CN102272376A - 用于水生环境的经处理的纺织材料 - Google Patents
用于水生环境的经处理的纺织材料 Download PDFInfo
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- CN102272376A CN102272376A CN2009801535167A CN200980153516A CN102272376A CN 102272376 A CN102272376 A CN 102272376A CN 2009801535167 A CN2009801535167 A CN 2009801535167A CN 200980153516 A CN200980153516 A CN 200980153516A CN 102272376 A CN102272376 A CN 102272376A
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- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical compound [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 claims description 4
- 229960002026 pyrithione Drugs 0.000 claims description 4
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- DEBDHBVDRMJAML-UHFFFAOYSA-N 1-(2,3-dihydroindol-1-yl)-2-phenylethanethione Chemical compound C1CC2=CC=CC=C2N1C(=S)CC1=CC=CC=C1 DEBDHBVDRMJAML-UHFFFAOYSA-N 0.000 claims description 3
- QJNFJEMGWIQMJT-UHFFFAOYSA-N 1-(4-chlorophenyl)cyclopentane-1-carboxylic acid Chemical compound C=1C=C(Cl)C=CC=1C1(C(=O)O)CCCC1 QJNFJEMGWIQMJT-UHFFFAOYSA-N 0.000 claims description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 3
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- UZIRFBMYVLTOHJ-UHFFFAOYSA-N 3-(2,4,6-trichlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC(Cl)=CC(Cl)=C1C1=CC(=O)NC1=O UZIRFBMYVLTOHJ-UHFFFAOYSA-N 0.000 claims description 3
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 claims description 3
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- FRGXNJWEDDQLFH-UHFFFAOYSA-N 4-propan-2-ylpyridine Chemical compound CC(C)C1=CC=NC=C1 FRGXNJWEDDQLFH-UHFFFAOYSA-N 0.000 claims description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
用于水生环境中的用防污剂处理过的纺织材料,其中防污剂包含:a)一种或多种有机防污生物杀伤剂;b)选自以下的聚合物粘合剂:(A)平均分子量Mn为1500-20000g/mol的聚烯属粘合剂,其可由以下单体获得:(A1)60-95重量%的乙烯,(A2)5-40重量%的至少一种选自以下的不饱和羧酸:(A2a)单烯属不饱和C3-C10单羧酸,和(A2b)单烯属不饱和C4-C10二羧酸,和(A3)任选的0-30重量%的可与(A1)和(A2)共聚的其它烯属不饱和单体,其中在各种情况下单体的量均基于所用所有单体的总量;(B)平均分子量Mn为40,000-250,000的聚(甲基)丙烯酸系粘合剂,其通过至少50重量%(基于所用所有单体的总量)的一种或多种式(I)的单体的自由基乳液聚合获得,其中R1、R2和R3独立地选自任选氟取代且为线性或支化的C1-C10烷基,或者取代或未取代的芳基;R1和R2任选为H;(C)聚氨酯粘合剂,其可由以下组分的反应获得:(C1)至少一种二异氰酸酯或多异氰酸酯;(C2)至少一种二元醇、三元醇或多元醇;(C3)任选的其它组分;和(C4)任选的其它添加剂;(D)含有式(II)的基团的聚异氰脲酸酯粘合剂,其中R4取决于异氰脲酸酯制备中所使用的异氰酸酯是亚烷基或亚芳基残基;c)水或包含至少65重量%(基于总溶剂混合物(c))的水的含水溶剂混合物。
Description
本发明涉及用防污剂处理过的纺织材料在水生环境中,例如在渔业或水产养殖中的用途,保护水生环境中的织物的方法和经处理的织物。
生物污损是微生物、植物和动物不希望地聚积于浸入淡水或海水中的人造表面上。生物污损可降低技术装置的热交换性质及流动性质且通过释放强有机酸来促进腐蚀。
生物污损因为以下原因在水产养殖,尤其在海水养殖中成为问题:
-其减少网箱内水中的氧;
-其减小水流动,从而减少天然食物供给,因此降低所饲养的有鳍鱼或贝类的生长速率;
-污损生物与养殖动物竞争营养物供给;
-污损生物可包藏疾病或捕食者或释放有毒物质;
-其在物理上损害设备(磨损、脆化、增加重量)。
换网(从水中取出、在空气中干燥且在洗网器中清洗)或原位清洗(高压清洁器)费用昂贵:
-手工劳动(尤其潜水员费用昂贵);
-取出网或清洗对鱼造成困难(2%死亡率;若干天不生长);
-逃逸的鱼增加;
-如果网在独立洗涤设施中洗涤,则它们需要消毒以避免传染。
有鳍鱼和贝类生产场所的最常见污损物种为:藻类、藤壶、蚌类、管虫、海鞘类和水螅虫。
连续定殖(生物污损)的早期阶段的特征在于快速生长物种,例如水螅虫、蔓足类动物(例如藤壶)、多毛目环节动物、苔藓虫及海鞘类的盛行。通常第一定殖者为细菌、藻类及水螅虫,接着为其它固着性水生生物。但在许多情况下,藤壶和/或海鞘类可能首先附着至表面。定殖速率和程度主要由深海或海岸或河口水域中存在的污损物种的生物量和多样性,以及食物丰度、生长因素、水污染物、磨损物质(例如潮汐带中的砂子)、水温和强水流或弱水流决定。这些因素还可以导致以一种或几种上述生物为主导的污损。
已进行若干尝试以通过用防污剂浸渍纺织材料来防止纺织材料(特别是用于水生环境中的网)的生物污损。
JP-A 04-142373公开了包含含有聚氧化烯基团的线性有机聚硅氧烷的聚硅氧烷橡胶组合物用于涂布鱼网的用途。
US 4,883,852公开了包含聚二甲基硅氧烷(甲基)丙烯酸烷基酯和任选的其它乙烯基聚合物的防污涂料。所有聚硅氧烷涂料的一般缺点在于仅当表面以相对于水产养殖装置常见速率更高的速率移动时才可移除水生生物的任何定殖。
JP-A 04-225904公开了通过用由乙氧基化(甲基)丙烯酸酯单体制备的一种或多种亲水性聚合物处理纤维或绳索来进行防污剂的溶解控制。
JP-A 01-061404公开了包含无机过氧化物的水下防污组合物。该发明的缺点是过氧化物释放持续时间短,因为过氧化物被海水中存在的许多其它物质消耗。
JP-A 60-094677(Kuraray KK)公开了通过用金属如铜、锡、镉、锌、铅、铋、锑、铬、汞和铍火焰喷涂有机纤维来对有机纤维进行防污处理。这些金属显然对所有水生生物有毒且因此对环境不友好。
JP-A 2002-069360公开了一种防污涂料组合物,其包含(A)(甲基)丙烯酸酯共聚物,该共聚物含有(a)(a-1)芳族乙烯基化合物(优选:苯乙烯)的单元和(a-2)(甲基)丙烯酸烷基酯组分的单元以及(b)(甲基)丙烯酸羟烷基酯组分的单元以及(B)有机防污剂。
W02005/030405公开了嵌段/无规共聚物通过例如共价结合生物杀伤剂如三氯生(将其羟基官能转化为醚键)在生物杀伤组合物中的用途。虽然共价键随时间水解而可以释放生物杀伤剂,但是化学改性产生了新的需要全新注册的生物杀伤剂。
JP-A 2006-188453公开了基于生物杀伤剂和某些低分子量(甲基)丙烯酸酯的用于涂布鱼网的防污剂,
尽管文献中已有许多关于防污组合物的提议,但仍然存在改进的充分空间,特别是就防污功效和经处理的纺织材料的耐久性而言。
现已发现某些聚合物粘合剂特别适用于浸渍在水生应用中使用的纺织材料。
因此,本发明一方面提供了用防污剂处理过的纺织材料在水生环境中的用途,所述防污剂包含:
a)一种或多种有机防污生物杀伤剂;
b)选自以下的聚合物粘合剂:
(A)平均分子量Mn为1500-20000g/mol的聚烯属粘合剂,其可由以下单体获得:
(A1)60-95重量%的乙烯,
(A2)5-40重量%的至少一种选自以下的不饱和羧酸:
(A2a)单烯属不饱和C3-C10单羧酸,和
(A2b)单烯属不饱和C4-C10二羧酸,和
(A3)任选的0-30重量%的可与(A1)和(A2)共聚的其它烯属不饱和单体,
其中在各种情况下单体的量均基于所用所有单体的总量;
(B)平均分子量Mn为40,000-250,000的聚(甲基)丙烯酸系粘合剂,其通过至少50重量%(基于所用所有单体的总量)的一种或多种式(I)的单体的自由基乳液聚合获得,
其中
R1、R2和R3独立地选自任选氟取代且为线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戌基、仲戊基、新戊基、1,2-二甲基丙基、异戌基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基,优选C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
R1和R2任选为H;
(C)聚氨酯粘合剂,其可由以下组分的反应获得:
(C1)至少一种二异氰酸酯或多异氰酸酯,优选脂族、环脂族、芳脂族和/或芳族异氰酸酯,更优选任选缩二脲化和/或异氰脲酸化的二异氰酸酯,最优选1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基亚甲基基环己烷(IPDI)和六亚甲基二异氰酸酯-1,6(HMDI);
(C2)至少一种二元醇、三元醇或多元醇,优选具有2-14个,优选4-10个碳原子的脂族、环脂族和/或芳脂族二元醇,更优选1,6-己二醇或新戊二醇;
(C3)任选的其它组分,优选己二酸或羰基二咪唑(CDI);和
(C4)任选的其它添加剂;
(D)含有式(II)的基团的聚异氰脲酸酯粘合剂,
其中R4取决于异氰脲酸酯制备中所使用的异氰酸酯为亚烷基或亚芳基残基;
c)水或包含至少65重量%(基于总溶剂混合物(c))的水的含水溶剂混合物。
本发明另一方面提供了一种在水生环境中保护纺织材料不受生物污损的方法,该方法包括用本发明的防污剂处理纺织材料的步骤。
本发明另一方面提供了用于在水生环境中应用的经处理的纺织材料。
本发明的经处理纺织材料具有优异的功效和稳定性(尤其是在海水中)。
纺织材料
用于水生环境,优选水下环境中的经处理材料为纺织材料。如本文所使用的术语“纺织材料”包括但不限于纤维、纱、编织物、非织造物、形成圈针织物、抽拉圈针织物。
在本发明的优选实施例中,纺织材料为织物材料且特别为网织品。织物材料或网织品可以由多种天然和合成纤维制成,也可以是编织或非织造形式的混纺织物,如针织品或纤维。天然纤维是例如棉花、羊毛、丝、黄麻或大麻。合成纤维可以由聚酰胺、聚酯、聚丙烯睛、聚烯烃如聚丙烯或聚乙烯、Teflon和纤维的混合物如合成纤维与天然纤维的混合物制成。聚酰胺、聚烯烃和聚酯优选作为纤维材料。尤其优选聚酰胺和聚烯烃。
优选网织品的网孔大小(在正方形网孔情况下)取决于待捕捉或养殖的生物大小。其通常为2-30mm,优选10-30mm,特别地15-30mm。
本领域技术人员已知网织品的网孔大小应与所饲养的生物在它们生长期间的大小相适应。网织品还可以用于防止捕食者(鱼或海洋哺乳动物,例如海豹、海狮、南极海豹等)捕食所饲养的动物。这种保护性网织品所用的网孔大小应与捕食者的大小相适应。
用本发明防污剂处理过的根据本发明的网织品通常由纺织纤维制备,这种纤维通常具有0.05-10mm的厚度。优选地,纤维以使所述网包括具有偶数边缘的网孔图案的方式排列,其中网孔选自:
·具有边a和b以及高度ha的菱形形状的四边形网孔,其中高度ha为2-30mm,并且长度与高度之比b/ha为1∶1-5∶1,
·具有三对平行边a、b、c且各对边之间的距离为ha、hb和hc的六边形网孔,其中距离ha为0.05-10mm,并且比率((hb+ha)/2)/ha为1∶1-5∶1,和
·具有四对平行边a、b、c和d且各对边之间的距离为ha、hb、hc和hd的八边形网孔,其中距离ha为2-30mm,并且比率((hb+hc+hd)/3)/ha为1∶1-5∶1,
其中术语“长度”和“高度”是指各自的孔径(网孔大小)。
防污剂
本发明的防污剂包含有机防污生物杀伤剂(a)、聚合物粘合剂(b)、溶剂组分(c)和任选的其它组分(d)。
有机防污生物杀伤剂(a)
如本文所使用的术语“有机防污生物杀伤剂”包括适合于控制引起水生环境中纺织材料污损的生物且包含至少一种有机组分的任何类型的活性成分。因此该术语包括一般生物杀伤剂、杀菌剂、除藻剂、杀软体动物剂、杀节肢动物剂、杀真菌剂、除草剂、驱避剂、灭菌剂、防粘剂(附着破坏)、生长抑制剂、运动抑制剂、变形抑制剂、麻醉和昏迷剂、阻断移殖所需特定酶或者破坏或阻碍该活性的酶(例如蛋白酶、水解酶、氧化酶、过氧化物酶、超氧化物permutase和过氧化氢酶等)的试剂;和/或pH降低剂。
合适的防污生物杀伤剂为例如:百菌清(四氯间苯二甲腈)、抑菌灵(N,N-二甲基-N′-苯基-N′-(氟二氯甲硫基)磺酰胺)、对甲抑菌灵(N,N-二甲基-N′-甲苯基-N′-二氯氟甲硫基磺酰胺)、敌草隆(1,1-二甲基-3-(3,4-二氯苯基)脲)、氟吡酰草胺(N-(4-氟苯基)-6-[3-(三氟甲基)苯氧基]-2-吡啶甲酰胺、二噻农(2,3-二氰基-1,4-二硫杂蒽醌)、Irgarol 1051(N′-叔丁基-N-环丙基-6-(甲硫基)-1,3,5-三嗪-2,4-二胺)、2,4,5,6-四氯间苯甲腈、4,5-二氯-2-辛基-3-(2H)-异噻唑啉-3-酮(DCOIT)、2-(氰硫基甲硫基)苯并噻唑、(氰硫基甲硫基)苯并噻唑、N-环己基二氮烯二氧化物(diazeniumdioxide)铜盐或钾盐(CuHDO、KHDO)、2-巯基苯并噻唑、2-巯基吡啶氧化物锌盐或2-巯基吡啶氧化物铜盐、二硫代氨基甲酸金属盐(例如亚乙基双(二硫代氨基甲酸)锌、亚乙基双(二硫代氨基甲酸)锰、亚乙基双(二硫代氨基甲酸)铁或亚乙基双(二硫代氨基甲酸)铜)、一硫化或二硫化亚乙基秋兰姆、巯基咪唑啉、二苯基胍、二邻甲苯基胍、N,N-二烷基二硫代氨基甲酸硫代酸酐、N-甲基二硫代氨基甲酸钠、N,N-二烷基二硫代氨基甲酸金属盐(Zn、Fe、Cd、Cr、Cu、Ni、Mn)、N-酰基-1,2,4-噻唑、N-酰基-1,3,4-噻唑、N-酰基-1,2,3-噻唑、N-酰基-1,2,5-噻唑、2-(4-噻唑基)苯并咪唑、衍生的g-内酯、苯并三唑类(例如2-(2′-羟基苯基)苯并三唑-5,5′-二甲酸)、取代的N-芳基二氯马来酰亚胺(例如N-(4-氟苯基)-2,3-二氯马来酰亚胺、2,4,6-三氯苯基马来酰亚胺)、N-(3,4-二氯苯基)氨基甲酸甲酯、环烷酸金属盐、硫化或二硫化四烷基秋兰姆或其金属盐、2,2-二硫代双(吡啶-O-氧化物)、根据JP 09227308的石脑油-呋喃衍生物、三苯基硼烷烷基胺配合物(例如三苯基吡啶硼烷、(4-异丙基吡啶基)甲基二苯基硼烷)、(氰硫基烷基)硫代苯并heterozole、N-苯基马来酰亚胺衍生物、N-苯基丁二酰亚胺衍生物、氟二氯甲基硫代邻苯二甲酰亚胺、二氯萘醌、氨基氯萘醌、N-三氯甲硫基环己-4-烯-1,2-二甲酰亚胺(=N-三氯甲硫基四氢邻苯二甲酰亚胺)或其它卤化N-烷硫基衍生物、N-硫代烷基邻苯二甲酰亚胺衍生物(例如N-(氟二氯甲硫基)邻苯二甲酰亚胺)、任选卤化或以其它方式取代的吡啶-8-磺酸酯、亚乙基-双-二硫代氨基甲酸或其金属盐(例如锌盐或锰盐)、二甲基二硫代氨基甲酸或其金属盐、2-(噻唑-4-基)苯并咪唑、四氯间苯二甲腈、取代的香豆素衍生物、2-硫代全氢-1,3,5-噻二唑酮衍生物、3-(3,4-二氯苯基)-1,1-二甲基脲、3,4-二氯苯氨基甲酸甲酯、N-丙酰基吲哚啉、取代的N-丙酰基苯胺衍生物、取代的N-硫代羰基吲哚啉衍生物(例如1-(苄基硫代羰基)吲哚啉)、二硫杂环戊二烯并(4,5-b)喹喔啉-2-(硫)酮、取代的(卤代炔基)芳基醚(例如五氯苯基-碘炔丙基醚)、烷基或三氟甲基取代的N-苯基苯甲酰胺、N-取代的4-苯基-1,3-噻唑啉-2-酮衍生物、1-(4-氯苯基)-1-环戊烷甲酸或其酰胺或酯、N-取代的5-(4-吡啶基甲基)-6-硫代-1-硫杂-3,5-二氮杂环己烷衍生物、联苄基二硫代碳酸金属(例如锌)盐、2-甲硫基-4,6-双(异丙基氨基)均三嗪、2-甲硫基-4-叔丁基氨基-6-环丙基氨基均三嗪、2-氨基-3-氯-1,4-萘醌、4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-甲腈、nostocarboline衍生物(EP 1783128)、取代的1,2-二羟基喹啉衍生物(例如6-乙氧基-1,2-二羟基-2,2,4-三甲基喹啉);1,4,2-噻嗪衍生物(例如5,6-二氢-3-(2-噻吩基)-1,4,2-噻嗪-4-氧化物、5,6-二氢-3-(苯并[b]噻吩-2-基)-1,4,2-噻嗪-4-氧化物、3-(4-氯苯基)-5,6-二氢-3-(2-噻吩基)-1,4,2-噻嗪-4,4-二氧化物)、1,2,3,4-四氢-2-甲基-1,4-二氧代-2-萘磺酸钠盐、N-丁基氨基甲酸3-碘炔丙基酯(IPBC)、3-(3-碘炔丙基)苯并唑-2-酮、3-(3-碘炔丙基)-6-氯苯并唑-2-酮和如EP-A 1142477中公开的其它3-异噻唑酮。
合适的杀软体动物剂为氯硝柳胺(niclosamide)。例如吡螨胺(tebufenpyrad)、哒螨酮(pyridaben)、喹螨醚(fenazaquin)等线粒体电子传递抑制剂也是合适的。
可能的抗粘着剂包括N,N,N′,N′-四甲基乙二胺、P-香豆酸的硫酸酯(对磺氧基肉桂酸)。驱避剂:12-epi-deoxoscalarin、α-乙酰氧基西松烯内脂(α-acetoxypukalide)、furospongolide、吲哚、苯基硫脲、鞣酸、苯甲酸和藻酸。
防污生物杀伤剂还可以是天然化合物或半合成活性物质,例如五倍子酸,鞣花酸及其水解产物,儿茶酚,间苯三酚;鞣酸类,例如来自栗子,含羞草或白雀树;barettin,8,9-二氢barettin;萜类,例如chloromertensine,aerothionine,homoaerothionine,其它天然试剂:萜类,例如海葵毒素(palitoxin),chloromertensine,renillafoulins,西松烯内脂(pukalide),环氧呋喃西松烯内脂(epoxypukalide),b-红没药烯(b-bisabolene);aerothionine,homoaerothionine,siphonodictidine,heteronemin,ambiolA,pallescensin A,idiadione,d-cadinen cyan,龙虾肌碱(homarine),蕈状海鞘素(eudistomin),2,5,6-三溴-1-甲基芦竹碱,吲哚衍生物(例如蕈状海鞘素或2,5,6-三溴-1-甲基芦竹碱)以及例如N.Fusetani,Nat.Prod.Rep.,2004,21,94-104或A.I.Railkin:Marine Biofouling,CRC Press 2004中描述的其它化合物。
还可以使用具有驱避效应或生物杀伤效应的天然化合物,水生生物(宿主生物)使用这些天然化合物作为生物防御以抵御试图污损其的生物(表生生物)。
本发明的有机防污生物杀伤剂可作为单一活性化合物使用、与其它生物杀伤剂或杀虫剂组合使用或与无机防污剂(尤其是铜及其盐,例如硫酸铜、异硫氰酸铜、2-巯基吡啶氧化物铜盐、链烷酸铜盐、硝酸铜、硫氰酸铜、氯化铜、硼酸铜、氧化亚铜和/或氧化锌、8-羟基喹啉铜、2-巯基吡啶氧化物锌盐、氟硅酸锌和/或氟硅酸铜、2-吡啶硫醇-1-氧化物的铜盐)组合使用。
本领域技术人员将意识到污损生物的多样性可能需要应用一种以上的活性物质,尤其是不同作用方式的活性物质的组合。作为实例,抗运动保护仅有效抵抗其分散形式能活动的那些物种。在大型藻类和许多微型污损物的不活动孢子情况下,其将明显无效。类似地,驱避剂和生物杀伤剂可能无法有效驱避或杀死所有固着性污损物。
优选作为有机防污生物杀伤剂的是CuHDO、氟吡酰草胺和二噻农。
用于本发明的防污生物杀伤剂及其降解产物应对人、其它哺乳动物、商业水产养殖生物(例如鱼)、软体动物(例如贻贝或扇贝等)、甲壳类动物和大型藻类不具有毒性或至少具有低毒性。
本领域技术人员可以根据配制剂的预定用途或更具体地待用配制剂处理的纺织材料的预定用途对合适的防污生物杀伤剂进行选择。
对在水产养殖中使用而言,还可与防污生物杀伤剂一起包含杀寄生物剂从而控制鱼、软体动物和甲壳类动物的寄生物,例如海虱。
本申请优选的是拟除虫菊酯,例如丙烯除虫菊(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、RS-氯氟氰菊酯(cyhalothrin)、苯醚氰菊酯(cyphenothrin)、氯氰菊酯(cypermethrin)、甲体氯氰菊酯(alpha-cypermethrin)、乙体氯氰菊酯(beta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、溴氰菊酯(deltamethrin)、烯炔菊酯(empenthrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、氯氟氰菊酯(lambda-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊酯I和II(pyrethrin I和II)、灭虫菊(resmethrin)、灭虫硅醚(silafluofen)、氟胺氰菊酯(tau-fluvalinate)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin)、丙氟菊酯(profluthrin)和四氟甲醚菊酯(dimefluthrin);
烟碱受体激动剂/拮抗剂化合物,例如噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、吡虫清(acetamip rid)、噻虫啉(thiaclop rid);
式(Г1)的噻唑化合物:
有机磷酸酯,例如敌敌畏(dichlorvos)和唑啶磷(azamethiphos);
和大环内酯杀虫剂,例如齐墩螨素(abamectin)、emamectin、伊维菌素(ivermectin)、米尔螨素(milbemectin)、lepimectin和艾克敌105(spinosad)。
优选氯氰菊酯、溴氰菊酯、吡虫啉、伊维菌素、敌敌畏和唑啶磷。
防污剂中防污生物杀伤剂的总量优选为0至1重量%+50重量%,特别是1-15重量%。聚合物粘合剂(b)
生物污损剂另外包含至少一种分散或乳化的聚合物粘合剂(b)。
在一个优选的实施方案中,聚合物粘合剂为聚烯属粘合剂(A),其至少含有乙烯(A1)和不饱和羧酸(A2)作为单体。
聚合物粘合剂(A)具有例如通过凝胶渗透色谱法(GPC)测定的1500-20000g/mol,优选2000-15000g/mol的平均分子量Mn。
聚合物粘合剂含有60-95重量%的乙烯作为单体(A1)。优选地,乙烯的量为70-80重量%。在各种情况下单体的量均基于所用所有单体的总量。
此外,聚合物粘合剂(A)含有至少一种选自单烯属不饱和C3-C10单羧酸(A2a)和单烯属不饱和C4-C10二羧酸(A2b)的单烯属不饱和羧酸(A2)。
优选选择至少一种通式(III)的羧酸作为单烯属不饱和羧酸(A2a):
其中变量如下所定义:
R5和R6相同或不同,并选自氢以及未支化和支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基;更优选C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;尤其是甲基;
R6非常特别优选为氢。
在本发明的一个实施方案中,R5为氢或甲基。R5非常特别优选为甲基。
在本发明的一个实施方案中,R5为氢或甲基并且R6为氢。
非常特别优选所用通式(III)的烯属不饱和羧酸为甲基丙烯酸。
单体(A2b)为至少一种通式(HOOC)R7C=CR8(COOH)(IV);和/或R7R8C=C(-(CH2)n-COOH)(COOH)(V)的单烯属不饱和二羧酸。
R7与Rw相互独立地为H或任选取代的具有1-20个碳原子的直链或支化烷基。优选烷基具有1-4个碳原子。更优选R7和/或R7为H和/或甲基。烷基还可以任选含有其它取代基,条件是它们对聚合物的性能特征或方法没有不利影响。
在式(IV)的情况下,R7与R8也可一起为具有3-20个碳原子的亚烷基,所述亚烷基也可任选进一步被取代。优选由双键和亚烷基形成的环含有5或6个碳原子。亚烷基的实例特别包括1,3-亚丙基或l,4-亚丁基,其也可含有其它烷基取代基。n为0-5,优选0-3,非常优选0或1的整数。
还可使用两种或更多种不同单体(A2b)的混合物。在(IV)的情况下,所述单体在各种情况下可为顺式形式和/或反式形式。单体也可以相应羧酸酐或其它可水解羧酸衍生物的形式使用。如果COOH基团位于这种形式时,则可特别有利地使用环状酸酐。
合适式(II)的单体(A2b)的实例包括马来酸、富马酸、甲基富马酸、甲基马来酸、二甲基马来酸以及如果合适的话相应的环状酸酐。式(V)的实例包括亚甲基丙二酸和衣康酸。优选使用式(IV)的单体,特别优选马来酸和/或马来酸酐。
全部不饱和羧酸(A2)的量总计为4-40重量%,优选20-30重量%。
除单体(A1)和(A2)外,可任选使用一种或多种可与(A1)和(A2)共聚的烯属不饱和单体(A3)。除这些之外,不使用其它单体。
单体(A3)用于微调共聚物的性能。当然,也可使用两种或更多种不同的单体(A3)。本领域技术人员根据共聚物的所需性能对其进行选择。
单体(A3)的实例包括烯烃,特别是α-烯烃如丙烯、1-丁烯、1-己烯、1-辛烯、1-癸烯或1-十二碳烯、苯乙烯或其它烯烃如2-丁烯或异丁烯;此外包括一种或多种烯属不饱和C3-C10羧酸的C1-C10烷基酯或α-羟基-C2-C10亚烷基酯如丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸正丁酯、(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-乙基己酯或甲基丙烯酸正丁酯。其它实例包括含有P-基团的单烯属不饱和单体如乙烯基膦酸。
另外的单体(A3)的量为0-30重量%,优选0-9重量%,非常优选0-4重量%。非常优选不存在单体(A3)。
一般而言,在160℃下在325g负荷下根据EN ISO 1133测量,聚合物粘合剂(A)具有1-150g/10min,优选5-20g/10min,更优选7-13g/10min的熔体流动速率(MFR)。
一般而言,根据DIN EN 2114测量,聚合物粘合剂(A)可具有30-190mgKOH/g蜡,优选155-180mg KOH/g蜡的酸值。
一般而言,根据DIN 51007通过DSC测量,聚合物粘合剂(A)的熔程为60-110℃,优选65-90℃。
一般而言,根据DIN 53479测量,聚合物粘合剂(A)的密度为0.89-0.99g/cm3,优选0.89-0.96g/cm3。
乙烯(A1)、烯属不饱和羧酸(A2)和任选的其它共聚单体(A3)的聚合物粘合剂(A)可以有利地在高压条件下例如在搅拌式高压釜或高压管式反应器中,优选在搅拌式高压釜与高压管式反应器的组合中通过自由基引发的共聚进行制备。搅拌式高压釜本身是已知的,其描述可在Ullmann′sEncyclopedia of Industrial Chemistry,第5版,登录标题:Waxes,第A 28卷,第146页及随后各页,Verlag Chemie Weinheim,Basle,Cambridge,New York,Tokyo,1996中找到。这类高压釜的长度/直径比主要为5∶1-30∶1,优选10∶1-20∶1。同样可使用的高压管式反应器同样可在Ullmann′s Encyclopedia of Industrial Chemistry,第5版,登录标题:Waxes,第A 28卷,第146页及随后各页,Verlag Chemie Weinheim,Basle,Cambridge,New York,Tokyo,1996中找到。
共聚的合适压力条件为500-4000巴,优选1500-2500巴。这类条件在下文中也称为高压。反应温度为170-300℃,优选195-280℃。
共聚可在调节剂存在下进行。合适的调节剂为本领域技术人员已知。实例已公开在WO 2007/009909,第8页第18行至第9页第4行中。
可用于自由基聚合的引发剂是典型的自由基引发剂如有机过氧化物、氧或偶氮化合物。两种或更多种自由基引发剂的混合物也是适合的。实例已公开在WO 2007/009909,第9页第10行至第10页第16行中。
共聚单体(A1)、(A2)和任选的(A3)通常一起或单独计量加入。共聚单体(A1)、(A2)和任选的(A3)可在压缩机中压缩至聚合压力。在本发明方法的另一个实施方案中,首先借助泵使共聚单体达到例如150-400巴,优选200-300巴,特别是260巴的增加的压力,并然后用压缩机使其达到实际聚合压力。
由于烯属不饱和羧酸通常比乙烯更易结合到聚合物粘合剂(A)中,因此在计量加入的情况下,共聚单体(A1)、(A2)和任选的(A3)的比例通常不恰好对应于聚合物粘合剂(A)中的单元比例。
共聚可任选在溶剂不存在和存在的情况下进行。合适溶剂的实例包括甲苯、异十二烷以及二甲苯的异构体。
聚合物粘合剂(A)以其水分散体的形式使用。优选地,粘合剂(A)的水分散体在单独的步骤中制备,且将该水分散体用于制备根据本发明的防污剂。然而,也可在聚合工艺之后将粘合剂(A)以固体分离,且以固体用于防污剂中。
根据本发明使用的聚合物粘合剂(A)例如可以用如下物质至少部分中和:碱金属的氢氧化物和/或碳酸盐和/或碳酸氢盐如氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、氢氧化锂;或优选一种或多种胺,例如氨和有机胺,例如烷基胺、N-烷基乙醇胺、链烷醇胺和多胺。例如可提及如下烷基胺:三乙胺、二乙胺、乙胺、三甲胺、二甲胺、甲胺、哌啶和吗啉。优选的胺为单链烷醇胺、N,N-二烷基链烷醇胺、N-烷基链烷醇胺、二链烷醇胺、N-烷基链烷醇胺和三链烷醇胺,其中在各种情况下在羟烷基中具有2-18个碳原子,如果合适的话在各种情况下在烷基中具有1-6个碳原子,优选在链烷醇基团中具有2-6个碳原子,如果合适的话在烷基中具有1或2个碳原子。非常特别优选乙醇胺、二乙醇胺、三乙醇胺、甲基二乙醇胺、正丁基二乙醇胺、N,N-二甲基乙醇胺和2-氨基-2-甲基丙-1-醇。非常特别优选氨和N,N-二甲基乙醇胺。例如可提及如下多胺:乙二胺、四甲基乙二胺(TMEDA)、二亚乙基三胺和三亚乙基四胺。
优选地,将聚合物粘合剂(A)部分中和,即将羧基中的至少三分之一,更优选至少60mol%,例如至多99mol%粘合剂(A)的羧基中和。此外,可使用至少一种表面活性剂作为粘合剂(A)在水中的分散体或乳状液的助剂。特别地,表面活性剂可以为阴离子型或优选为非离子型。
阴离子型表面活性剂的实例包括C8-C12的碱盐或铵盐。
特别优选为非离子型表面活性剂,包括但不限于烷氧基化C10-C30链烷醇,优选含有3-100摩尔C2-C4氧化烯,特别是烷氧基化羰基合成醇或脂肪醇。非常优选的烷氧基化物的实例包括:
正C18H37O-(CH2CH2O)80-H;
正C18H37O-(CH2CH2O)70-H;
正C18H37O-(CH2CH2O)60-H;
正C18H37O-(CH2CH2O)50-H;
正C18H37O-(CH2CH2O)25-H;
正C18H37O-(CH2CH2O)12-H;
正C16H33O-(CH2CH2O)80-H;
正C16H33O-(CH2CH2O)70-H;
正C16H33O-(CH2CH2O)60-H;
正C16H33O-(CH2CH2O)50-H;
正C16H33O-(CH2CH2O)25-H;
正C16H33O-(CH2CH2O)12-H;
正C13H27O-(CH2CH2O)70-H;
正C13H27O-(CH2CH2O)60-H;
正C13H27O-(CH2CH2O)50-H;
正C13H27O-(CH2CH2O)25-H;
正C13H27O-(CH2CH2O)12-H;
正C12H25O-(CH2CH2O)11-H;
正C12H25O-(CH2CH2O)18-H;
正C12H25O-(CH2CH2O)25-H;
正C12H25O-(CH2CH2O)50-H;
正C12H25O-(CH2CH2O)80-H;
正C30H61O-(CH2CH2O)8-H;
正C10H21O-(CH2CH2O)9-H;
正C10H21O-(CH2CH2O)7-H;
正C10H21O-(CH2CH2O)5-H;
正C10H21O-(CH2CH2O)3-H;
包括其任何混合物,其中下标应以通常方式理解为平均数。
聚合物粘合剂(A)的分散体可以通过将粘合剂(A)、水和任选的表面活性剂和/或碱在至少70℃的温度下混合而制备。
在其它优选的实施方案中,聚合物粘合剂(b)是通过至少50重量%(基于所用所有单体的总重量)的一种或多种式(I)的单体(作为组分B1)的自由基乳液聚合获得的平均分子量Mn为40,000-250,000的聚(甲基)丙烯酸系粘合剂(B):
其中
R1、R2和R3独立地选自任选氟取代且可为线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基,优选C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
R1和R2可以另外为H。
优选R1为H或甲基。R2优选为H。R3优选为甲基、乙基、正丁基或2-乙基己基。
更优选R1为H或甲基,R2为H,R3为甲基、乙基、正丁基或2-乙基己基。
最优选地,式(I)的单体(组分B1)选自丙烯酸2-乙基己基酯、丙烯酸正丁基酯、丙烯酸甲酯、甲基丙烯酸甲酯和丙烯酸乙酯。最优选使用可通过至少两种不同式(I)的丙烯酸系单体聚合获得的共聚物。
最优选将通过如下组分的乳液聚合得到的聚(甲基)丙烯酸系粘合剂用作组分(b):
B1)作为组分B1的至少50重量%(基于所用所有单体的总重量)的一种或多种式(I)的单体:
其中
R1、R2和R3独立地为线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基,优选C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
R1和R2任选为H;
优选R1为H或甲基;R2优选为H;R3优选为甲基、乙基、正丁基或2-乙基己基;
更优选R1为H或甲基,R2为H,R3为甲基、乙基、正丁基或2-乙基己基;
B2)作为组分B2的任选且优选的至少一种式(VI)的单体:
其中
R9、R10、R11和R12独立地为H、线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基和正癸基;优选R9、R10、R11和R12选自H、可为线性或支化的C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
更优选R9为H或甲基,R10、R11和R12优选相互独立地为H;
最优选R9为H或甲基,R10、R11和R12为H;
B3)作为组分B3的任选的至少一种式(VII)的单体:
其中
R13和R14独立地为H、线性或支化的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基和正癸基;优选R13和R14选自H、线性或支化的C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
最优选R13和R14为H;
X为H、OH、NH2、OR15OH、缩水甘油基、羟丙基、
下式的基团:
其中
R15为C1-C10亚烷基,例如亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基;优选C1-C4亚烷基,例如亚甲基、亚乙基、亚丙基、亚丁基;取代或未取代的亚芳基,优选取代或未取代的C6-C10亚芳基,更优选取代或未取代的C6亚芳基,例如亚苯基;最优选X为乙酰乙酰基;
R16为支化或线性的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基;优选可为支化或线性的C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
B4)可与上述单体共聚的任选其它单体,其选自:
B41)极性单体,优选(甲基)丙烯腈;和/或
B42)非极性单体,优选苯乙烯和/或α-甲基苯乙烯。
聚(甲基)丙烯酸系粘合剂通过以下组分的乳液聚合获得:
B1)50-100重量%,优选50-99重量%的组分B1;
B2)0-5重量%的组分B2;
B3)0-5重量%,优选1-4重量%,更优选0.2-3重量%的组分B3;
B4)可与上述单体共聚的其它单体,其选自:
B41)0-30重量%,优选0-25重量%,更优选5-20重量%的组分B41;和/或
B42)0-40重量%,优选0-30重量%,更优选5-20重量%的组分B42;其中组分B1与任选的B2、B3和B4的和为100重量%。
在其它优选的实施方案中,聚(甲基)丙烯酸系粘合剂通过以下组分的乳液聚合获得:
B1)50-100重量%,优选50-99重量%,更优选50-95重量%的至少一种如上所定义的丙烯酸系粘合剂(组分B1),其包含:
B11)基于丙烯酸系粘合剂为10-90重量%,优选15-85重量%,更优选30-85重量%的丙烯酸正丁酯;
B12)基于丙烯酸系粘合剂为10-90重量%,优选12-85重量%,更优选15-65重量%的至少一种不同于丙烯酸正丁酯的式(I)的单体;
B2)基于丙烯酸系粘合剂为0-5重量%的至少一种式(VI)的单体(组分B2);
B3)基于丙烯酸系粘合剂为0-5重量%,优选0.1-4重量%,更优选0.2-3重量%的至少一种式(III)的单体(组分B3);
B4)可与上述单体共聚的其它单体(组分B4),其选自:
B41)基于丙烯酸系粘合剂为0-30重量%,优选0-25重量%,更优选5-20重量%的至少一种极性单体,优选(甲基)丙烯腈(组分B1d1);和/或
B42)基于丙烯酸系粘合剂为0-40重量%,优选0-30重量%,更优选5-20重量%的至少一种非极性单体,优选苯乙烯和/或α-甲基苯乙烯(组分B1d2);
其中组分B1、B2与任选的B3和B4的和为100重量%。
聚(甲基)丙烯酸系粘合剂可包含本领域技术人员已知的其它添加剂,例如成膜剂和增塑剂,例如己二酸酯、邻苯二甲酸酯、丁基二甘醇、可通过二羧酸与可为线性或支化的醇反应而制备的二酯的混合物。适合的二羧酸和醇为本领域技术人员已知。
最优选地,聚合(甲基)丙烯酸系粘合剂通过如下组分的乳液聚合获得:
B1)作为组分B1的50-100重量%的至少一种式(I)的单体,
其中
R1为H或甲基,R2为H,R3为甲基、乙基、正丁基或2-乙基己基,作为组分B1,最优选组分B1为丙烯酸2-乙基己基酯、丙烯酸正丁酯、丙烯酸甲酯、甲基丙烯酸甲酯或丙烯酸乙酯;
B2)作为组分B2的0-5重量%的至少一种式(VI)的单体:
其中R9为H或甲基,R10、R11和R12各自为氢;
B3)作为组分B3的0-10重量%,优选1-7重量%,更优选2-5重量%的至少一种式(VII)的单体:
其中R13和R14为氢,X为H、OH、NH2、OR15OH、缩水甘油基或下式的基团:
其中
R15选自C1-C10亚烷基,例如亚甲基、亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基;优选C1-C4亚烷基,例如亚甲基、亚乙基、亚丙基、亚丁基;取代或未取代的亚芳基,优选取代或未取代的C6-C10亚芳基,更优选取代或未取代的C6亚芳基,例如亚苯基;R16选自可为支化或线性的C1-C10烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、仲戊基、新戊基、1,2-二甲基丙基、异戊基、正己基、异己基、仲己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基;优选可为支化或线性的C1-C4烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基;取代或未取代的芳基,优选取代或未取代的C6-C10芳基,更优选取代或未取代的C6芳基,例如苯基或甲苯基;
最优选X为乙酰乙酰基;
B4)可与上述单体共聚的其它单体,其选自:
B41)0-30重量%,优选0-25重量%,更优选5-20重量%的组分B41,优选(甲基)丙烯腈;和/或
B42)0-40重量%,优选0-30重量%,更优选5-20重量%的组分B42,优选苯乙烯和/或α-甲基苯乙烯;
其中组分B1、B2与任选的B3和B4的和为100重量%。
在其它最优选的实施方案中,作为组分B11的丙烯酸正丁酯的量为30-90重量%,如上所述对其它组分B12和任选的其它式(I)的单体,组分B2、B3和B4进行选择,其中组分B1、B2、B3和B4的和为100重量%。
聚(甲基)丙烯酸系粘合剂通过上述单体的乳液聚合获得。合适的工艺条件为本领域技术人员已知并且例如公开于WO-A 2005/064072中。
在根据本发明的聚(甲基)丙烯酸系粘合剂中,通常可加入至多10重量%,优选0.05-5重量%的含有反应性或交联基团的单-或二烯属不饱和单体。这种单体的实例特别是α,β-烯属不饱和C3-5羧酸的酰胺,特别是丙烯酰胺、甲基丙烯酰胺和马来酸二酰胺,及其N-羟甲基衍生物如N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺,α,β-单烯属不饱和C3-5羧酸的N-烷氧基甲基酰胺如N-甲氧基甲基丙烯酰胺和N-正丁氧基甲基丙烯酰胺,乙烯基磺酸,丙烯酸和甲基丙烯酸与链烷二醇如乙二醇、丁二醇-1,4、己二醇-1,6和3-氯丙二醇-1,2的单酯,以及α,β-烯属不饱和单-和二羧酸的烯丙基和甲基烯丙基酯如马来酸二烯丙酯、富马酸二甲基烯丙酯、丙烯酸烯丙酯和甲基丙烯酸烯丙酯、邻苯二甲酸二烯丙酯、对苯二甲酸二烯丙酯、对二乙烯基苯、亚甲基双丙烯酰胺和乙二醇二烯丙基醚。
所得到的非交联乳液聚合物的分子量通常为40,000-250,000(通过GPC测定)。分子量通常通过使用常规量的常规链终止剂控制。常规链终止剂例如为磺基有机化合物。
本发明的聚(甲基)丙烯酸系粘合剂以其水分散体的形式获得并优选以水分散体的形式用于本发明的生物杀伤剂。
在其它优选的实施方案中,聚合物粘合剂是可通过以下组分的反应获得的聚氨酯(C):
C1)作为组分C1的至少一种二异氰酸酯或多异氰酸酯,优选脂族、环脂族、芳脂族和/或芳族异氰酸酯,更优选任选缩二脲化和/或异氰脲酸化的二异氰酸酯,最优选1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基亚甲基环己烷(IPDI)和六亚甲基二异氰酸酯-1,6(HMDI);
C2)作为组分C2的至少一种二元醇、三元醇或多元醇,优选具有2-14个,优选4-10个碳原子的脂族、环脂族和/或芳脂族二元醇,更优选1,6-己二醇或新戊二醇;
C3)作为组分C3的任选的其它组分,优选己二酸或羰基二咪唑(CDI);和
C4)作为组分C4的任选的其它添加剂。
聚氨酯优选可通过以下组分的反应获得:
C1)基于聚氨酯为55-99重量%,优选70-98重量%,更优选75-90重量%的至少一种二异氰酸酯或多异氰酸酯(组分C1),优选脂族、环脂族、芳脂族和/或芳族异氰酸酯,更优选任选缩二脲化和/或异氰脲酸化的二异氰酸酯,更优选亚烷基单元中具有4-12个碳原子的亚烷基二异氰酸酯,如1,12-十二烷二异氰酸酯、2-乙基四亚甲基二异氰酸酯-1,4、2-甲基五亚甲基二异氰酸酯-1,5、四亚甲基二异氰酸酯-1,4、赖氨酸酯二异氰酸酯(lysinester diisocyanate)(LDI)、六亚甲基二异氰酸酯-1,6(HMDI)、环己烷-1,3-和/或-1,4-二异氰酸酯、2,4-和2,6-六氢甲苯二异氰酸酯以及相应异构混合物、4,4’-、2,2’-和2,4’-二环己基甲烷二异氰酸酯以及相应混合物、1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷(IPDI)、2,4-和/或2,6-甲苯二异氰酸酯、4,4’-、2,4’和/或2,2’-二苯基甲烷二异氰酸酯(单体MDI)、多苯基多亚甲基多异氰酸酯(聚合MDI)和/或包含至少2种上述异氰酸酯的混合物;可以使用含有酯-、脲-、脲基甲酸酯-、羰二亚胺-、二氮杂环丁二酮-和/或氨基甲酸酯基团的其它二-和/或多异氰酸酯;最优选1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基亚甲基环己烷(IPDI)和六亚甲基二异氰酸酯-1,6(HMDI);C2)基于聚氨酯为10-90重量%,优选12-85重量%,更优选15-65重量%的至少一种二元醇、三元醇或多元醇(组分C2),优选具有2-14个,优选4-10个碳原子的脂族、环脂族和/或芳脂族二元醇,更优选多元醇,其选自聚醚醇如聚四氢呋喃、聚酯醇、聚硫醚多元醇、含羟基的聚乙缩醛和含羟基的脂族聚碳酸酯或至少2种上述多元醇的混合物。优选聚酯醇和/或聚醚醇。多羟基化合物的羟值通常为20-850mg KOH/g,优选25-80mg KOH/g。另外,使用分子量通常为60g/摩尔至<400g/摩尔,优选60-300g/摩尔的二元醇和/或三元醇。合适的二元醇为具有2-14个,优选4-10个碳原子的脂族、环脂族和/或芳脂族二元醇,例如乙二醇,丙二醇-1,3,癸二醇-1,10,邻-、间-、对二羟基环己烷,二甘醇,二丙二醇,优选丁二醇-1,4、新戊二醇、己二醇-1,6和双(2-羟乙基)氢醌,三元醇,如1,2,4-、1,3,5-三羟基环己烷,甘油和三羟甲基丙烷,基于环氧乙烷和/或1,2-环氧丙烷的低分子量含羟基的聚氧化烯和前述二元醇和/或三元醇的混合物;
C3)基于聚氨酯为0-10重量%,优选0.1-5重量%,更优选1-5重量%的其它组分(组分C3,优选己二酸或羰基二咪唑(CDI));和
C4)基于聚氨酯为0-10重量%,优选0.1-5重量%,更优选0.5-5重量%的其它添加剂(组分C4);
其中组分C1、C2、C3和C4的和为100重量%。
聚氨酯通过本领域已知方法制备。另外,本领域技术人员已知的添加剂可以在制备聚氨酯的方法中使用。
在其它优选的实施方案中,聚合物粘合剂是含有下式(II)的基团的聚异氰脲酸酯(D):
其中R4取决于异氰脲酸酯制备中所使用的异氰酸酯为亚烷基或亚芳基残基。
聚异氰脲酸酯通常通过异氰酸酯的环化三聚制备。优选的异氰酸酯为与上文就聚氨酯粘合剂(组分C1)所述相同的异氰酸酯。用于制备聚异氰脲酸酯的制备方法和条件为本领域技术人员已知。
聚合物粘合剂(b)可以是两种组分(A)、(B)、(C)和(D),特别是聚氨酯(C)和聚异氰脲酸酯(D)的混合物。
溶剂组分(c)
优选仅使用水作为防污剂的溶剂。然而,可以另外使用少量(例如小于50重量%)可与水混溶的有机溶剂。这类另外的溶剂可以用于改善待处理表面的湿润或改善疏水性杀虫剂或其它组分在配制剂中的溶解性/分散性。另外的溶剂的实例包括水混溶性醇,例如一元醇如甲醇、乙醇或丙醇;高级醇如乙二醇或聚醚多元醇以及醚醇如丁基乙二醇或甲氧基丙醇。如果使用含水混合物,则该混合物优选包含至少65重量%、更优选至少80重量%,非常优选至少95重量%的水。这些数值在各种情况下均基于全部溶剂的总量。
另外的组分(d)
取决于具体粘合剂(b)和待处理的纺织材料的预定用途,防污剂可以进一步包含一种或多种选自以下的组分:固定剂,防腐剂,洗涤剂,填料,抗冲改性剂,防雾剂,发泡剂,澄清剂,成核剂,偶联剂,电导增强剂(抗静电剂),稳定剂如抗氧化剂、碳和氧自由基清除剂和过氧化物分解剂等,阻燃剂,脱模剂,具有UV保护性能的试剂,铺展剂,防结块剂,防迁移剂,起泡剂,防污剂,增稠剂,其它生物杀伤剂,润湿剂,增塑剂和成膜剂,粘合剂或防粘剂,光学增白剂(荧光增白剂),颜料和染料。
具体地,在丙烯酸酯粘合剂(B)和聚氨酯粘合剂(C)的情况下,聚合物粘合剂可以有利地与固定剂一起应用以改改善生物杀伤剂在材料上的附着。固定剂可以含有游离的异氰酸酯基团。
合适的固定剂例如为含有游离异氰酸酯基团的异氰酸酯或异氰脲酸酯。优选异氰脲酸酯是基于亚烷基单元中具有4-12个碳原子的亚烷基二异氰酸酯,如1,12-十二烷二异氰酸酯,2-乙基四亚甲基二异氰酸酯-1,4,2-甲基五亚甲基二异氰酸酯-1,5,四亚甲基二异氰酸酯-1,4,赖氨酸酯二异氰酸酯(LDI),六亚甲基二异氰酸酯-1,6(HMDI),环己烷-1,3-和/或-1,4-二异氰酸酯,2,4-和2,6-六氢甲苯二异氰酸酯以及相应异构混合物,4,4’-、2,2’-和2,4’-二环己基甲烷二异氰酸酯以及相应的混合物,1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷(IPDI),2,4-和/或2,6-甲苯二异氰酸酯,4,4’-、2,4’和/或2,2’-二苯基甲烷二异氰酸酯(单体MDI),多苯基多亚甲基多异氰酸酯(聚合MDI)和/或包含至少2种上述异氰酸酯的混合物。更优选异氰脲酸酯基于六亚甲基二异氰酸酯-1,6(HMDI)。
还优选异氰脲酸酯是用基于环氧乙烷和/或1,2-环氧丙烷的聚氧化烯,优选聚环氧乙烷亲水化的异氰脲酸酯。
用作固定剂的异氰脲酸酯可通过本领域已知的方法制备。优选基于用作制备异氰脲酸酯的原料的异氰酸酯的量为5-25重量%,更优选7-20重量%,最优选10-15重量%的异氰酸酯基团为游离的异氰酸酯基团。
优选地,将用作固定剂的异氰脲酸酯溶解于极性非质子溶剂如THF、DMF或碳酸异丙烯酯或碳酸亚乙酯中。
其它优选的固定剂为用聚环氧乙烷亲水化且溶于碳酸异丙烯酯中(70重量%的在30重量%碳酸异丙烯酯中的HMDI)的基于HMDI的异氰脲酸酯。游离异氰酸酯基团的量基于用作制备异氰脲酸酯的原料的异氰酸酯的量为11-12重量%。
如果使用固定剂,则防污剂通常包含基于组合物的固体含量为1-8重量%,优选1-5重量%,更优选2-4重量%的至少一种固定剂。
作为其它另外的组分(d),表面活性剂可用于稳定配制剂中的防污生物杀伤剂(a)和/或聚合物粘合剂(b)。特别优选阴离子和/或非离子型表面活性剂。典型实例如上所述。
合适的消泡剂例如为硅消泡剂。保护UV敏感性杀虫剂的合适UV保护剂例如为对氨基苯甲酸(PABA)、辛基甲氧基sinameth、茋、苯乙烯基或苯并三唑衍生物、苯并唑衍生物、羟基取代的二苯甲酮、水杨酸酯、取代的三嗪、肉桂酸衍生物(任选被2-氰基取代)、吡唑啉衍生物、1,1’-联苯基-4,4’-双-2-(甲氧基苯基)乙烯基或其它UV保护剂。合适的光学增白剂为二氢喹啉酮衍生物,1,3-二芳基吡唑啉衍生物,芘,萘酸酰亚胺,4,4,-二苯乙烯基联苯,4,4’-二氨基-2,2’-茋二磺酸,香豆素衍生物,通过-CH=CH-桥连接的苯并唑、苯并异唑或苯并咪唑体系或其它荧光增白剂。
可以用于防污剂的典型颜料为用于颜料染色或印刷方法或用于塑料着色的颜料。
根据它们的化学性质颜料可以为无机或有机的。无机颜料主要用作白色颜料(例如金红石或锐钛矿形式的二氧化钛、ZnO、白垩)或黑色颜料(例如炭黑)。由于潜在的有毒危害,也可以但不优选使用有色无机颜料。就赋予色彩而言,优选有机颜料或染料。有机颜料可以为单偶氮或双偶氮、萘酚、苯并咪唑酮、(硫代)靛蓝类、二嗪、喹吖啶酮、酞菁、异吲哚啉酮、花、紫环酮、金属配合物或二酮吡咯并吡咯类颜料。颜料可以粉末或液体形式(即作为分散体)使用。优选的颜料为颜料黄83、颜料黄138、颜料橙34、颜料红170、颜料红146、颜料紫19、颜料紫23、颜料蓝15/1、颜料蓝15/3、颜料绿7、颜料黑7。其它合适的颜料为本领域技术人员已知。
典型的染料为粉末或液体形式的瓮染料、阳离子染料和分散染料。优选使用瓮染料形式。瓮染料可以为阴丹酮类型,例如C.I.瓮蓝4、6或14;或黄烷士酮类型,例如C.I.瓮黄1;或皮蒽酮类型,例如C.I.瓮橙2和9;或异苯并蒽酮(异宜和蓝酮)类型,例如C.I.瓮紫1;或二苯并蒽酮(紫蒽酮)类型,例如C.I.瓮蓝16、19、20和22,C.I.瓮绿1、2和9和C.I.瓮黑9;或蒽醌咔唑类型,例如C.I.瓮橙11和15,C.I.瓮棕1、3和44,C.I.瓮绿8和C.I.瓮黑27;或苯并蒽酮吖啶酮类型,例如C.I.瓮绿3和13以及C.I.瓮黑25;或蒽醌唑类型,例如C.I.瓮红10;或花四甲酸二酰亚胺类型,例如C.I.瓮红23和32;或咪唑衍生物,例如C.I.瓮黄46;或氨基三嗪衍生物,例如C.I.瓮蓝66。其它合适的瓮染料为本领域技术人员已知。典型的分散染料和阳离子染料为本领域技术人员已知。
防污剂的制备
防污剂可以通过使用合适的混合和/或分散聚集体将所有成分与水和任选的其它溶剂混合在一起而形成。一般而言,配制剂在10-70℃,优选15-50℃,更优选20-40℃的温度下形成。
可使用固体防污生物杀伤剂(a)、固体聚合物粘合剂(b)和任选的其它添加剂(d)可将它们分散于溶剂组分(c)中。
然而,优选使用事先已单独制备的聚合物粘合剂(b)在水中的分散体以及防污生物杀伤剂(a)在水中的配制剂。这类单独的配制剂可包含其它添加剂以稳定各配制剂中的(a)和/或(b),且可商购。在第二工艺步骤中,加入这类原料配制剂和任选的其它任何另外的溶剂组分(c)。
组合也是可以的,即使用(a)和/或(b)的预先形成的分散体且将其与固体(a)和/或(b)混合。
聚合物粘合剂(b)的分散体可以是已由化学品制造商制备的预先制备的分散体。
可将防污剂制成最终产品,从而最终用户可轻易地将其用于根据本发明的方法中。
然而,当然也可制备浓缩物,最终用户可用另外的溶剂(c)将该浓缩物稀释至使用所需浓度。
此外,可以将配制剂以至少包含如下组分的试剂盒运送至最终用户:
·包含至少一种防污生物杀伤剂(a)的第一组分;和
·包含至少一种聚合物粘合剂(b)的第二组分。
其它添加剂(d)可以是试剂盒的单独的第三组分,或可以已经与组分(a)和/或(b)混合。
最终用户可以通过仅将水加入试剂盒的组分中并混合而制备配制剂以供使用。
试剂盒的组分可以是干燥组合物的形式如粉末、胶囊、片剂或泡腾片剂。干燥形式的合适杀虫剂以可通过人工搅拌或振摇轻易地溶解成均匀配制剂的泡腾片剂或可润湿性粉末获得。
试剂盒的组分可以是在水或含水溶剂混合物中的配制剂。当然,可将一种组分的含水配制剂与其它组分的干燥配制剂组合。
在本发明的优选实施方案中,试剂盒包括:
·防污生物杀伤剂(a)与任选的溶剂(c)的一种配制剂;和
·至少一种聚合物粘合剂(b)、溶剂组分(c)与任选的组分(d)的单独的第二配制剂。
组分浓度
本领域技术人员根据待使用的浸渍技术而对组分(a)、(b)、(c)和任选的(d)的浓度进行选择。
一般而言,生物杀伤剂(a)的量基于所有组分(a)、(b)和(d)一起即除含水溶剂(c)外的所有组分的量可为至多50重量%,优选20-50重量%。
聚合物粘合剂(b)的量基于所有组分(a)、(b)和(d)一起的量可为30-95%。
如果存在另外的组分(d),则其量基于(a)、(b)和(c)一起的量通常为0.1-50%,优选0.5-35%。如果存在颜料和/或染料,则其合适的量基于(a)、(b)和(c)通常为0.01-20重量%,优选0.1-10重量%,更优选0.2-5重量%。
可用于浸渍方法中的典型防污剂包含0.01-25%,优选0.1-20%的组分(a)、(b)和任选的(d),其中余量为含水溶剂(c)。
待由最终用户稀释的浓缩物的典型浓度可包含10-70%的组分(a)、(b)和任选的(d),其中余量为含水溶剂(c)。
浸渍方法
本发明的防污剂特别适于浸渍用于渔业和水产养殖的聚酯网织品。
浸渍方法不限于特定处理技术。浸渍可通过将纺织材料浸入配制剂中或通过将配制剂喷涂至纺织材料的表面上来进行。处理之后,可将经处理的非生物材料在环境温度下简单干燥。
取决于聚合物粘合剂(b)和具体应用,可能不需要在较高温度下进行干燥、交联或其它后处理步骤,但是进行这些另外的步骤当然在本发明的范围内。
本发明的配制剂可以在加工为所需产品之前即当仍为纱线或板材形式时,或在产品制备之后应用于织物材料或网织品上。
在优选实施方案中,在织物和/或网织品的情况下,本发明提供了一种浸渍织物和/或网织品材料的方法,该方法至少包括如下步骤:i)通过选自如下的任何程序步骤用防污剂处理织物和/或网织品:
(i1)使织物材料或网织品通过防污剂;或
(i2)使织物材料或网织品与部分或全部浸入防污剂中且将防污剂提取至网织品或织物材料与辊接触一侧的辊接触,或
(i3)将该材料浸入防污剂中;或
(i4)将防污剂喷涂至织物材料或网织品上;或
(i5)将防污剂刷涂至织物材料或网织品之上或之中;或
(i6)以泡沫应用防污剂;或
(i7)将防污剂涂覆于织物材料或网织品上;
ii)任选通过在辊之间挤压材料或借助于刮刀除去过量的配制剂;和
iii)干燥和/或固化/固定织物材料或网织品。
在原材料包含在先生产过程的残余物如胶料、纺丝油剂、其它助剂和/或杂质的情况下,可能有益的是可在浸渍之前进行洗涤步骤。
具体地,对步骤i)、ii)和iii)而言,如下细节是重要的。
步骤i1)
配制剂通过使织物或网织品通过含水防污剂而应用。本领域技术人员已知该步骤为轧染。在优选的实施方案中,将织物或网织品完全浸入含水防污剂中或含有液体的槽中,或者使织物或网织品通过保持在两个水平方向的辊之间的防污剂。根据本发明,可使织物材料或网织品通过配制剂,或可使防污剂通过织物或网织品。防污剂的吸收量受以下因素影响:浓浴液的稳定性、含量分布的需要、织物或网织品的密度以及节省干燥和固化步骤能源成本的想法。通常的液体吸收量基于材料的重量可为40-150%。本领域技术人员熟知最佳值的确定。步骤a1)优选用于浸渍随后裁成网的原幅材料。
在步骤a1)、a2)或a3)中,织物材料或网织品的浸渍典型地在5-70℃,优选10-50℃,更优选15-40℃的温度下进行。
步骤i3)
可以通过将网织品浸入处理浴液中来浸渍网织品。这可以在适当大小的槽或桶中或在用于清洗网织品以防污损的洗涤机中进行。本领域技术人员可以选择应用可由网织品物理上吸收的处理浴液的体积。
步骤i4)
喷涂可以连续法或分批法在配备有喷涂装置的合适纺织机中实施,例如在开口式衣物洗涤机/脱水机中。该设备尤其适于浸渍现成的网。
步骤i6)
泡沫包含比上述溶液或乳状液更少的水。因此干燥过程可以非常短。可通过将气体或气体混合物(例如空气)注入其中而进行处理。可能需要加入表面活性剂,优选具有成膜性能的表面活性剂。合适的表面活性剂和所需技术设备为本领域技术人员已知。
步骤i7)
涂覆方法可优选以刮刀法进行。工艺条件为本领域技术人员已知。
步骤ii)
过量的溶液或乳状液通常通过挤压织物或网织品,优选通过使织物材料或网织品通过本领域已知的辊而除去,由此获得限定的液体吸收量。挤出的液体可以再使用。或者,过量的水溶液或含水乳状液或水分散体可通过离心或真空抽吸而除去。
步骤iii)
主动干燥过程通常在大规模加工过程中进行。干燥通常在低于200℃的温度下进行。优选温度为50-170℃,更优选为60-150℃。温度选择由防污剂的热稳定性和所浸渍纺织材料的热稳定性决定。干燥可以在通常配备加热的用于清洁网织品的鼓式洗涤机中进行。干燥还可以在环境温度下进行。
在干燥后或干燥时,任选将经浸渍的纺织材料最终固化和/或固定。本领域技术人员知道如何进行固化和/或固定。通常在可以高于干燥温度的温度下进行固化过程。固化的优选温度为60-170℃,优选70-170℃,更优选80-150℃。干燥和固化可有利地在单一过程中,例如在具有可加热至不同温度的不同隔室的展幅机中进行。如果使用反应性交联剂,则可降低温度,例如30-130℃,优选30-100℃。
干燥和/或固化例如可以在通常在非生物研磨中用于这些目的的任何设备,例如展幅机、悬环式干燥机、热烟道、转鼓干燥机、浸轧汽蒸机等中实现。在本发明的一个实施方案中,使用连续干燥和/或固化的设备。在本发明的另一个实施方案中,使用非连续(分批)干燥和/或固化的设备。该设备可以包括专业洗衣店中所用的旋转干燥机或转鼓干燥机、可加热至处理温度的组合式洗衣/干燥机(例如牛仔裤石磨洗)。处理化学品可作为液体加入或喷涂于网织品材料上,然后在干燥/固化之前或期间通过旋转湿材料使其均匀分布。如果可例如通过离心移除过量液体,则可加入过量的处理液体。本领域技术人员将意识到在相同温度下的处理时间可能比连续法更长。
固化过程还可以包括以下步骤或由其组成:使纺织材料在加压下通过加热表面,例如熨斗或加热辊。在干燥处理和固化期间,优选以防止变形(例如收缩或尺寸变形)的方式机械固定纺织材料。此外,防止将生物杀伤剂洗掉。或者可以通过结合热和UV光的双重固化法或仅通过UV光进行固化和/或固定。合适的方法为本领域技术人员所知。
用于水产养殖(淡水或海水(海水养殖))的织物可为以下形式:用于鱼网箱的网织品、用于保护贝类养殖的网织品、用于果胶培养的天窗网织品、锚和停泊缆绳或其它织物设备。用于水产养殖的织物可由聚烯烃、聚酯、聚酰胺或其它合适的纤维制成,并具有适于该目的的任何颜色、网孔大小和但尼尔强度。
取决于防污生物杀伤剂的效率,经浸渍的网织品或织物中生物杀伤剂(a)的典型量为织物材料或网织品(干燥)重量的0.1-25%(干重)。取决于杀虫剂和/或驱避剂,优选的量为织物材料或网织品的0.5-20重量%。
聚合物粘合剂(b)的典型量为织物或网织品的(干燥)重量的0.1-25重量%(干重)。作为通用准则,防污生物杀伤剂和粘合剂(b)之间的重量比应大致恒定,即防污生物杀伤剂的量越高,则粘合剂(b)的量也越高。粘合剂(b)的优选量为织物或网织品(干燥)重量的0.5-20重量%,更优选1-20重量%。
应用于水生环境中的本发明经处理的纺织材料优选包含选自以下的至少一种防污生物杀伤剂:敌草隆、氟吡酰草胺、Irgarol 1051、2,4,5,6-四氯间苯甲腈、4,5-二氯-2-辛基-3-(2H)-异噻唑啉-3-酮(DCOIT)、2-(氰硫基甲硫基)苯并噻唑、(氰硫基甲硫基)苯并噻唑、N-环己基二氮烯二氧化物铜盐或钾盐(CuHDO、KHDO)、2-巯基苯并噻唑、2-巯基吡啶氧化物锌盐或2-巯基吡啶氧化物铜盐、二硫代氨基甲酸金属盐(例如亚乙基双(二硫代氨基甲酸)锌、亚乙基双(二硫代氨基甲酸)锰、亚乙基双(二硫代氨基甲酸)铁或亚乙基双(二硫代氨基甲酸)铜)、一硫化或二硫化亚乙基秋兰姆、巯基咪唑啉、二苯基胍、二邻甲苯基胍、N,N-二烷基二硫代氨基甲酸硫代酸酐、N-甲基二硫代氨基甲酸钠、N,N-二烷基二硫代氨基甲酸金属盐(Zn、Fe、Cd、Cr、Cu、Ni、Mn)、N-酰基-1,2,4-噻唑、N-酰基-1,3,4-噻唑、N-酰基-1,2,3-噻唑、N-酰基-1,2,5-噻唑、2-(4-噻唑基)苯并咪唑、衍生的g-内酯、苯并三唑类(例如2-(2′-羟基苯基)苯并三唑-5,5′-二甲酸)、取代的N-芳基二氯马来酰亚胺(例如N-(4-氟苯基)-2,3-二氯马来酰亚胺、2,4,6-三氯苯基马来酰亚胺)、N-(3,4-二氯苯基)氨基甲酸甲酯、环烷酸金属盐、硫化或二硫化四烷基秋兰姆或其金属盐、2,2-二硫代双(吡啶-O-氧化物)、根据JP 09227308的石脑油-呋喃衍生物、三苯基硼烷烷基胺配合物(例如三苯基吡啶硼烷、(4-异丙基吡啶基)甲基二苯基硼烷)、(氰硫基烷基)硫代苯并heterozole、N-苯基马来酰亚胺衍生物、N-苯基丁二酰亚胺衍生物、氟二氯甲基硫代邻苯二甲酰亚胺、二氯萘醌、氨基氯萘醌、N-三氯甲硫基环己-4-烯-1,2-二甲酰亚胺(=N-三氯甲硫基四氢邻苯二甲酰亚胺)或其它卤化N-烷硫基衍生物、N-硫代烷基邻苯二甲酰亚胺衍生物(例如N-(氟二氯甲硫基)邻苯二甲酰亚胺)、任选卤化或以其它方式取代的吡啶-8-磺酸酯、亚乙基-双-二硫代氨基甲酸或其金属盐(例如锌盐或锰盐)、二甲基二硫代氨基甲酸或其金属盐、2-(噻唑-4-基)苯并咪唑、四氯间苯二甲腈、取代的香豆素衍生物、2-硫代全氢-1,3,5-噻二唑酮衍生物、3-(3,4-二氯苯基)-1,1-二甲基脲、3,4-二氯苯氨基甲酸甲酯、N-丙酰基吲哚啉、取代的N-丙酰基苯胺衍生物、取代的N-硫代羰基吲哚啉衍生物(例如1-(苄基硫代羰基)吲哚啉)、二硫杂环戊二烯并(4,5-b)喹喔啉-2-(硫)酮、取代的(卤代炔基)芳基醚(例如五氯苯基-碘炔丙基醚)、烷基或三氟甲基取代的N-苯基苯甲酰胺、N-取代的4-苯基-1,3-噻唑啉-2-酮衍生物、1-(4-氯苯基)-1-环戊烷甲酸或其酰胺或酯、N-取代的5-(4-吡啶基甲基)-6-硫代-1-硫杂-3,5-二氮杂环己烷衍生物、联苄基二硫代碳酸金属(例如锌)盐、2-甲硫基-4,6-双(异丙基氨基)均三嗪、2-甲硫基-4-叔丁基氨基-6-环丙基氨基均三嗪、2-氨基-3-氯-1,4-萘醌、4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-甲腈、nostocarboline衍生物、取代的1,2-二羟基喹啉衍生物(例如6-乙氧基-1,2-二羟基-2,2,4-三甲基喹啉);1,4,2-噻嗪衍生物(例如5,6-二氢-3-(2-噻吩基)-1,4,2-噻嗪-4-氧化物、5,6-二氢-3-(苯并[b]噻吩-2-基)-1,4,2-噻嗪-4-氧化物、3-(4-氯苯基)-5,6-二氢-3-(2-噻吩基)-1,4,2-噻嗪-4,4-二氧化物)、1,2,3,4-四氢-2-甲基-1,4-二氧代-2-萘磺酸钠盐、N-丁基氨基甲酸3-碘炔丙基酯(IPBC)、3-(3-碘炔丙基)苯并唑-2-酮、3-(3-碘炔丙基)-6-氯苯并唑-2-酮和如EP-A 1142477中公开的其它3-异噻唑酮。
优选地,聚合物粘合剂选自(B)、(C)或(D)并且生物杀伤剂选自上述生物杀伤剂。
典型地为网织品形式的本发明经处理的纺织材料优选用于渔业和水产养殖。
根据本发明的处理保护纺织材料免受生物污损。如本文中使用的术语“生物污损”定义为微生物、植物和动物不希望地积聚于材料,例如浸入海水或淡水中的织物上。
生物污损由包括以下的各种生物引起:
细菌;藻类,例如硅藻、红藻、褐藻、绿藻和海藻;
动物,例如原生生物,例如异养鞭毛虫和纤毛虫;海绵;腔肠动物,例如水螅虫、钵水母、珊瑚和海葵(actinia)(海葵(sea anemone));多毛目环节动物;甲壳类动物,例如藤壶(蔓足类动物);软体动物,例如石鳖、腹足纲和贻贝(双壳类);苔藓虫;内肛动物;棘皮动物,例如ophiurs、海胆和海星;海鞘;以及鱼。
来自不同组的具体实例包括:
细菌,例如无色杆菌属(achromabacter sp.)、交替单胞菌属(alteromonas sp.)、艾氏交替单胞菌(a.espejina)、芽胞杆菌属(bacillus sp.)、杆菌属(bacterium sp.)、柄杆菌属(caulobacter sp.)、海洋德莱氏菌(deleyamarina)(假单胞菌属(pseudomonas))、埃希氏菌属(escherichia sp.)、大肠杆菌、黄杆菌属(flavobacterium sp.)、海洋盐单胞菌(halomonas marina)、生丝微菌属(hyphomicrobium sp.)、微球菌属(micrococcus sp.)、假单胞菌属(pseudomonas sp.)、大西洋植物杆菌(p.atlantica)、海洋假单胞菌(p.marina)、绿脓杆菌(p.pyocyanea)、玫瑰杆菌属(roseobacter)、八叠球菌属(sarcina sp.)、粘质沙雷氏菌(serrratia marcescens)、聚球蓝细菌属(synechococcus sp.)、弧菌属(vibrio sp.)、坎氏弧菌(v.campbelli)和创伤弧菌(v.vulnificus);
藻类:
硅藻,例如曲壳藻属(achnanthes sp.)、双眉藻属(amphora sp.)、咖啡双眉藻(a.coffeaeformis)、链状硅藻属(bacillaria sp.)、南极硅藻属(berkeleyasp.)、盒形藻属(biddulphia sp.)、卵形藻属(cocconeis sp.)、脆杆藻属(fragilaria sp.)、斑条藻属(grammotophora sp.)、楔形藻属(licmophora sp.)、直链藻属(melosira sp.)、舟形藻属(navicula sp.)、菱形藻属(nitschia sp.)、新月拟菱形藻(n.closterium)、杆线藻属(rhabdonema sp.)、缢缩辐节藻(stauroneis constricta)和针杆藻属(synedra sp.);
红藻,例如伊谷藻属(ahnfeltia)、土布藻(a.tobuchiensis)、绢丝藻属(callithamnion sp.)、刺瓜(c.corymbosum)、珊瑚藻(corallina officinalis)、gelidium coulteri、发状念珠藻(gigartina canaliculata)、星芒杉藻(g.stellata)、胭脂藻(hildenbrandia)、水网藻(hydrolithon boergesenii)、石叶藻(lithophillum)、石枝藻(lithothamnium)、点亮叶藻(nitophyllumpunctatum)、橡叶藻属(phycodris sp.)、育叶藻属(phyllophora sp.)、卜若地(ph.brodiae)、海头红(plocamium hamatum)、多管藻(polysiphoniadeusta)、哈维藻(p.harveyi)和掌状红皮(rhodymenia palmata);
褐藻,例如球型褐藻(ascophyllum nodosum)、爱尔兰海藻(chondruscrispus)、囊叶藻(cystoseira barbata)、黑藻(ecklonia stolonifera)、水云属(ectocarpus sp.)、如长囊水云(e.siliculosus)、墨角藻属褐藻(f. distichus)、岩藻(focus evanescens)、膨大墨角藻(f. inflatus)、齿缘墨角藻(f. serratus)、墨角藻(f.vesiculosus)、昆布属(laminaria sp.)、狭叶海带长叶变种(I.angustata var.longissima)、极北海带(I.hyperborean)、海带(I.japonica)、糖海带(I.saccharina)、巨藻(macrocystis pyrifera)、团扇藻属(padina sp.)、褐色大型藻(phyllospora comosa)、三角藻(sargassum tortile)和裙带菜(undaria pinnatifida);
绿藻,例如衣藻(chlamydomonas)、岩生刚毛藻(cladophora rupestris)、杜氏藻属(dunaliella sp.)、杜氏金藻(d.galbana)、浒苔属(enteromorphasp.)、肠浒苔(e.intestinalis)、缘管浒苔(e.linza)、仙掌藻属(halimeda sp.)、网纹狸藻(u.reticulata)、丝藻属(ulothrix sp.)、石莼(ulva)、裂片石莼(u.fasciata)、石莼(u.lactuca)、梵天花(u.lobata)和尾孢藻(urospora);
海藻,例如大叶藻(zostera marina);
动物:
包括异养鞭毛虫在内的原生生物,例如波豆虫(bodo)、鞭毛虫(codonosiga)、微细鞭毛虫(metromonas)、领鞭毛虫(monosiga)、膜滴虫(pteridomonas)和肉鞭虫(spumella)(滴虫(monas)),和
纤毛虫(ciliates),包括尾草履虫(paramecium caudatum);
海绵,例如管状海绵动物(aplisina fistularis)、小轴海绵属(axinella sp.)、穿贝海绵属(cliona sp.)、倔海绵(dysidea amblia)、洛海绵属(eurispongiasp.)、面包软海绵(halichondria panicea)、蜂海绵属(haliclona sp.)、灰质海绵(h.cinerea)、筒菌海绵(h.tubifera)、肉海绵(halisarca dujardini)、花葱海绵(leoselia idia)、山海绵(mycale)、塞氏山海绵(m.cecila)、涡虫海绵(ophlitaspongia seriata)、角骨海绵(phyllospongia papyracea)和希氏海绵属(siphonodictyon sp.);
包括水螅虫的腔肠动物,例如柄兜水母(clava multicornis)、柄有鳞目(clava squamata)、柄田毛壶(coryne uchidai)、强叶螅(dynamena pumila)、殖口螅(gonothyraea loveni)、贝螅(hydractinia echinata)、水螅(laomedeaflexuosa)、双叉薮枝螅(obelia longissima)、掌状红皮藻(rhodymeniapalmata)、桧叶螅(sertularella miurensis)、筒螅(tubularia)、六爪贝(t.crocea)和目喉筒螅(t.larynx);
钵水母类(scyphonzoas),例如海月水母(aurelia aurita)、仙女座水母(cassiopea andromeda)及霞水母属(cyanea sp.);
珊瑚,例如鹿角珊瑚(acropora)、合叶珊瑚(agaricia humilis)、橙珊瑚(a.tenuifolia)、粗糙盔形珊瑚(galaxea aspera)、柳珊瑚(leptogorgiavirgulata)、弱柳珊瑚(I.setacea)、巨星珊瑚(montastrea cavernosa)、白干手佛珊瑚(pachycerianthus multiplicatus)、纽扣珊瑚(palythoa toxia)、软珊瑚(parerythropodium fulvum fulvum)、珊瑚虫(renilla reniformis)、短指软珊瑚属(sinularia sp.)、台湾海域软珊瑚(s.cruciata)和绿岛产软珊瑚(xeniamacrospiculata);
红海葵(海葵),例如细指海葵属(metridium sp.);
多毛环节环旋虫(polychaetes circeis spirillum)、右旋虫(dexiospirabrasiliensis)(参见栉虫(neodexiospira brasiliensis))、龙介虫(eupolymnianebulosa)、覆瓦哈鳞虫(imbricata)、盘管虫(hydroides dianthus)、华美盘管虫(h.elegans)、内刺盘管虫(h.norvegica)、简氏栉虫(januabrasiliensis)(参见栉虫(neodexiospira brasiliensis))、管栖多毛虫(mercierellaenigmatica)、栉虫(neodexiospira(janua)brasiliensis)、环带沙蚕(nereiszonata)、海蛹(Ophelia bicornis)、笔帽虫(pectinaria coreni)、沙堡虫(phragmatopoma)、环毛沙堡虫(ph.californica)、拉比沙堡虫(ph.lapidos)、线虫(pigospio elegans)、海洋蠕虫岩虫(platinereis dumerilii)、才女虫属(polydora sp.)、长角佛蝗(p.antennata)、纤毛虫(p.ciliata)、文蛤(pomatoceros lamarckii)、原节虫(protodrilus symbioticus)、管栖多毛虫(salmacina tribranchiata)、尖锥虫(scoloplos armiger)、螺旋虫属(spirorbissp.)、北方水绵(s.borealis)、s.corallinae、珊瑚螺旋虫(s.rupestris)、螺旋虫(s.spirorbis)和三刺螺旋虫(s.tridentatus);
甲壳类动物,例如寄居蟹(eupagurus);
藤壶(蔓足类动物),例如藤壶属(balanus sp.),纹藤壶(b.amphitrite)、藤壶(b.balanus)、龋藤壶(b.cariosus)、缺刻藤壶(b.crenatus)、象牙藤壶(b.eburneus)、致密藤壶(b.improvisus)、钻孔藤壶(b.perforatus)、网状藤壶(b.reticulatus)、海绵状藤壶(b.spongicola)、台湾黑藤壶(chironaevermanni)、小藤壶(chtamalus dalli)、星地藤壶(ch.stellatus)、软柄藤壶(conchoderma)、颚足藤壶(elminius modestus)、茗荷几(lepas)、海氏茗荷(I.hili)、茗荷(I.pectinata)、红巨藤壶(megabalanus rosa)、钟巨藤壶(megabalanus tintinnabulum)、刺苋藤壶(pollicipes spinosus)、海藻藤壶(semibalanus balanoides)、谲诈藤壶(solidibalanus fallax)和疣状藤壶属(verruca sp.);
包括石鳖的软件动物,例如函馆锉石鳖(ischnochiton hakodadensis);
腹足纲,例如翼足螺(archidoris pseudoargus)、网螺(bittiumreticulatum)、鲍属(haliotis sp.)、鲍螺(haliotis discus)、红鲍(h.rufescens)、黍螺(littorina littorea)、玉黍螺(littorina sitkana)、火山透孔螺(megathuracrenulata)、黑草席钟螺(monodonta neritoides)、星笠螺(patella pontica)、诗博加蓑海牛(phestilla sibogae)、眼螺(rissoa splendida)、龟甲笠螺(testudinalia tessellata)、鸢尾螺(tritonia plebeia)和马蹄钟螺(trochusniloticus);
贻贝(双壳类),例如皇后海扇蛤(aequipecten opercularis)、海湾扇贝(agropecten irradians)、蛀船虫(bankia)、短齿蛤(brachyodontes lineatus)、壹湾蚬(corbicula fluminea)、长牡蛎(crassostrea gigas)、北美牡蛎(c.virginica);斑马贝属(dreissena sp.),日氏斑纹贻贝(d.bugensis)、斑马纹贻贝(d.polymorpha)、岁纹贻贝(geukensia demissa)、红鲍(haliotisrufescens)、小鳞贻贝(heteronomia squamula)、北极裂蛤(hiatella arctica)、马特海笋(martesia)、硬壳蛤(mercenaria mercenaria)、虾夷扇贝(mizuhopecten yessoensis)、偏顶蛤(modiolus modiolus)、贻贝(mytilus)、加州贻贝(m.califonianus)、紫贻贝(m.edulis)、地中海贻贝(m.gallop rovincialis)、油黑壳菜蛤(m.trossulus);牡蛎属(ostrea)、欧洲牡蛎(o.edulis)、马形牡蛎(o.equestris)、虾夷扇贝(patinopecten yessoensis)、海扇属(pecten sp.)、欧洲大扇贝(p.maximus)、海丝(pinna nobilis)、海扇贝(placopecten magellanicus)、康氏囊牡蛎(saccostrea commercialis)、蛀船虫(teredo)、普通船蛆(t.navalis)、长梗毛莨船蛆(t.pedicellatus)和食木船蛆(xylophaga);
苔藓虫,包括海冠苔藓虫属(alcyonidium sp.)、多毛苔藓虫(a.hirsutum)、聚合软苔虫(a.polyoum);口苔虫属(bowerbankia sp.),疙疸口苔虫(b.pustulosa);草台虫属(bugula sp.),多室草苔虫(bugula neritina)、太平洋草苔虫(b.pacifica)、单纯草台虫(b.simplex)、葡茎草苔虫(b.stolonifera)、云斑草苔虫(b.turrita)、网络丽苔虫(callopora craticula)、透明小分胞苔虫(celleporella hyalina);纱帐苔虫属(conopeum sp.),塞氏纱帐苔虫(c.seurati)、环节动物(cribrillina annulata);琥珀苔藓虫属(electra sp.),皮壳琥珀苔虫(e.pilosa):frustrellidra hispida;膜苔藓虫属(membraniporasp.),膜孔苔虫(m.membranacea);太平洋苔虫(philodophora pacifica);独角裂孔苔虫(schizoporella unicornis);三胞苔虫(tricellaria occidentalis);苔虫(watersipora cucullata)和苔藓虫(zoobotryon pellucidum);
内肛动物,包括海蛇类,例如针尾海蛇(ophiopholux aculeata);
海胆,例如海胆(abracia punctulata)、刺参(apostichopus japonicus)、海钱(dendraster excentricus)、普通沙钱(echinarachnius parma)、花海胆(lytechinus pictus)、拟球海胆(paracentrotus lividius)、绿海胆(strongylocentrotus)、中间球海胆(s.intermedius)和紫色球海胆(s.purpuratus)
海星,例如罗氏海星(asteria rubens)和长棘海星(pisaster giganteus);
海鞘类,例如加州海鞘(aplidium californicum),星状海鞘(a.stellatum)、archidistoma psammion、冠瘤海鞘(ascidia mentula)、黑海鞘(ascidia nigra)、巨菊海鞘(botryllus gigas)、黑菊海鞘(b.niger)、史氏菊海鞘(b.schlosseri)、鲍氏海鞘(bowerbankia gracilis);海鞘(ciona)、玻璃海鞘(c.intestinalis);深海海鞘(clavelina lepadiformis)、裂片海鞘(cystodoteslobatus)、柄海鞘(dendrodoa grossularia);二段海鞘属(didemnum sp.),二段海鞘(d.candidum)、群体海鞘(diplosoma listerianum)、红树海鞘(ecteinascidia turbinata)、蕈状海鞘(eudistoma olivaceum),毛海鞘(e.gladulosum)、皮海鞘(molgula citrina)、平扁海鞘(m.complanata)、眼斑海鞘(morchellium argus)、拉氏海鞘(polysyncraton lacazei)、皱瘤海鞘(piurastolonifera)、裂瘤海鞘(styela partita)、褶瘤海鞘(s.plicata)、鲁氏海鞘(s.rustica)、刺海鞘(styelopsis grossularia)和三段海鞘属(trididemnum sp.);以及
鱼类,例如大头鲋(blennius pholis)。
当用于渔业时,经处理的纺织材料优选为网,尤其是渔网。
渔网可为任何类型的渔网,例如拖网、围网、三层刺网、桩围鱼网、漂网、刺网、中国网、掩网、手网或捕捉器,例如龙虾捕捉器。
此外,本发明经处理的纺织材料优选用于水产养殖,尤其是海水养殖,例如鱼类养殖、小虾养殖、对虾养殖或贝类养殖,例如贻贝养殖或牡蛎养殖。纺织材料优选以网的形式使用,例如形成网箱的网。
鱼类包括生活在淡水、海水和池塘水中的所有大小的食用鱼、养殖鱼、观赏鱼和装饰鱼。食用鱼和养殖鱼包括例如鲤鱼、鳗鱼、鳟鱼、白鲑、鲑鱼、鳊鱼、石斑鱼、红眼鱼、鲢鱼、鳎鱼、鲽鱼、大比目鱼、日本黄尾鲥(Japanese yellowtail)(五条鲥(Seriola quinqueradiata))、日本鳗鱼(鳗鱼(Anguilla japonica))、真鲷(red sea bream)(Pagurus major))、海鲈(舌齿鲈(Dicentrarchus labrax))、鲻鱼(grey mullet)(鲻鱼(Mugilus cephalus))、鲳鲹(pompano)、gilthread sea bream(金头鲷(Sparus auratus))、罗非鱼(Tilapiaspp.)、chichlid物种,例如异鳞石首鱼(plagioscion)和河鲶(channel catfish)。
在本发明的特定实施例中,除防污生物杀伤剂外,本发明的纺织材料包含一种或多种用于控制鱼类中寄生物的杀虫剂。
优选的杀虫剂已在上文提及。纺织材料中杀虫剂的浓度通常为0.1-25%,优选0.5-20%。
本发明经处理的织物可控制的鱼类的寄生物包括鳋(Ergasilus)、盗鱼蚤(Bromolochus)、软刺鱼蚤(Chondracaushus)、鱼虱属(Caligus)(短鱼虱(Caligus curtus))、疮痂鱼虱(lepeophtheiraus)(苏格兰海虱(L.salmonis)、红鱼虱(Elythrophore)、迪氏鱼虱(Dichelestinum)、鲈鱼鳃虱(Lamproglenz)、海氏鱼虱(Hatscheikia)、李氏鱼虱(Leosphilus)、扁隆头鱼虱(Symphodus)、苏氏鱼虱(Ceudrolasus)、方瓢鱼虱(Pseudocycmus)、锚头鳗(Lernaea)、颚虱(Lernaeocera)、彭氏鱼虱(Pennella)、阿氏鱼虱(Achthares)、巴氏鱼虱(Basanistes)、住鲑小吸虫(Salmincola)、臂颚虱(Brachiella)、鳃虱(Epibrachielle)和拟马颈鱼虱(Pseudotracheliastes),和剑水蚤科(Ergasilidae)、Bromolochidae、软刺鳋科(Chondracanthidae)、软刺鱼蚤科(Calij idae)、管口水蚤科(Dichelestiidae)、鲶蚤科(Philichthyidae)、伪鱼虱科(Pseudocycnidae)、鲻头鳋科(Lernaeidae)、颚虱科(Lernaepodidae)、锤虱科(Sphyriidae)和塞氏鱼虱(Cectropidae),以及鳃虱科(Branchiuriae)(鲤虱)与鲺科(Argulidae)和鲺属(Argulus spec.);和蔓足纲(Cirripediae)(蔓足类动物;藤壶)和细角鳃虫(Ceratothoa gaudichaudii)。
本发明通过以下实施例阐述,所述实施例并不由此对本发明构成限定。
实施例
所用材料
网织品
使用可得自Egersund Rabben,Bekkjarvik,Norway的两种聚酰胺网。所有测试网具有30×30cm的尺寸。网(N1)具有约15×15mm的网孔大小且线丝直径为2mm。网(N1)的重量为约310g/m2。网(N2)具有约25×25mm的网孔大小且线丝直径为约3mm,网(N2)的重量为约390g/m2。
有机防污生物杀伤剂(a)
使用包含以下活性成分的有机污损生物杀伤剂类型:
生物杀伤剂(A1):70重量%的二噻农(WG配制剂)
生物杀伤剂(A2):75重量%的氟吡酰草胺(商购WG配制剂)
6.5重量%的CuCO3,
7.5重量%的乙二胺,
(其中66重量%为惰性化合物)。
聚合物粘合剂(b)
制备三种聚合物粘合剂:
粘合剂(B1):粘合剂(B1)为平均摩尔质量Mn是1500-20000g/mol
的基于大于60重量%乙烯的聚烯属粘合剂(A),
粘合剂(B2):粘合剂(B2)基于聚(甲基)丙烯酸酯(B):
59.9重量%丙烯酸正丁酯,
21.1重量%丙烯酸乙酯,
18.6重量%甲基丙烯酸甲酯,
2.4重量%丙烯酸,
0.3重量%甲基丙烯酰胺。
粘合剂(B3):粘合剂体系(B3)由聚(甲基)丙烯酸酯粘合剂(B)和作
为固定剂的聚合异氰酸酯交联剂组成,所述聚(甲基)
丙烯酸酯粘合剂(B)基于(重量%):
81%丙烯酸丁酯,
16%丙烯腈,
2%甲基丙烯酸-羟甲基酰胺,
1%丙烯酸,
所述聚合异氰酸酯交联剂基于六亚甲基二异氰酸酯(HMDL)(11-12重量%的游离异氰酸酯基团)。
通用程序
在预试验中测定最大吸液量(约60%)。将液体(包含生物杀伤剂)置于1L烧杯中。手动移动和揉捏网样品直到液体完全吸收,并实现在材料上的良好分布(约5分钟),然后将该样品在强制通风的干燥室中于50℃下干燥15分钟。
表1列举了根据该程序制备的根据本发明的网。
表1
BN=粘合剂,FA=固定剂
Claims (15)
1.用防污剂处理过的纺织材料在水生环境中的用途,所述防污剂包含:
a)一种或多种有机防污生物杀伤剂;
b)选自以下的聚合物粘合剂:
(A)平均分子量Mn为1500-20000g/mol的聚烯属粘合剂,其由以下单体获得:
(A1)60-95重量%的乙烯,
(A2)5-40重量%的至少一种选自以下的不饱和羧酸:
(A2a)单烯属不饱和C3-C10单羧酸,和
(A2b)单烯属不饱和C4-C10二羧酸,和
(A3)任选的0-30重量%的可与(A1)和(A2)共聚的其它烯属不饱和单体,
其中在各种情况下单体的量均基于所用所有单体的总量;
(B)平均分子量Mn为40,000-250,000的聚(甲基)丙烯酸系粘合剂,其通过至少50重量%(基于所用所有单体的总量)的一种或多种式(I)的单体的自由基乳液聚合获得:
其中
R1、R2和R3独立地选自任选氟取代且为线性或支化的C1-C10烷基,或者取代或未取代的芳基,和
R1和R2任选为H;
(C)聚氨酯粘合剂,其由以下组分的反应获得:
(C1)至少一种二异氰酸酯或多异氰酸酯;
(C2)至少一种二元醇、三元醇或多元醇;
(C3)任选的其它组分;和
(C4)任选的其它添加剂;
(D)含有式(II)的基团的聚异氰脲酸酯粘合剂:
其中R4为亚烷基或亚芳基残基;
c)水或包含至少65重量%(基于总溶剂混合物(c))的水的含水溶剂混合物。
2.如权利要求1要求的用途,其中有机防污生物杀伤剂(a)选自:百菌清(四氯间苯二甲腈),抑菌灵(N,N-二甲基-N′-苯基-N′-(氟二氯甲硫基)磺酰胺),对甲抑菌灵(N,N-二甲基-N′-甲苯基-N′-二氯氟甲硫基磺酰胺),敌草隆(1,1-二甲基-3-(3,4-二氯苯基)脲),氟吡酰草胺(N-(4-氟苯基)-6-[3-(三氟甲基)苯氧基]-2-吡啶甲酰胺,二噻农(2,3-二氰基-1,4-二硫杂蒽醌),Irgarol1051(N′-叔丁基-N-环丙基-6-(甲硫基)-1,3,5-三嗪-2,4-二胺),2,4,5,6-四氯间苯甲腈,4,5-二氯-2-辛基-3-(2H)-异噻唑啉-3-酮(DCOIT),2-(氰硫基甲硫基)苯并噻唑,(氰硫基甲硫基)苯并噻唑,N-环己基二氮烯二氧化物铜盐或钾盐(CuHDO、KHDO),2-巯基苯并噻唑,2-巯基吡啶氧化物锌盐或2-巯基吡啶氧化物铜盐,二硫代氨基甲酸金属盐,例如亚乙基双(二硫代氨基甲酸)锌、亚乙基双(二硫代氨基甲酸)锰、亚乙基双(二硫代氨基甲酸)铁或亚乙基双(二硫代氨基甲酸)铜),一硫化或二硫化亚乙基秋兰姆,巯基咪唑啉,二苯基胍,二邻甲苯基胍,N,N-二烷基二硫代氨基甲酸硫代酸酐,N-甲基二硫代氨基甲酸钠,N,N-二烷基二硫代氨基甲酸金属盐(Zn、Fe、Cd、Cr、Cu、Ni、Mn),N-酰基-1,2,4-噻唑,N-酰基-1,3,4-噻唑,N-酰基-1,2,3-噻唑,N-酰基-1,2,5-噻唑,2-(4-噻唑基)苯并咪唑,衍生的g-内酯,苯并三唑类,例如2-(2′-羟基苯基)苯并三唑-5,5′-二甲酸,取代的N-芳基二氯马来酰亚胺,例如N-(4-氟苯基)-2,3-二氯马来酰亚胺、2,4,6-三氯苯基马来酰亚胺,N-(3,4-二氯苯基)氨基甲酸甲酯,环烷酸金属盐,硫化或二硫化四烷基秋兰姆或其金属盐,2,2-二硫代双(吡啶-O-氧化物),根据JP 09227308的石脑油-呋喃衍生物,三苯基硼烷烷基胺配合物,例如三苯基吡啶硼烷、(4-异丙基吡啶基)甲基二苯基硼烷,(氰硫基烷基)硫代苯并heterozole,N-苯基马来酰亚胺衍生物,N-苯基丁二酰亚胺衍生物,氟二氯甲基硫代邻苯二甲酰亚胺,二氯萘醌,氨基氯萘醌,N-三氯甲硫基环己-4-烯-1,2-二甲酰亚胺(=N-三氯甲硫基四氢邻苯二甲酰亚胺)或其它卤化N-烷硫基衍生物,N-硫代烷基邻苯二甲酰亚胺衍生物,例如N-(氟二氯甲硫基)邻苯二甲酰亚胺,任选卤化或以其它方式取代的吡啶-8-磺酸酯,亚乙基-双-二硫代氨基甲酸或其金属盐,例如锌盐或锰盐,二甲基二硫代氨基甲酸或其金属盐,2-(噻唑-4-基)苯并咪唑,四氯间苯二甲腈,取代的香豆素衍生物,2-硫代全氢-1,3,5-噻二唑酮衍生物,3-(3,4-二氯苯基)-1,1-二甲基脲,3,4-二氯苯氨基甲酸甲酯,N-丙酰基吲哚啉,取代的N-丙酰基苯胺衍生物,取代的N-硫代羰基吲哚啉衍生物,例如1-(苄基硫代羰基)吲哚啉,二硫杂环戊二烯并(4,5-b)喹喔啉-2-(硫)酮,取代的(卤代炔基)芳基醚,例如五氯苯基-碘炔丙基醚,烷基或三氟甲基取代的N-苯基苯甲酰胺,N-取代的4-苯基-1,3-噻唑啉-2-酮衍生物,1-(4-氯苯基)-1-环戊烷甲酸或其酰胺或酯,N-取代的5-(4-吡啶基甲基)-6-硫代-1-硫杂-3,5-二氮杂环己烷衍生物,联苄基二硫代碳酸金属(例如锌)盐,2-甲硫基-4,6-双(异丙基氨基)均三嗪,2-甲硫基-4-叔丁基氨基-6-环丙基氨基均三嗪,2-氨基-3-氯-1,4-萘醌,4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-甲腈,nostocarboline衍生物(EP 1783128),取代的1,2-二羟基喹啉衍生物,例如6-乙氧基-1,2-二羟基-2,2,4-三甲基喹啉;1,4,2-噻嗪衍生物,例如5,6-二氢-3-(2-噻吩基)-1,4,2-噻嗪-4-氧化物、5,6-二氢-3-(苯并[b]噻吩-2-基)-1,4,2-噻嗪-4-氧化物、3-(4-氯苯基)-5,6-二氢-3-(2-噻吩基)-1,4,2-噻嗪-4,4-二氧化物,1,2,3,4-四氢-2-甲基-1,4-二氧代-2-萘磺酸钠盐,N-丁基氨基甲酸3-碘炔丙基酯(IPBC),3-(3-碘炔丙基)苯并唑-2-酮,3-(3-碘炔丙基)-6-氯苯并唑-2-酮和其它3-异噻唑酮。
3.如权利要求2要求的用途,其中有机防污生物杀伤剂(a)选自CuHDO、氟吡酰草胺和二噻农。
4.如权利要求1-3中任一项要求的用途,其中聚合物粘合剂(b)是聚烯属粘合剂(A)。
5.如权利要求4要求的用途,其中聚合物粘合剂(A)含有至少一种选自单烯属不饱和C3-C10单羧酸(A2a)和单烯属不饱和C4-C10二羧酸(A2b)的单烯属不饱和羧酸(A2)。
6.如权利要求1-3中任一项要求的用途,其中聚合物粘合剂(b)是聚(甲基)丙烯酸系粘合剂(B)。
7.如权利要求6要求的用途,其中聚(甲基)丙烯酸系粘合剂(B)通过如下组分的乳液聚合获得:
B1)作为组分B1的至少50重量%(基于所用所有单体的总重量)的一种或多种式(I)的单体:
其中
R1、R2和R3独立地是线性或支化的C1-C10烷基,或者取代或未取代的芳基;
R1和R2任选为H;
B2)作为组分B2的任选的至少一种式(VI)的单体:
其中
R9、R10、R11和R12独立地是H、为线性或支化的C1-C10烷基、取代或未取代的芳基;
B3)作为组分B3的任选的至少一种式(VII)的单体:
其中
R13和R14独立地是H、为线性或支化的C1-C10烷基、取代或未取代的芳基;X为H、OH、NH2、OR15OH、缩水甘油基、羟丙基、
下式的基团:
其中
R15是C1-C10亚烷基、取代或未取代的亚芳基;
R16是支化或线性的C1-C10烷基、取代或未取代的芳基,和
B4)可与上述单体共聚的任选的其它单体,其选自:
B41)极性单体,优选(甲基)丙烯腈和/或(甲基)丙烯酸甲酯;和/或
B42)非极性单体,优选苯乙烯和/或α-甲基苯乙烯。
8.如权利要求1-4、6或7中任一项要求的用途,其中防污剂包含固定剂(d)。
9.如权利要求1-8中任一项要求的用途,其中经处理的纺织材料为网的形式。
10.如权利要求9要求的用途,其中所述网的网孔大小为2-30mm。
11.如权利要求9或10要求的用途,其中所述网孔具有四边形、六边形或八边形的形状。
12.如权利要求1-11中任一项要求的用途,其中除生物杀伤剂(a)外,经处理的纺织材料还包含选自拟除虫菊酯、烟碱受体激动剂/拮抗剂化合物、有机磷酸酯和大环内酯杀虫剂的杀寄生物剂。
13.如权利要求12要求的在水产养殖中保护养殖动物免受寄生物危害的用途。
14.一种保护纺织材料在水生环境中免受生物污损的方法,所述方法包括用如权利要求1-8中任一项公开的防污剂处理纺织材料的步骤。
15.一种如权利要求1-12中任一项公开的应用于水生环境的纺织材料。
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CN107474617A (zh) * | 2017-07-15 | 2017-12-15 | 佛山实瑞先导材料研究院(普通合伙) | 一种水性环保抗菌防污涂料 |
CN108084070A (zh) * | 2017-12-14 | 2018-05-29 | 浙江海洋大学 | 一种黄原酸酯的制备及其在防污涂料中的应用 |
CN116970617A (zh) * | 2023-09-25 | 2023-10-31 | 烟台大学 | 红条毛肤石鳖ArWz-1基因在重金属污染中的应用 |
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DE202012100443U1 (de) | 2012-02-09 | 2012-02-28 | Wenko-Wenselaar Gmbh & Co. Kg | Duschvorhang mit Antibewuchs-Ausrüstung |
CN104211637A (zh) * | 2013-06-25 | 2014-12-17 | 四川大学 | 含三苯基吡啶和叔丁基的芳香二胺及其制备方法 |
US9758692B2 (en) * | 2014-07-25 | 2017-09-12 | Tommie Copper Ip, Inc. | Article with reactive metals bound to its surface and method of application |
PT108096B (pt) * | 2014-12-12 | 2019-07-12 | Inst Superior Tecnico | Processo de funcionalização de biocidas para imobilização em matrizes poliméricas |
JP6578745B2 (ja) * | 2015-05-29 | 2019-09-25 | 住友化学株式会社 | 水中に生息する有害生物防除用樹脂製剤 |
CN105365323A (zh) * | 2015-12-11 | 2016-03-02 | 桐乡市玉溪针织有限公司 | 高透湿防水面料 |
GB201718899D0 (en) * | 2017-11-15 | 2017-12-27 | Jotun As | Antifouling coating composition |
WO2023036492A1 (en) | 2021-09-07 | 2023-03-16 | Dsm Ip Assets. B.V. | Composite elongated body |
CN114775162B (zh) * | 2022-04-13 | 2023-06-06 | 中国水产科学研究院东海水产研究所 | 一种矩形深远海养殖分隔网的制备方法 |
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GB2188938B (en) * | 1985-12-27 | 1990-03-21 | Nippon Oils & Fats Co Ltd | Antifouling coating composition comprising a polymer having siloxane and/or alkylsilyl groups |
DE4409039A1 (de) * | 1993-12-21 | 1995-06-22 | Bayer Ag | Antifouling-Mittel |
DE19644224A1 (de) * | 1996-10-24 | 1998-04-30 | Bayer Ag | Antifoulingbeschichtung |
US6267079B1 (en) * | 1999-08-26 | 2001-07-31 | Lisa A. Eby | Fish cage |
GB0330023D0 (en) * | 2003-12-24 | 2004-01-28 | Basf Ag | Microbicidal compositions |
UA85488C2 (ru) * | 2005-06-03 | 2009-01-26 | Басф Акциенгезелльшафт | Инсектицидная композиция, ее применение для нанесения на неживой материал, способ пропитки, пропитанный материал и способ покрытия |
DE102005034215A1 (de) * | 2005-07-19 | 2007-01-25 | Basf Ag | Verfahren zur Beschichtung von Oberflächen |
MY147339A (en) * | 2007-06-12 | 2012-11-30 | Basf Se | Aqueous formulation and process for the impregnation of non-living-materials imparting a protective activity against pests |
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Cited By (4)
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CN107474617A (zh) * | 2017-07-15 | 2017-12-15 | 佛山实瑞先导材料研究院(普通合伙) | 一种水性环保抗菌防污涂料 |
CN108084070A (zh) * | 2017-12-14 | 2018-05-29 | 浙江海洋大学 | 一种黄原酸酯的制备及其在防污涂料中的应用 |
CN108084070B (zh) * | 2017-12-14 | 2020-04-14 | 浙江海洋大学 | 一种硫代亚磺酸酯类化合物的制备及其在防污涂料中的应用 |
CN116970617A (zh) * | 2023-09-25 | 2023-10-31 | 烟台大学 | 红条毛肤石鳖ArWz-1基因在重金属污染中的应用 |
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JP2012507637A (ja) | 2012-03-29 |
KR20110093863A (ko) | 2011-08-18 |
ES2398685T3 (es) | 2013-03-21 |
DK2352876T3 (da) | 2013-03-04 |
AU2009312901A1 (en) | 2010-05-14 |
CL2011001003A1 (es) | 2011-09-16 |
TW201030109A (en) | 2010-08-16 |
CA2742231A1 (en) | 2010-05-14 |
US20110217348A1 (en) | 2011-09-08 |
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EP2352876A1 (en) | 2011-08-10 |
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