246和Zephrym PD2206。
特别优选必须经批准用于杀虫剂用途的聚合物表面活性剂。在美国，例如这将需要经EPA批准以下列列表用于杀虫剂用途：例如“Inert ingredients permitted in pesticide products：non-food inert ingredients(杀虫剂制品中允许的惰性成分：非食品惰性成分)”或者EPA列表例如40 CFR § 180.910“Inert ingredients used pre-and post-harvest；exemptions from the requirement of a tolerance(收获前后所用惰性成分；免除容许量规定)”、40 CFR § 180.950“Tolerance exemptions for minimal risk active and inert ingredients(容许量免除最低风险活性成分和惰性成分)”或40 CFR § 180.960“Polymers；exemptions from the requirement of a tolerance(聚合物；免除容许量规定)”。
适合用于本发明高固体分散体的抗沉降剂为蒸汽沉积二氧化硅、碳酸钙、改性蓖麻油、改性纤维素聚合物、皂土、水辉石或化学改性衍生物。任选这些抗沉降剂与作为活化剂的碳酸丙烯酯联合使用。
这些抗沉降剂的具体实例为：
-Bentone 38是季铵18-水辉石(CSA 12001-31-9)，由Elementis Specialties市售；
-Bentone gel MIO V是季铵18-水辉石(CAS 12001-31-9)和碳酸丙烯酯在矿物油中的混合物，由Elementis Specialties市售；
-Tixogel MIO-1584是季铵90-皂土(CAS 226226-22-8)与碳酸丙烯酯和矿物油的混合物，由Süd-Chemie市售；
-蒸汽沉积二氧化硅(亦已知为热解硅石)；及
-超细碳酸钙。
或者，根据所用载液可利用其他化学物质类型的抗沉降剂，例如：
-Ircothix 2000是购自Lubrizol Advanced Materials的羧化凝胶基流变剂；
-Crayvallac CVP氢化蓖麻油基流变剂；及
-Rhodapol 23黄原胶。
适合用于本发明高固体分散体的载液为异构烷烃溶剂、脱芳烃脂肪烃液体、重芳烃、石蜡油、甲苯、乙苯、三甲苯、二甲苯、邻苯二甲酸二异壬酯和氧化丙烯聚醚多元醇或它们的混合物。特定组的载液为异构烷烃溶剂、脱芳烃脂肪烃液体、重芳烃、石蜡油、二甲苯、邻苯二甲酸二异壬酯和氧化丙烯聚醚多元醇。
这样的载液的具体实例为：
-购自ExxonMobil的异构烷烃溶剂，例如Isopar C、E、G、H、K、L、M和V；
-购自ExxonMobil、商品名Exxsol的脱芳烃脂肪烃液体，例如Exxsol戊烷80、Exxsol penthylpentane naphta、Exxsol己烷、Exxsol庚烷、Exxsol异戊烷S、Exxsol异己烷、Exxsol环戊烷S、Exxsol D30、Exxsol D40、Exxsol D50、Exxsol D60、Exxsol D80、Exxsol D95等；
-购自ExxonMobil、商品名Solvesso的重芳烃，例如Solvesso 100、Solvesso 150、无萘(naphthalene depleted)Solvesso 150、Solvesso 200、无萘Solvesso 200、Solvesso 200S等；
-购自Petrochem Carless、商品名Brisopar的石蜡油；
-烷基苯，例如甲苯、乙苯、三甲苯和二甲苯；
-DINP(邻苯二甲酸二异壬酯)；及
-氧化丙烯聚醚多元醇，如购自Dow Chemical的Voranol产品、购自Elastogran的Lupranol或购自Huntsman的Jeffol多元醇。
术语“载液”应当理解为既指单数，又指复数，多于一种载液的混合物亦旨在为由术语“载液”所涵盖。
任选的配制剂为例如用于含较少量杀生物剂的本发明高固体分散体的惰性填充剂。这样的惰性填充剂为例如滑石。其它任选的配制剂例如为树脂如印尼松香，粘合剂如Neocryl B-725；购自DSM Neoresins的固体丙烯酸(BMA/MMA)共聚物。
因此，本发明提供一种分散体，包含：
a)含量可达80％重量的杀生物剂，选自曲洛比利、吡啶硫酮锌或对甲抑菌灵或它们的组合；
b)含量为0.1～30％重量的聚合物表面活性剂，选自聚乙二醇醇酸树脂和ABA聚羟基酯-PEG-聚羟基酯共聚物；
c)含量为0.01～10％重量的抗沉降剂，选自蒸汽沉积二氧化硅、碳酸钙、改性蓖麻油、改性纤维素聚合物、皂土、水辉石或者它们的化学改性衍生物或混合物，以及任选的碳酸丙烯酯；
d)载液，选自异构烷烃溶剂、脱芳烃脂肪烃液体、重芳烃、石蜡油、甲苯、乙苯、三甲苯、二甲苯、邻苯二甲酸二异壬酯和氧化丙烯聚醚多元醇，或它们的混合物；及
e)任选的其它配制剂。
本发明分散体具有可达总分散体80％重量的高固体含量。在一实施方案中，所述分散体具有20-80％重量的固体含量，或30-60％重量的固体含量。
本发明高固体分散体具有无需稀释所述高固体分散体即令它们能够直接用于涂料或油漆的制备的粘度水平。在测量时，高固体分散体的粘度优选低于10000mPa.s，更优选低于5000mPa.s。
对于简单的牛顿流体，粘度(η)由应用的剪切应力(τ)和测量的剪切率(γ)之间的比值得出，即：
η＝τ/γ
然而，当粘度取决于应用的剪切率时，本文所述系统经常表现出更为复杂的剪切稀化、假塑性流变学。上面引述的值通过以下方式确定：测量一系列剪切率时的粘度，并通过将粘度数据拟合到“Dispersion of Powders in Liquids(液体中的粉末分散体).第三版.Parfitt 1981 Applied Science Publishers ISBN 0-85334-990-8”所述的Casson方程中来外推获得限制性牛顿高剪切平稳期时的流动粘度。
τ0.5＝τ0 0.5+A.(γ0.5)
其中，τ0是所谓的屈服值，其是在样品开始移动之前需要应用的力，A是依赖于被测量系统的常数。
表面活性剂的量范围为0.1-30％重量，或0.5-10％重量。
抗沉降剂的量范围为0.01-10％重量，或0.1-5％重量。
代表性制剂实例：
制剂1：
制剂1通过在约60℃的温度下熔化聚合物表面活性剂Hypermer B246并将其与载液Exxsol D80混合直至得到澄清均相溶液来制备。之后，相继加入对甲抑菌灵粉末和抗沉降剂Bentone gel MIO-V，其中每次在加入下一组分之前利用盘状叶轮混合将分散体均质化。
Figure BPA00001347364600061
制剂2：
制剂2通过在约60℃的温度下熔化聚合物表面活性剂Hypermer B246并在持续搅拌下将其与载液Exxsol D80混合直至得到澄清均相溶液来制备。之后，相继加入曲洛比利粉末和抗沉降剂Bentone 38，其中每次在加入下一组分之前利用盘状叶轮混合将分散体均质化。为活化Bentone 38，在利用转子-定子混合机高度剪切制剂时加入碳酸丙烯酯。
Figure BPA00001347364600071
制剂3：
制剂3通过在约60℃的温度下液化聚合物表面活性剂Atlox 4914并在持续搅拌下将其与载液Exxsol D60混合直至得到澄清均相溶液来制备。之后，相继加入吡啶硫酮锌粉末、曲洛比利粉末和抗沉降剂Bentone gel MIO V，其中每次在加入下一组分之前利用盘状叶轮混合将分散体均质化。
Figure BPA00001347364600072
制剂4：
制剂4通过在持续搅拌下将聚合物表面活性剂Zephrym PD 2206与由二甲苯和Isopar K的混合物组成的载液混合直至得到澄清均相溶液来制备。之后，相继加入曲洛比利粉末和抗沉降剂Bentone 38，其中每次在加入下一组分之前利用盘状叶轮混合将分散体均质化。为活化Bentone 38，在利用转子-定子混合机高度剪切制剂时加入碳酸丙烯酯。
Figure BPA00001347364600081
制剂5：
制剂5通过在约60℃的温度下熔化聚合物表面活性剂Hypermer B246并在持续搅拌下将其与载液Isopar L混合直至得到澄清均相溶液来制备。之后，相继加入吡啶硫酮锌粉末和抗沉降剂Bentone 38，其中每次在加入下一组分之前利用盘状叶轮混合将分散体均质化。为了活化Bentone 38，在利用转子-定子混合机剪切制剂时加入碳酸丙烯酯。将滑石加入混合物中，并利用盘状叶轮再次混合整个系统直至获得均相分散体。
Figure BPA00001347364600082
制剂6：
制剂6通过在约60℃的温度下液化聚合物表面活性剂Atlox 4914并在持续搅拌下将其与载液Solvesso 150 n.d.混合直至得到澄清均相溶液来制备。之后，相继加入曲洛比利粉末和抗沉降剂Bentone gel MIO V，其中每次在加入下一组分之前利用盘状叶轮混合将分散体均质化。最后在持续混合下将印尼松香溶于分散体中。
Figure BPA00001347364600091
比较制剂1：无聚合物表面活性剂
比较制剂1通过将曲洛比利粉末加入到载液中并利用盘状叶轮混合机均质化来制备。
Figure BPA00001347364600092
比较制剂1为半液体糊，可搅拌但不能完全倒出。不能够利用购自TAinstruments的AR2000流变仪测量该制剂。因为样品流动性不足，该仪器不能将心轴向下带至所需间隙。
比较制剂2：无抗沉降剂
比较制剂2通过在约60℃的温度下熔化聚合物表面活性剂Hypermer B246并在持续搅拌下将其与载液Exxsol D80混合直至得到澄清均相溶液来制备。加入曲洛比利粉末，并利用盘状叶轮混合将分散体均质化。
Figure BPA00001347364600093
比较制剂2极似液体、可倒出，并可利用购自TAinstruments的AR2000流变仪处理。
比较制剂3：无聚合物表面活性剂
比较制剂3通过将吡啶硫酮锌粉末加入到载液中并利用盘状叶轮混合机均质化来制备。
Figure BPA00001347364600101
比较制剂3为触变液体，其可通过购自TA instruments的带4cm 2°锥体心轴的AR2000流变仪处理。该制剂表现出不包含任何抗沉降剂的高casson屈服值。
比较制剂4：无抗沉降剂
比较制剂4通过在约60℃的温度下熔化聚合物表面活性剂Hypermer B246并在持续搅拌下将其与载液Isopar M混合直至得到澄清均相溶液来制备。之后，加入吡啶硫酮锌粉末，并利用盘状叶轮混合将分散体均质化。
Figure BPA00001347364600102
比较制剂4不能通过带4cm 2°锥体心轴的AR2000流变仪处理，因为样品是液态，以致不能填满锥体。利用AR2000的双同心柱结构可以测量该样品。比较制剂4具有近似的牛顿流动特性。
比较制剂5：无聚合物表面活性剂
比较制剂5通过将吡啶硫酮锌粉末加入载液并利用刮铲均质化来制备。
比较制剂5为不能用盘状叶轮混合机混合的糊状固体。
比较制剂6：无抗沉降剂
比较制剂6通过在约60℃的温度下熔化聚合物表面活性剂Hypermer B246并在持续搅拌下将其与载液Isopar M混合直至得到澄清均相溶液来制备。之后，加入吡啶硫酮锌粉末，并利用盘状叶轮混合将分散体均质化。
Figure BPA00001347364600111
比较制剂6为极似液体的分散体，其可通过AR2000流变仪处理。
粘度
利用TA Instruments的AR2000流变仪作为流变学仪器，通常在25℃使用4cm 2°锥板结构(因其低粘度，利用双同心柱替代锥板结构测量比较实例4)。通过将粘度数据拟合到“Dispersion of Powders in Liquids(液体中的粉末分散体).第三版.Parfitt 1981 Applied Science Publishers ISBN 0-85334-990-8”所述的Casson方程中，确定Casson流动粘度和Casson屈服值。
Figure BPA00001347364600112
Figure BPA00001347364600121
贮藏稳定性
将样品贮藏于恒温橱中40℃的密封玻璃小瓶中，并基于恒定基础通过测量样品上方澄清的上清液层的形成来评估沉降度。其表示为液体总重量的百分比，在贮藏31天后得到的值记录于下表。正如可看到的，几乎无流变结构且Casson屈服值低的样品产生高沉降率。
Figure BPA00001347364600122

Claims (14)

1.一种分散体，包含：
a)含量可达80％重量的杀生物剂，选自曲洛比利、吡啶硫酮锌或对甲抑菌灵或它们的组合；
b)含量为0.1～30％重量的聚合物表面活性剂，选自聚乙二醇醇酸树脂和ABA聚羟基酯-PEG-聚羟基酯共聚物；
c)含量为0.01～10％重量的抗沉降剂，选自蒸汽沉积二氧化硅、碳酸钙、改性蓖麻油、改性纤维素聚合物、皂土、水辉石或者其化学改性衍生物或其混合物，以及任选的碳酸丙烯酯；
d)载液，选自异构烷烃溶剂、脱芳烃脂肪烃液体、重芳烃、石蜡油、甲苯、乙苯、三甲苯、二甲苯、邻苯二甲酸二异壬酯和氧化丙烯聚醚多元醇、或其混合物；及
e)任选的其它配制剂。
2.如权利要求1所述的分散体，其中所述杀生物剂为曲洛比利。
3.如权利要求1所述的分散体，其中所述杀生物剂为吡啶硫酮锌。
4.如权利要求1所述的分散体，其中所述杀生物剂为对甲抑菌灵。
5.如权利要求1所述的分散体，其中所述杀生物剂存在含量为20-80％重量。
6.如权利要求5所述的分散体，其中所述杀生物剂存在含量为30-60％重量。
7.如上述权利要求中任一项所述的分散体，其中聚合物表面活性剂含量为0.5-10％重量。
8.如上述权利要求中任一项所述的分散体，其中抗沉降剂含量为0.1-5％重量。
9.如上述权利要求中任一项所述的分散体，其中所述聚合物表面活性剂为聚乙二醇醇酸树脂。
10.如上述权利要求中任一项所述的分散体，其中所述聚合物表面活性剂为ABA聚羟基酯-PEG-聚羟基酯共聚物。
11.如上述权利要求中任一项所述的分散体，其中抗沉降剂选自季铵18-水辉石、季铵18-水辉石和碳酸丙烯酯的混合物以及季铵90-皂土与碳酸丙烯酯的混合物。
12.如上述权利要求中任一项所述的分散体，其中所述载液选自异构烷烃溶剂、脱芳烃脂肪烃液体、重芳烃、石蜡油、二甲苯、邻苯二甲酸二异壬酯和氧化丙烯聚醚多元醇。
13.如权利要求12所述的分散体，其中所述载液选自脱芳烃脂肪烃液体。
14.如上述权利要求中任一项所述的分散体，其中所述其它配制剂选自一种或多种惰性填充剂、树脂或粘合剂。
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