CN114514258A - 基于自交联聚氨酯分散体的水性涂料组合物 - Google Patents
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Abstract
本发明涉及一种水性聚氨酯分散体,其包含:‑阴离子聚氨酯颗粒,其包含式‑COO‑M+的游离羧酸盐侧基和羧酸酯侧基二者,其中M+为用碱中和羧酸基团所产生的阳离子,所述羧酸酯侧基由用环氧硅烷酯化游离羧酸基团所产生,‑由水不溶性过渡金属化合物制成的交联颗粒。还涉及一种涂布基材的方法,包括将这种水性聚氨酯分散体施加到基材上并使其干燥,优选不施加任何热或辐射。
Description
本发明涉及基于成膜聚氨酯分散体的水性自交联组合物,所述成膜聚氨酯分散体用由环氧硅烷部分酯化的阴离子羧酸根基团官能化,并且还包含过渡金属化合物颗粒作为交联剂。
基于溶剂的聚氨酯涂料在防水建筑材料技术领域,例如在屋顶和阳台系统中已经使用了几年。这些基于溶剂的防水组合物的出于其耐久性和易于应用是众所周知的。它们提供了25年的合格耐久性(ETAG 005,Guidelines for European Technical Approval ofLiquid Applied Roof Waterproofing Kits)。
然而,由于溶剂的易燃性和游离异氰酸酯单体的存在(当其以> 0.1%的浓度存在时),基于溶剂的组合物表现出对施用者的健康危险,其被认为在与皮肤接触时和在吸入的情况下是有害的。
出于上述原因,基于溶剂的聚氨酯涂料目前主要限于专业用途。
在所有种类的技术领域中,将基于溶剂的体系转化为水性体系是普遍的趋势。
因此,几年前已经提出了成膜的水性聚氨酯分散体(PUD)。它们不含异氰酸酯单体且不含聚合物上的残余异氰酸酯基团。
然而,它们在意在用于潮湿环境中的基材的胶粘或涂布领域,尤其是防水领域中的使用不令人满意,因为它们具有非常长的干燥时间、耐晚雨性(late rain resistance),并且遭受高的吸水率,并且甚至在施加、成膜和水蒸发之后数周,它们的机械性能随后衰退。低耐水性归因于PUD的高电荷密度(稳定表面活性剂或聚合物链的电荷)和成膜仅由于聚合物颗粒的聚结而不伴随化学交联的事实。
为了克服PU膜的低耐水性,已经提出可交联的甲硅烷基封端的PUD (参见例如US6,046,295、US 5,919860和US 2017/0174815)。在这些文献中,异氰酸酯封端的预聚物与包含两个或三个烷氧基甲硅烷基和异氰酸酯反应性基团如-NH、OH或SH的硅烷化合物反应。然而,这种甲硅烷基封端的PUD仍然不能总是允许制备快速干燥和充分耐水的涂料或粘合剂。事实上,由于交联甲硅烷基仅存在于聚合物链的末端,它们的密度不可以随意增加。
本发明基于以下想法将交联甲硅烷基不作为端基而是作为全部沿着聚氨酯链的侧基引入,从而自由地调节甲硅烷基的数目,即交联基团的数目。
因此,本发明人具有通过使部分羧酸根侧基与环氧硅烷反应而官能化的阴离子聚氨酯。硅烷的环氧基与阴离子聚氨酯的羧酸根基团酯化,从而降低分散的聚合物颗粒的总阴离子电荷密度并将烷氧基甲硅烷基共价键合到聚合物上。PU颗粒上的阴离子电荷的减少可以通过监测反应时间期间负ζ电势的减少而容易地跟踪。
在其实验研究期间,本发明人已观察到难以且也不期望酯化超过约一半的PUD羧酸根基团。剩余的未反应的羧酸根基团为甲硅烷基官能的PU分散体提供稳定性。然而,如果酯化后在PUD上留下太多的阴离子电荷,则它们的亲水性不允许充分地降低吸水率并提高所得干燥涂层的耐久性和机械性能。
本发明人惊奇地发现,然而,通过使用特定的交联颗粒作为附加的交联剂,可以利用这些剩余的阴离子电荷,并且从而进一步提高最终涂层的耐久性,而不会在施加到基材上之前使聚氨酯分散体不稳定。
本申请的第一个主题是一种水性聚氨酯分散体,其包含:
-阴离子聚氨酯颗粒,其包含式-COO- M+的游离羧酸盐侧基和羧酸酯侧基二者,其中M+为用碱中和羧酸基团所产生的阳离子,所述羧酸酯侧基由用环氧硅烷酯化游离羧酸基团所产生,
-由水不溶性过渡金属化合物制成的交联颗粒。
在第二方面,本发明涉及制备这种水性聚氨酯分散体的方法,所述方法包括
-通过使阴离子聚氨酯分散体的羧酸根侧基与环氧硅烷反应来将其酯化,
-将水不溶性过渡金属化合物颗粒分散在阴离子聚氨酯分散体中。
用于本发明的聚氨酯分散体在现有技术中是公知的,并且它们的制备例如描述于US 7,345,110中。
异氰酸酯封端的预聚物首先通过多元醇与化学计量过量的多异氰酸酯反应制备,NCO/OH比通常包括1.2至5。
多异氰酸酯可以是脂族多异氰酸酯,如例如1,6-六亚甲基-二异氰酸酯、异佛尔酮-二异氰酸酯、2,4-六氢甲苯-二异氰酸酯、2,6-六氢甲苯二异氰酸酯、二环己基甲烷-二异氰酸酯、四甲基二甲苯-二异氰酸酯、降冰片烷-二异氰酸酯、双-异氰酸根合甲基)环己烷、四亚甲基-1,4-二异氰酸酯、环己烷-1,4-二异氰酸酯、1,12-十二烷-二异氰酸酯和2,2,4-三甲基六亚甲基-二异氰酸酯。
也可使用芳族多异氰酸酯。它们选自例如亚二甲苯基-二异氰酸酯、2,4-甲苯-二异氰酸酯、2,6-甲苯-二异氰酸酯和亚甲基-二苯基-二异氰酸酯。
多元醇是例如聚醚-多元醇、聚酯-多元醇或聚碳酸酯-多元醇,或其混合物。
为了将阴离子电荷引入聚合物中,将二羟基化的羧酸如二羟甲基丙酸(DMPA)与多元醇和多异氰酸酯一起共聚。
然后将所得带有羧酸侧基的异氰酸酯预聚物在剪切下分散在水中,加入胺型碱以中和羧酸基团。
制备阴离子PUD的第三步是通过加入多胺,通常是二胺进行扩链,其与异氰酸酯基团反应形成脲键。由此获得具有中和的侧羧酸根的不含异氰酸酯的聚(脲/氨基甲酸酯)。
优选的PUD由芳族二异氰酸酯和聚醚-多元醇制备。
如上所述,阴离子羧酸根基团通过与环氧硅烷反应而部分酯化,剩余的未酯化的羧酸根基团可用于在涂层干燥时稳定PUD和与过渡金属化合物颗粒交联。
本发明人已经发现,PUD在与环氧硅烷反应之前优选不应具有过高量的阴离子羧酸根基团。它们的酸值(中和一克化学物质所需的KOH的质量,以毫克计)优选包括5至25,更优选10至18,并且还更优选12至17。
具有酸值高于上述范围上限的PUD需要过高量的环氧硅烷和/或交联颗粒。在羧酸根侧基的酯化步骤期间加入太多的环氧硅烷将导致分散体早期胶凝/凝结,并且将不能制备稳定的自交联PU分散体。另一方面,加入非常高水平的交联颗粒意味着使用大量的分散剂(表面活性剂),其将使所得的干燥涂层更亲水且耐水性更低。
控制非酯化PUD的总初始阴离子电荷、选择两种不同类型的交联剂(环氧硅烷&交联颗粒)并以适量使用它们中的每一种,使得本发明人能够制备基于水的、无毒、自交联的聚氨酯分散体,其具有至少几个月的储存寿命,并且在干燥和交联之后,其产生具有耐水性和机械性能与由基于溶剂的多异氰酸酯/多元醇体系获得的那些相当的聚氨酯涂层。
任何水溶性环氧硅烷都可用于部分酯化PUD的阴离子羧酸根基团。单体环氧硅烷包含单个环氧基,也称为缩水甘油基,和两个或三个连接到硅上的可水解的烷氧基。优选的单体环氧硅烷选自3-缩水甘油基氧丙基-三烷氧基硅烷、3-缩水甘油基氧丙基-二烷氧基烷基硅烷、环氧环己基乙基三烷氧基-硅烷、环氧环己基-乙基二烷氧基烷基硅烷。烷氧基优选是乙氧基。
本发明人还使用了包含具有侧环氧基的短硅氧烷链的水溶性环氧硅烷低聚物。这类低聚物的制备例如描述在EP1896522中,并且它们可以以编号CoatOSil MP 200从Momentive获得。
相对于PUD的干重,环氧硅烷以包括0.3至5.0重量%,优选0.4至4.0重量%,并且更优选0.5至3.0重量%的量加入到PUD中。当加入PUD中的环氧硅烷的量高于约4.0至5.0重量%时,反应混合物在反应时间期间胶凝,并且不再适合作为涂料组合物。对于低于约0.3至0.4重量%的量,PUD上剩余的阴离子电荷密度太高,并且需要加入过量的交联颗粒。然而,交联颗粒的量不可以随意增加,因为存在沉降的风险或需要过高量的分散剂。
为了使PUD与环氧硅烷反应,在室温下并且在搅拌下将环氧硅烷缓慢地,优选逐滴地加入到PUD中,并使混合物反应至少几小时。不必将反应混合物保持在搅拌下,也不必加热反应混合物。在室温(20℃)下的反应时间通常包括10小时至100小时,更优选20至80小时,更优选40至75小时。
优选在部分阴离子羧酸根基团已经用环氧硅烷酯化之后将交联颗粒并入聚氨酯分散体中。
形成用于本发明的交联颗粒的过渡金属化合物必须不溶于PUD的水相中,水不溶性过渡金属化合物在本申请中定义为在20℃下在蒸馏水中的溶解度小于0.001%的化合物。事实上,PUD组合物必须不包含显著量的自由多价过渡金属阳离子,其将立即导致羧化的聚合物的早期交联,并且然后引起分散体胶凝、沉淀或沉降。因此,本发明的PUD组合物基本上不含自由多价过渡金属离子,即它们包含小于0.1重量%,优选小于0.01重量%的水溶性过渡金属盐,如例如描述在例如US 4,061,720中的碳酸锆钾或碳酸锆铵。
过渡金属化合物优选选自过渡金属盐、过渡金属氧化物和过渡金属氢氧化物。特别优选过渡金属氧化物。过渡金属有利地选自锌、铝、锡、钨和锆,优选由锌、铝、锡和钨组成,锌和铝是特别优选的。本发明人已经用氧化锌颗粒获得了优异的结果。
通过过渡金属化合物颗粒交联羧化的聚合物是已知的,并且例如描述于US 8,236,903和US 2008/0255273中。这些现有技术文献特别描述了纳米颗粒,即具有亚微细粒尺寸的颗粒,其当完全并入聚合物基质中时,提供了用于有效交联的大接触表面。发明人当其发现非纳米尺度颗粒也可以用于有效地有助于羧化的聚氨酯分散体的交联时,感到惊讶。与文献中描述的纳米颗粒相比,具有平均粒度大于约1微米的这些颗粒便宜得多,并且从环境的观点来看问题更少。
出于上述原因,本发明中使用的由过渡金属化合物制成的水不溶性交联颗粒优选具有通过激光衍射测量的包括1.0μm至20μm,优选1.5μm至10μm的重均粒径。
本发明中使用的交联颗粒的量使得交联颗粒与阴离子聚氨酯颗粒的重量比优选包括0.01至0.40,更优选0.2至0.25,并且特别是0.03至0.15。
必须有效地分散交联颗粒并稳定分散体,以便在储存期间颗粒将不会沉降。这可以通过将足够量的分散剂和/或增稠剂与交联颗粒一起并入到水性PUD中来实现。
分散剂可以是例如表面活性剂,优选非离子表面活性剂,并且增稠剂通常是水溶性有机聚合物如纤维素衍生物、聚丙烯酸的盐及其共聚物、黄原胶和聚乙烯醇、非离子聚氨酯缔合增稠剂。这些有助于分散和稳定过渡金属化合物颗粒的辅助剂应该以相当低的量使用。它们的亲水性质通过促进吸水性确实可以赋予干燥涂层或粘合剂的耐久性。
分散剂和/或增稠剂的总量不应高于相对于PUD干重的约10重量%。相对于PUD的干重,其优选包括1至10重量%,更优选2至9重量%,并且特别3至8重量%。
本发明的聚氨酯分散体还可包含一种或多种矿物填料,其总量相对于分散体的总干重为0.1至70重量%,优选1.0至40重量%,更优选5至30重量%。
当然,填料不同于交联颗粒的过渡金属化合物。它们可选自例如碳酸钙、硫酸钡、粘土、滑石、白云石、云母、硅砂、粉碎的玄武岩、高岭土,特别是煅烧的高岭土。
还可以将包含具有部分酯化的羧酸根基团的阴离子聚氨酯和交联颗粒的PUD与任何其它种类的聚合物胶乳混合。这种胶乳可选自例如聚(乙酸乙烯酯/乙烯)胶乳、聚(丙烯酸酯)胶乳、聚(苯乙烯/丙烯酸酯)胶乳、聚(乙酸乙烯酯)胶乳、聚(苯乙烯/丁二烯)胶乳、聚(丙烯酸酯/乙酸乙烯酯)胶乳、聚(乙酸乙烯酯/叔碳酸乙烯酯)胶乳、聚(丙酸乙烯酯/丙烯酸酯)胶乳、天然橡胶胶乳、预硫化的天然橡胶胶乳、聚(苯乙烯-丁二烯/苯乙烯)胶乳或聚(乙酸乙烯酯/乙烯/氯乙烯)胶乳,或其混合物。与PUD混合的胶乳优选还包含可与本发明中使用的交联颗粒交联的阴离子基团。
也可以将本发明的PUD与任何种类的沥青的水性分散体组合。
当将上述胶乳或沥青分散体与上述PUD混合时,PUD和胶乳/沥青分散体的各自量应使得所得干涂层或干粘合剂具有可接受的耐久性和耐水性。
在所得PUD /胶乳混合物或所得PUD /沥青混合物的优选实施方案中,羧化并酯化的聚氨酯聚合物的干重应高于胶乳或沥青。
本发明的聚氨酯分散体的水量包括相对于分散体总重量的30%至95%,优选35至75%。当PUD与其它胶乳或沥青分散体混合时,该水含量应当理解为这些分散体的混合物的水含量。
本发明的水性聚氨酯分散体是自交联组合物,也称为单组分组合物,即它们不需要在即将将分散体施加到待涂布、处理、胶合或粘结的基材上之前引入催化剂或任何额外的交联剂。这使得它们作为涂料组合物、底漆、粘合剂、粘结剂、密封剂等的用途非常简单和方便。本发明的PUD可以被施加到基材上或施加到两个基材之间,并且将干燥而无需施加热或辐射形式的能量。在PUD被施加在两个基材之间的情况下,它们中的至少一个应该是充分多孔的或水可渗透的以允许PUD的水蒸发。
因此,本发明的另一主题是一种涂布基材的方法,特别是对基材进行防水的方法,包括将上述水性聚氨酯分散体施加到基材上或基材之间,并使其干燥,优选不施加任何热或辐射。
本发明的自交联聚氨酯分散体也可与第二交联组分,如例如多异氰酸酯组分组合使用。这种组分应该容易地与本发明的水性分散体混合。可与本发明的PUD组合使用的水分散性多异氰酸酯例如可以以Bayhydur®由Covestro获得。当分散在本发明的水性PUD中时,这些化合物是自交联的,并且可增强所得的聚合物涂层。
本发明的水性自交联聚氨酯分散体可用于其中需要在基材上或基材之间形成耐水和耐温涂层的各种技术领域中。
PUD可例如用作涂料组合物,特别是基材的防水组合物,例如用于外部建筑基材如屋顶、立面或阳台的基材的防水组合物,用作木材、地板、石材、混凝土、抹灰、灰泥、金属或聚合物基材的涂料组合物,用作粘合剂,用作密封剂,用作底漆。
PUD也可用于涂布基材以改善其耐久性、机械和/或耐化学性。
它们还可用作瓷砖下面的防水基材的底涂层,或用作建筑构件如屋顶、工业或装饰地板、地下室、阳台、露台(terrace)、桥梁构件的涂层。
实施例
如下制备具有下表1中所列组成的四种水性聚氨酯分散体:
实施例1:制备阴离子聚氨酯的水性分散体,其由聚醚-多元醇、芳族二异氰酸酯、二羟甲基丙酸和作为扩链剂的乙二胺制备。所得聚氨酯分散体(PUD)具有干物质含量42%,并且酸值为16.1 mg KOH/g。在一小时时间内将0.5重量%(相对于PUD的干重)的3-缩水甘油基氧丙基-三乙氧基硅烷逐滴加入到PUD中。将容器封闭,并令混合物在不搅拌的情况下反应72小时。反应72小时后,在搅拌下加入分散剂和消泡剂。搅拌5分钟后,立刻加入ZnO和填料(硫酸钡、碳酸钙),并在30分钟期间通过高速混合分散。最后,用剩余的水、丙二醇和增稠剂(非离子聚氨酯缔合增稠剂)的混合物调节粘度。
ZnO颗粒的粒度参数如下:
D90:9.83 µm;D50:3.35 µm,D10:0.72 µm且D平均 : 4.64 µm。
如实施例1制备对比例2,除了PUD不与3-缩水甘油基氧丙基-三乙氧基硅烷反应,并且没有ZnO颗粒并入到分散体中。
对比例3如实施例1制备,其中唯一的区别在于PUD不与3-缩水甘油基氧丙基-三乙氧基硅烷反应。
如实施例1制备对比例,其中唯一的区别在于组合物中未并入ZnO颗粒。
表1
实施例1(本发明) | 对比例2 | 对比例3 | 对比例4 | |
PUD | 60 | 60 | ||
环氧硅烷-PUD | 60 | 60 | ||
ZnO | 3 | 3 | ||
分散剂 | 0.1 | 0.1 | 0.1 | 0.1 |
消泡剂 | 0.5 | 0.5 | 0.5 | 0.5 |
硫酸钡 | 10 | 10 | 10 | 10 |
碳酸钡 | 15 | 18 | 15 | 18 |
滑石 | 5 | 5 | 5 | 5 |
单丙二醇 | 1 | 1 | 1 | 1 |
增稠剂 | 2 | 2 | 2 | 2 |
水 | 3.4 | 3.4 | 3.4 | 3.4 |
然后将聚氨酯分散体以1 mm的湿厚度涂布到聚乙烯膜上,并令其在室温下干燥/固化7或28天。然后将涂层从聚乙烯基材上剥离,并且将膜切割成样品。然后将干燥7天的膜称重,在室温下在蒸馏水中浸没24小时或14天,再次称重,并计算重量增加(吸水率),并相对于样品的初始干重表示。根据ASTM D412测量在水浸没前后的机械性质,即断裂伸长率(EaB)和拉伸强度(TS)。
结果示于表2。
表2
实施例1 | 对比例2 | 对比例3 | 对比例4 | |
固化7天后的EaB | 372 % | 340 % | 350 % | 360 % |
固化28天后的EaB | 305 % | 285 % | 320 % | 335 % |
固化7天后的TS | 5.40 MPa | 3.20 MPa | 3.70 MPa | 3.90 MPa |
固化28天后的TS | 5.45 MPa | 3.95 MPa | 4.10 MPa | 4.30 MPa |
浸没24小时后的吸水率 | 0.5 % | 7.61 % | 7.25 % | 6.43 % |
浸没14天后的吸水率 | 2.0 % | 18.0 % | 12.0 % | 9.0 % |
浸没48小时后的EaB | 410 % | 810 % | 620 % | 600 % |
浸没48小时后的TS | 4.91 MPa | 2.70 MPa | 3.40 MPa | 4.05 MPa |
浸没14天后的EaB | 546 % | 950 % | 750 % | 710 % |
浸没14天后的TS | 4.52 MPa | 2.40 Mpa | 3.20 Mpa | 3.90 MPa |
可以看出,实施例1的聚氨酯膜固化得比对比例2-4的聚氨酯膜快得多。其拉伸强度在仅固化7天后几乎不增加。
实施例1的膜进一步吸收少得多的水。在24小时浸没后其吸水率几乎与在相同条件下测试的单组分基于溶剂的聚氨酯树脂(来自Maris Polymers的Mariseal® 250)的吸水率相同。
最重要的是,本发明的聚氨酯膜(实施例1)的机械性能在浸没期间的劣化远小于对比例2-4的膜的机械性能的劣化。
因此,这些实验实施例表明,环氧硅烷和过渡金属化合物颗粒的交联颗粒的组合使用产生无毒、无溶剂、不易燃、稳定的成膜聚氨酯分散体,当将其涂布到基材上时,形成耐水性涂层,所述耐水性涂层显示出其机械性能的良好保持性。
Claims (13)
1.一种水性聚氨酯分散体,其包含,
-阴离子聚氨酯颗粒,其包含式-COO- M+的游离羧酸盐侧基和羧酸酯侧基二者,其中M+为用碱中和羧酸基团所产生的阳离子,所述羧酸酯侧基由用环氧硅烷酯化游离羧酸基团所产生,
-由水不溶性过渡金属化合物制成的交联颗粒。
2.根据权利要求1所述的水性聚氨酯分散体,其中水不溶性过渡金属化合物选自过渡金属盐、过渡金属氧化物和过渡金属氢氧化物,优选选自过渡金属氧化物。
3.根据权利要求1或2所述的水性聚氨酯分散体,其中过渡金属选自锌、铝、锡和钨,优选锌和铝。
4.根据前述权利要求中任一项所述的水性聚氨酯分散体,其中交联颗粒与阴离子聚氨酯颗粒的重量比包括0.01至0.40,优选0.2至0.25,并且更优选0.03至0.15。
5.根据前述权利要求中任一项所述的水性聚氨酯分散体,其中所述交联颗粒具有通过激光衍射测量的包括1.0μm至20μm,优选1.5μm至10μm的重均粒径。
6.根据前述权利要求中任一项所述的水性聚氨酯分散体,其中环氧硅烷选自3-缩水甘油基氧丙基-三烷氧基硅烷、3-缩水甘油基氧丙基-二烷氧基烷基硅烷、环氧环己基乙基三烷氧基-硅烷、环氧环己基-乙基二烷氧基烷基硅烷和水溶性环氧硅烷低聚物。
7.根据前述权利要求中任一项所述的水性聚氨酯分散体,其还包含0.1至70重量%,优选1.0至40重量%的矿物填料。
8.根据前述权利要求中任一项所述的水性聚氨酯分散体,其还包含分散剂和/或增稠剂,所述分散剂优选选自非离子表面活性剂,所述增稠剂优选选自水溶性有机聚合物。
9.根据前述权利要求中任一项所述的水性聚氨酯分散体,其中相对于所述分散体的总重量,水的量包括30%至95%,优选35%至75%。
10.一种制备根据权利要求1-9中任一项所述的水性聚氨酯分散体的方法,包括
-通过使阴离子聚氨酯分散体的羧酸根侧基与环氧硅烷反应来将其酯化,
-将水不溶性过渡金属化合物颗粒分散在阴离子聚氨酯分散体中。
11.根据权利要求10的制备水性聚氨酯分散体的方法,其中相对于PUD的干重,用于酯化的环氧硅烷的量包括0.3至5.0重量%,优选0.4至4.0重量%,并且更优选0.5至3.0重量%。
12.一种涂布基材的方法,包括将根据前述权利要求中任一项的水性聚氨酯分散体施加到基材上并使其干燥,优选在不施加任何热或辐射的情况下。
13.根据权利要求1至9中任一项的水性聚氨酯分散体作为基材的防水组合物,作为木材、地板、石材、混凝土、抹灰、灰泥、金属或聚合物基材的涂料组合物,作为粘合剂,作为密封剂,作为底漆的用途。
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EP (2) | EP3808788A1 (zh) |
CN (1) | CN114514258A (zh) |
AR (1) | AR120097A1 (zh) |
BR (1) | BR112022006257A2 (zh) |
CL (1) | CL2022000936A1 (zh) |
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EP4265662A1 (en) | 2022-04-20 | 2023-10-25 | Saint-Gobain Weber France | Polyurethane-based coatings with high solar reflectance index |
IT202200009029A1 (it) * | 2022-05-04 | 2023-11-04 | Central Chimica S R L | Guaina impermeabilizzante liquida fibrata |
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US20030055171A1 (en) * | 2000-03-09 | 2003-03-20 | Overbeek Gerardus Cornelis | Aqueous polymer compositions |
WO2006099918A2 (de) * | 2005-03-22 | 2006-09-28 | Relius Coatings Gmbh & Co. Kg | Zubereitung zur beschichtung von substratoberflächen |
CN109804103A (zh) * | 2016-10-11 | 2019-05-24 | 杰富意钢铁株式会社 | 锌系镀覆钢板用表面处理液,带有表面处理皮膜的锌系镀覆钢板的制造方法和带有表面处理皮膜的锌系镀覆钢板 |
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US5554686A (en) | 1993-08-20 | 1996-09-10 | Minnesota Mining And Manufacturing Company | Room temperature curable silane-terminated polyurethane dispersions |
US5919860A (en) | 1997-12-17 | 1999-07-06 | Bayer Corporation | Aqueous polyurethane/urea dispersions containing alkoxysilane groups |
DE102004017436A1 (de) | 2004-04-08 | 2005-10-27 | Bayer Materialscience Ag | Verfahren zur kontinuierlichen Herstellung einer wässrigen Polyurethandispersion |
US7893183B2 (en) | 2005-04-07 | 2011-02-22 | Momentive Performance Materials Inc. | Epoxy silane oligomer and coating composition containing same |
US20080255273A1 (en) | 2006-11-20 | 2008-10-16 | Air Products And Chemicals, Inc. | Particulate Filled Polymers |
US8236903B2 (en) | 2007-08-07 | 2012-08-07 | Shaffer Jay M | Transition metal crosslinking of acid-containing polymers |
US10351653B2 (en) | 2014-05-28 | 2019-07-16 | 3M Innovative Properties Company | Polyurethane-polyurea dispersions comprising hydrazine or hydrazide chain extenders |
JP7079117B2 (ja) * | 2018-03-01 | 2022-06-01 | 三井化学株式会社 | ガスバリア性積層体の製造方法 |
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2019
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- 2020-09-28 AR ARP200102680A patent/AR120097A1/es unknown
- 2020-10-13 CN CN202080072177.6A patent/CN114514258A/zh active Pending
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Publication number | Priority date | Publication date | Assignee | Title |
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US20030055171A1 (en) * | 2000-03-09 | 2003-03-20 | Overbeek Gerardus Cornelis | Aqueous polymer compositions |
WO2006099918A2 (de) * | 2005-03-22 | 2006-09-28 | Relius Coatings Gmbh & Co. Kg | Zubereitung zur beschichtung von substratoberflächen |
CN109804103A (zh) * | 2016-10-11 | 2019-05-24 | 杰富意钢铁株式会社 | 锌系镀覆钢板用表面处理液,带有表面处理皮膜的锌系镀覆钢板的制造方法和带有表面处理皮膜的锌系镀覆钢板 |
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PE20220880A1 (es) | 2022-05-27 |
BR112022006257A2 (pt) | 2022-06-21 |
EP4045557A1 (en) | 2022-08-24 |
IL292179A (en) | 2022-06-01 |
AR120097A1 (es) | 2022-02-02 |
EP3808788A1 (en) | 2021-04-21 |
WO2021074134A1 (en) | 2021-04-22 |
US20230081580A1 (en) | 2023-03-16 |
CO2022004648A2 (es) | 2022-04-29 |
CL2022000936A1 (es) | 2023-01-20 |
MX2022004421A (es) | 2022-05-24 |
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