CN1039339C - 存放稳定的快速固化水基涂料及其应用 - Google Patents

存放稳定的快速固化水基涂料及其应用 Download PDF

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CN1039339C
CN1039339C CN90104773A CN90104773A CN1039339C CN 1039339 C CN1039339 C CN 1039339C CN 90104773 A CN90104773 A CN 90104773A CN 90104773 A CN90104773 A CN 90104773A CN 1039339 C CN1039339 C CN 1039339C
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polyfunctional amine
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伏朗克·兰帝
安德鲁·墨求里奥
罗依·富莱恩
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Abstract

公开了一种存放稳定的快速固化水基涂料。此涂料含有一种阴离子稳定的胶乳聚合物、一种多官能胺和一种挥发性碱,碱的用量足以使胺的共轭酸去质子化。

Description

存放稳定的快速固化水基涂料及其应用
本发明涉及水基涂料,特别是施用后很快干燥的路面标志用的水基涂料。
技术界曾公开了各种努力,试图生产一和水基路面标志涂料来代替溶剂基涂料。但一个重大难题是水基涂料干得不够快。
欧洲专利申请200249号公开了将一种高聚物的水基分散体涂敷在路面上,然后用一种水溶性盐与该组合物相接触,使涂料迅速干燥,並且在施用5分钟后即能承受雨水的冲刷。该公开需要用两种组合物来喷涂,这就必须使用额外的设备。
欧洲专利申请0066108号公开了一种路标用组合物,其中的粘合剂是纯丙烯酸树脂、羧基化的苯乙烯/反丁烯二酸二丁酯共聚物和一种聚合物的多官能胺(如聚丙烯亚胺)的混合物。该申请声明,所公开的组合物在存放48小时后不再稳定,必须再加入多官能胺以恢复活性。
本发明提供了一种涂料组合物,它能迅速干燥,施用后很快就产生防水性,並且在存放后保持活性。
这种水基涂料组合物含有玻璃化温度高于  0℃的阴离子稳定的胶乳聚合物、一种有效数量的多官能胺和一种挥发性碱,挥发性碱的用量要能将组合物的pH提高到足以使多官能胺基本上处于不电离状态(去质子化),从而排除了多胺与阴离子稳定的乳液及涂料中的阴离子组分的相互作用。
本发明的一个方面是提供了一种公路或人行道用的水基路标涂料。本发明的公路或人行道用的水基路标涂料可用于标志各种成分的路面或停车场通道上的行道线或符号,例如可用在沥青的、柏油的、或加或不加集填料或敷面材料的混凝土铺砌的路面上。这种水基路标涂料干燥迅速,很快就产生耐冲刷和抗轮胎花纹印记的性能。
水基涂料组合物由以下物质制成:
(A)一种阴离子稳定化的胶乳聚合物;
(B)一种可溶的或可分散的(最好是可溶的)聚合物,形成此聚合物的单体中有20%至100%(重量)的单体含有胺基;
(C)一种挥发性碱,其用量能将组合物的PH升高到足以使多官能胺基本上处于不离解状态(去质子化),从而排除了聚胺与阴离子稳定化的胶乳和涂料中的阴离子组分之间的相互作用。此挥发性碱必须有足够的挥发性,以便能在空气干燥的条件下逸出。
阴离子稳定的胶乳聚合物
阴离子稳定的胶乳聚合物可以用发表在诸如D.C.Blackley的“乳液聚合:理论与实践”(Wiley公司出版,1975)和F.A.Bovey等的“乳液聚合”(Inter-Science Publishers公司出版,1965)这类教科书中的已知方法制备。通常,阴离子稳定的胶乳是由诸如以下各种单体制备的聚合物或共聚物:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己基酯、丙烯酸癸酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、苯乙烯、丁二烯、乙烯、乙酸乙烯酯、“Versatie”酸的乙烯基酯(Versatic酸是一种有c9、c10和c11链长的三级一元羧酸,其乙烯基酯也称为 Vinyl versatate”)、氯乙烯、乙烯基吡啶、1,1-二氯乙烯、丙烯腈、氯丁二烯、丙烯酸、甲基丙烯酸、亚甲基丁二酸、顺丁烯二酸和反丁烯二酸。最好是用α-β位上有不饱和烯基的单体及其酯的、尤其是丙烯酸酯和甲基丙烯酸酯的聚合物和共聚物,而且最好采用“丙烯酸类单体的乳液聚合:1966年5月“(Rohm and Haas公司出版,费城、宾州)一书中列出的方法来制备。该书在这里引用作为参考。
分散的胶乳粒子上的负电荷可以由几种方式获得,最常见的是用阴离子表面活性剂或分散剂作为乳液聚合期间的、或是聚合后加到乳液之中的稳定剂。在这些阴离子稳定的胶乳的聚合期间或之后,胶乳中当然也可以加有非离子表面活性剂。可用的表面活性剂和分散剂有:脂族松香酸和环烷酸的盐、萘磺酸和甲醛的低分子量缩合产物、具有适当的HLR值(亲水、亲油平衡值)的羧酸型聚合物与共聚物、高级烷基硫酸盐(例如十二烷基硫酸钠)、烷基芳基磺酸盐(例如十二烷基苯磺酸盐、异丙基苯磺酸钠或钾、异丙基萘磺酸钠或钾)、磺化丁二酸酯(如琥珀酸二辛酯磺酸钠、丁二酸高级烷基酯磺酸碱金属盐、例如丁二酸辛酯磺酸钠)、N-甲基-N-棕榈酰牛磺酸钠、油酰羟乙磺酸钠、烷基芳基聚乙氧基乙醇硫酸酯或磺酸酯的碱金属盐,例如有1至5个氧乙烯单元的叔辛基苯氧基聚乙氧基乙基硫酸钠,以及工艺上已知的其它各种阴离子表面活性剂和分散剂。
另一类带负电的胶乳,其电荷是得自于聚合物中包含着的少量酸性基团,这些酸性基团可以是盐的形式,例如碱金属盐或铵盐。这类酸性基团的实例包括由结合进去的引发剂片段、顺丁烯二酸、乙烯基磺酸、2-丁烯酸、丙烯酸、甲基丙烯酸、亚甲基丁二酸等产生的基团。
聚合物的玻璃化温度(Tg)必须高于0℃。Tg低于0℃的聚合物一般不能使用,因为它们太软,结果使耐磨性变差,而且促进脏物的累积。本发明也可以用形态更复杂的聚合物,例如用核一壳结构的颗粒来实施。这些形态复杂的聚合物常常显示出多个玻璃化温度,並且有可能多个Tg中的一个低于0℃,但是聚合物的平均的、或有效的Tg值必须在0℃以上。
为制备胺官能聚合物与阴离子稳定的胶乳聚合物的贮存稳定的组合物,要加入足够数量的挥发性碱,将组合物的pH升高到或接近于使所有的胺官能团基本上处于非离子状态(去质子化)的pH值,于是胺官能团基本上维持在非离子状态,从而不会与阴离子稳定的胶乳聚合物相互作用。为达到此pH值所需要的挥发性碱的数量的起点估算值可以根据为中和胶乳聚合物中所有酸性基团(即由共聚的带羧酸单体、表面活性剂或引发剂形成的酸性基团)和胺碱的共轭酸所需要的碱的当量数计算。如果胺没有充分去质子化,则乳液将显示可观察到的随时间不稳定的迹象,例如粘度增大和显微镜下可看到的“粒子熔合”,这是聚结/胶凝的早期阶段。一当量的挥发性碱(根据胶乳酸和聚胺的滴定度)常常足以得到稳定的体系,但是若要实现更长期的稳定可能需要更多的挥发性碱(~3至4当量)。可以采用更多量的碱而不背离本发明的精神,但是涂料的“快干”性能可能会降低。如果在制造过程中所用的设备,在从加入挥发性碱到产品封装在密封容器内的任何阶段存在着由于蒸发而损失挥发性碱的可能性,则应增加加到生产装置中的挥发碱量,以抵消此项损失。
在涂敷之后,挥发性碱蒸发,于是组合物的pH降低。当组合物的pH降至某个数值时,聚胺开始质子化,变成阳离子型的。据信,在阴离子稳定的胶乳聚合物存在下,是聚胺向阳离子聚合物的转化引发了快速干燥,虽然造成快速干燥性能的准确机理尚未建立。
多官能胺
本发明组合物含有一种多官能胺,最好是一种聚合物,其单体中有20%至100%,最好是至少50%(重量)含有胺基。含胺单体的实例包括下列各类物质:
各类胺
1.氨基烷基乙烯基醚或硫醚,其中烷基可以是直链或支链型,有2至3个碳原子,其中氮原子可以是伯氮、仲氮或叔氮原子(美国专利2879178),在后一种情形里,剩余氢原子中的一个可以被烷基、羟烷基或烷氧基烷基取代,其烷基组分可以有1至4个碳原子,最好是只有一个碳原子。具体实例包括:β-氨乙基乙烯基醚、β-氨乙基乙烯基硫醚、N-一甲基-β-氨乙基乙烯基醚或硫醚、N-一乙基-β-氨乙基乙烯基醚或硫醚、N-一丁基-β-氨乙基乙烯基醚或硫醚、和N-一甲基-3-氨丙基乙烯基醚或硫醚。
2.如下列化学式II表示的丙烯酰胺或丙烯酸酯:
Figure C9010477300081
其中
R是H或CH3
n是O或1;
X是O或N(H);
若n为O,则A为O(CH2)x,其中X是2或3,或是(氧-亚烷基〕y,其中(氧-亚烷基〕y是一个聚(氧化烯基〕y,其分子量在88至348之间,其中各亚烷基是1,2-亚乙基,或是1,2-亚丙基,可以相同或不同;若n为1,则A是一个有2-4个碳原子的亚烷基;R*是H、甲基或乙基;
R0是H、苯基、苄基、甲基苄基、环己基或(C1-C6)烷基。
化学式II的化合物实例包括:
丙烯酸或甲基丙烯酸的二甲基氨基乙酯;丙烯酸或甲基丙烯酸β-氨基乙酯;N-β-氨乙基丙烯酰胺或甲基丙烯酰胺;N-(一甲基氨乙基)丙烯酰胺或甲基丙烯酰胺;丙烯酸或甲基丙烯酸N-(一正丁基)-4-氨基丁酯;甲基丙烯酰氧基乙氧基乙胺;和丙烯酰氧基丙氧基丙氧基丙胺。
3.N-丙烯酰氧基烷基-噁唑烷和N-丙烯酰氧基烷基四氢-1,3-噁嗪及其中“烷基”链被烷氧烷基和聚(烷氧烷基)取代的相应组分,它们均可用化学式III表示:其中
R为H或CH3
m是从2到3的整数;
R1在不与R2直接相连时,选自H、苯基、苄基和(C1-C12)烷基;
R2在不与R1直接相连时,选自H和(C1-C4)烷基;
R1和R2当直接相连时与化学式环中所联结的碳原子一起形成一个5至6元碳环,即,当R1与R2连在一起时,选自1,5-亚戊基和1,4-亚丁基;
A′是O(CmH2m)-或(氧-亚烷基)n,其中(氧-亚烷基)n是一个聚(氧化烯)基,分子量为88至348,其中各亚烷基为1,2-亚乙基或1,2-亚丙基,可以相同或不同。
化学式III的化合物可以在各种条件下水解成仲胺。水解产生了化学式IV所代表的产物:在由同一受让人掌握的美国专利3,037,006和3,502,627以及和它们相应的在国外的申请及专利中对式III的化合物有所披露,而且其中披露的任一单体化合物都可用来制备用于本发明组合物中的共聚物。
化学式III的化合物实例包括:
甲基丙烯酸噁唑烷基乙酯;丙烯酸噁唑烷基乙酯;3-(r-甲基丙烯酰氧基丙基)-四氢-1,3-噁嗪;3-(β-甲基丙烯酰氧基乙基)-2,2-五亚甲基噁唑烷;3-(β-甲基丙烯酰氧基乙基-2-甲基-2-丙基噁唑烷;N-2-(2-丙烯酰氧基乙氧基)乙基噁唑烷;N-2-(2-甲基丙烯酰氧基乙氧基)乙基噁唑烷;N-2-(2-甲基丙烯酰氧基乙氧基)乙基-5-甲基噁唑烷;N-2-(2-丙烯酰氧基乙氧基)乙基-5-甲基噁唑烷;3-〔2-(2-甲基丙烯酰氧基乙氧基)乙基)〕-2,2-五亚甲基噁唑烷;3-〔2-(2-甲基丙烯酰氧基乙氧基)乙基)〕-2,2-二甲基噁唑烷;3-〔2-(甲基丙烯酰氧基乙氧基)乙基〕-2-苯基噁唑烷。
4.容易通过水解而产生胺的单体的聚合物可以用作为本粘合剂组合物的含胺组分或用它产生含胺组分聚合物。这类单体的实例是丙烯酰氧基-酮亚胺和醛亚胺,例如以下化学式V和VI所代表的:
           H2C=(CR)-COOA"N=Q           (V)
Figure C9010477300111
其中
R是H或CH3
Q则选自具有以下结构式的基团:R6是H或在一个CHR6单元中为甲基;R5选自(C1-C12)烷基和环己基;
R4选自(C1-C12)烷基和环己基;
R3选自苯基、卤代苯基、(C1-C12)烷基、环己基、和(C1-C4)烷氧苯基;
A″是一个(C1-C12)亚烷基;
A0,B和D是氧化烯基,它们可以相同或不相同,其化学式为-OCH(R7)-CH(R7)-,其中R7为H、CH3或C2H5
X是整数4或5;
n0是1到200的整数;
n′是1到200的整数;
n″是1到200的整数,n0-1、n′-1与n″-1的总和为2到200。
化学式V和VI的实例化合物有:
甲基丙烯酸2-〔4-(2,6-二甲基亚庚基)氨基〕乙酯、甲基丙烯酸3-〔2-(4-甲基亚戊基)氨基〕丙酯、甲基丙烯酸β-(亚苄基氨基)乙酯、甲基丙烯酸3-〔2-(4-甲基亚戊基)氨基〕乙酯、丙烯酸2-〔4-(2,6-二甲基亚庚基)氨基乙酯、甲基丙烯酸-12-(环亚戊基氨基)十二烷基酯,N-(1,3二甲基亚丁基)-2-(2-甲基丙烯酰氧基乙氧基)乙胺、N-(亚苄基)甲基丙烯酰氧基乙氧基乙胺、N-(1,3-二甲基亚丁基)-2-(2-丙烯酰氧基乙氧基)乙胺、N-(亚苄基)-2-(2-丙烯酰氧基乙氧基)乙胺。
化学式V和VI的化合物在酸性、中性或碱性的水介质中水解,生成相应的伯胺或盐,其中化学式中的-N=Q基团变成-NH2和O=Q。式V和VI的化合物已在美国专利3,037,969和3,497,485中公开,其中所公开的任何单体化合物都可用来制备本发明组合物的水溶性聚合物部分所用的共聚物。
聚合物溶解度
水溶性  胺官能聚合物包括完全溶解的与部分溶解的两类聚合物。水溶性胺官能聚合物一词是指以游离碱、中性的或盐的形式能完全溶解的聚合物。某些聚合物在所有pH值时均能溶解,而另一些则在某一pH范围,例如从约5到10时才溶解。其它的含胺聚合物通常在高pH时不溶,在酸性pH值,尤其是在pH从5到7的范围内溶解或部分溶解。所谓部分溶解有两种情形,一是一部分聚合物溶于水中,二是整个聚合物以胶束或单个分子的聚集体(一般是高度地被水溶胀的聚集体)的形式溶解。后一种常称为胶体溶液。最好是在酸性pH值下大部 分聚合物可以溶解。
胺聚合物制备
一般来说,胺官能聚合物可以通过在水介质中溶液聚合来得到,介质可以是中性、酸性或碱性,这取决于所要合成的具体的聚合物。这是工艺上一般都了解的,例如在美国专利4,119,600号中所述。聚合反应通常在含有少量酸的水介质中进行,酸可以是无机酸也可以是有机酸,例如醋酸或盐酸。胺官能聚合物中有最高达80%(重量)的一种或多种单烯基不饱和单体(例如丙烯酸甲酯、丙烯酰胺和甲基丙烯酰胺)构成的共聚物。制备水溶性聚合物时也可以用少量的相对不溶性的共聚物。而不溶性聚合物中可能含这种共聚单体比较多。这类单体包括:丙烯酸与(C1至C18)醇的酯和甲基丙烯酸与(C1至C18)醇、特别是(C1-C4)链烷醇的酯;苯乙烯、乙烯基甲苯、醋酸乙烯、氯乙烯、1,1-二氯乙烯、取代的苯乙烯、丁二烯、取代的丁二烯、乙烯,以及丙烯酸或甲基丙烯酸的腈和酰脘。在制备指定的胺官能聚合物中所用的具体的共聚单体取决于在制备共聚物中所用的含胺单体的比例。因此这种聚合物或共聚物是阳离子型,或者也可以是非离子型的乙烯基单体的聚合物或共聚物。阳离子型单体的实例是胺和亚胺;所述的其它单体是非离子型的。因此,除了由于所用单体中的杂质或在合成。存放与使用期间因少量水解而可能生成痕量酸性基团之外,这些水溶性共聚物并不含有酸性基团。
挥发性碱
所用的挥发性碱的类型和数量必须是足以使组合物的pH增加到某个数值,在此PH值下多官能胺是不离解的(去质子化),以避免与阴离子稳定的乳液相互作用。挥发性碱最好用氨,可以只用氨,或是用氨与其它挥发性或不挥发性碱的混合物作为挥发性碱。可以使用的其它挥发性碱有吗啉、低级烷基胺、2-二甲基氨基乙醇、N-甲基吗啉、乙二胺等。
在本发明组合物中还可以使用工艺上已知的填料、扩充料、颜料和其它添加剂。如果在交通用涂料组合物中使用颜料,则颜料体积分数一般为50%至60%。可以使用的颜料实例包括粘土、碳酸钙、滑石粉、二氧化钛、碳黑和各种彩色颜料。
在选择添加剂的类型和用量时必须小心,以避免将组合物的pH改变得影响其存放稳定性,或是将pH缓冲到某种程度,以致在涂敷后pH的下降不足以引发聚胺的质子化。例如,用PKa值较低的聚胺和太大量的碳酸钙作为填料制备的涂料,其固化时间可能会延长到不合要求的程度。
交通用涂料组合物的固体含量一般是从35%至70%(体积),其粘度为5.8至17泊。本发明所提供的涂料也可用于其它的外用涂料,例如维修涂料、房屋涂料等。
下列实例说明了本发明的某些方面,但是不要认为这是对说明书和权利要求中所述的本发明范围的限制。
缩写的含义:
AM=丙烯酰胺
DMAEMA=甲基丙烯酸二甲基氨基乙酯
DMAPMA=二甲基氨丙基甲基丙烯酰胺
HEMA=甲基丙烯酸羟乙酯
MMA=甲基丙烯酸甲酯
OXEMA=甲基丙烯酸噁唑烷基乙酯
P-OXEMA=聚甲基丙烯酸噁唑烷基乙酯
涂料制备
按下列标准涂料配方,将列为研磨组分的成分一起研磨,然后加入列在稀释剂中的其它组分,以制备试验涂料。阴离子稳定的胶乳粘合剂是丙烯酸丁酯、甲基丙烯酸甲酯和甲基丙烯酸的阴离子型共聚物,其Tg为20℃,粒子大小为200纳米。研磨组分                        用量(千克/389.9升)乳液(50%固体)                        207.7水                                    12.88Tamol 850(聚甲基丙烯酸钠盐分散剂,    3.22Rohm&Haas公司提供)Triton CF-10(烷基芳基醚润湿剂,       1.27Union Carbide公司提供)DrewL-493                             0.45(消泡剂,Drew化学公司提供)Tipure R900(二氧化钛)                 45.36(二氧化钛颜料,E.I.duPont de Nemours & Company提供)Silverbond B                          70.90(石英二氧化硅增充剂,Tammsco Inc.提供)Snowflake(天然研磨的碳酸钙增    270.30充剂,ECC提供)稀释剂Texanol(2,2,4-三甲基-1,3-戊  10.39二醇单异丁酸酯)酯醇凝聚剂,East-man化学公司提供)甲醇                            6.80Drew L 493                      0.91羟乙基纤维素250MR               6.80增稠剂,Hercules化学公司提供(2.5%水溶液)试验方法                    636.98千克干燥时间试验
此试验与在室温下干燥有机涂层的标准试验ASTMD1640相似。用适当方法将试验膜涂敷在一个无孔基底(玻璃板或金属板)上,形成一个厚度为0.030±0.0025cm的湿膜。      将ASTM试验法修改成仅使用轻微的姆指压力。将姆指在保持与膜接触的情形下转动90°。记下转动时膜不破裂的时间为干燥时间。
早期耐冲刷性
象为干燥时间试验一样制备试验膜。在膜于25.6℃的温度和50%相对湿度下干燥15分钟后,将样品置于冷自来水流(水压643-756升/小时)之下,之下,水流与涂料膜表面所成的角度从近乎直角到斜角。样品在水流下保持5分钟。在5分钟末从试验水流中取出样品,目测检查分级。无明显变化者定为合格;膜有轻微破坏者为免强合格;膜有破裂或脱落者为不合格。
耐擦洗性
制备0.00889cm厚的干膜,在25±1.1℃和40-55%的相对湿度下固化24小时。按照ASTMD2486进行试验。记下某一部位的涂料膜被完全擦洗掉时的擦洗次数。
加热老化试验
将0.47升试验涂料置于密封桶内,在封闭的循环热气炉中于48.9℃下存放一周。由炉中取出桶,观察涂料。如果涂料仍为流体並且无明显的稠化或分离迹象,则定为合格。
实例
对照例A——将多官能胺加到阴离子稳定的胶乳粘合剂中,形成的涂料在存放时不稳定。
将4.54千克聚OXEMA(28.5%固体)加到按上述配方制备的涂料中。此涂料在室温老化16小时后,其稠度由流体混合物变成固化了的大块物。
实例1——加入挥发性碱而形成的涂料在存放时稳定。
重复对照例的步骤,只是在加聚OXEMA之前先加入1.77千克的氢氧化铵(28%)。此涂料在室温下存放时保持为流体,加热老化试验合格。
实例2——各种含量的多官能胺
象实例1一样,加入表中所示数量的多官能胺(聚OXEMA)制备试验涂料,此数量为涂料固体重量的百分数。将涂料涂敷于载体上进行试验。用不加任何胺官能聚合物的标准涂料作为对照。结果列在下面的表中。多官能胺含量       早期耐冲刷性    耐擦洗性(为涂料固体的%)                          对照样              不合格        950次0.27% P-OXEMA     勉强合格0.62% P-OXEMA       合格         760次1.25% P-OXEMA       合格         950次2.5%  P-OXEMA       合格         910次
以上数据表明,胺官能聚合物导致了早期耐冲刷性和合格格的耐擦洗性。另外,含1.25%聚OXEMA的涂料在干燥时间试验中于10分钟内干燥。而不含多官能胺的对照涂料的干燥时间为20分钟。
实例3——列出的各种胺官能单体的聚合物与共聚物的使用。
用所列出的胺官能聚合物按实例1的步骤制备涂料。以不加任何胺官能聚合物的涂料作为对照。将胺官能聚合物按表中所示数量(为涂料固体的重量%)加到标准配方中制得样品。将胶乳样品涂敷在基底上进行试验。结果列在下面的表中:在路标涂料配方中的多官能胺    早期耐冲     48.9℃(1.25%固/固)类型             刷性      老化7天
   无聚OXEMA                         不合格      合格OXEMA/HEMA 50/50                合  格      合格OXEMA/MMA  70/30                合  格      合格DMAPMA/AM  70/30       合格    合格DMAPMA/HEMA 70/30      合格    合格(0.44%固/固)聚DMAEMA               合格    合格
以上数据表明,根据本发明的标记涂料具有早期耐冲刷性,而且即使在高温下存放时也是稳定的。

Claims (9)

1.一种涂料组合物,它含有
(a)阴离子稳定的胶乳聚合物,其玻璃化温度高于0℃;
(b)一种可溶的或可分散的聚合物多官能胺,形成此聚合物的单体中有20%至100%(重量)的单体含有胺基;
(c)一种挥发性碱,其用量足以将组合物的pH升高到某一数值,此时多官能胺基本上处于不离解状态。
2.权利要求1的涂料组合物,其中多官能胺的含量为胶乳固体重量的0.25%至10%。
3.权利要求2的涂料组合物,其中多官能胺的含量为胶乳固体重量的0.4%至5%。
4.权利要求3的涂料组合物,其中多官能胺的含量为胶乳固体重量的0.6%至2.5%。
5.权利要求1的涂料组合物,其中多官能胺为聚甲基丙烯酸恶唑烷基乙酯。
6.权利要求1的涂料组合物,其中的多官能胺含有二甲基氨基丙基甲基丙烯酰胺。
7.权利要求1的涂料组合物,其中的多官能胺含有甲基丙烯酸恶唑烷基乙酯。
8.权利要求1的涂料组合物,其中的多官能胺含有甲基丙烯酸二甲基氨基乙酯。
9.权利要求1-8任一项所述的涂料组合物用于存放稳定的快速固化水基交通用涂料的应用。
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AU5911390A (en) 1991-01-24
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CN1048868A (zh) 1991-01-30
SG74550A1 (en) 2000-08-22
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KR0156742B1 (ko) 1999-02-01
ZA905500B (en) 1991-04-24
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US5527853A (en) 1996-06-18
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JPH03157463A (ja) 1991-07-05
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