CN110431161A - 具有开放时间添加剂的涂料配制物 - Google Patents
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Abstract
本发明涉及中和的多阶段聚合物颗粒的水分散体,所述中和的多阶段聚合物颗粒包含羧酸官能化第一阶段的碱金属碱或高沸点胺盐和低Tg第二阶段(壳)。所述分散体可用作开放时间添加剂。
Description
背景技术
本发明涉及涂料配制物,所述涂料配制物包含a)开放时间添加剂的水分散体,其为中和的聚合物颗粒的分散体;b)粘结剂;和c)流变改性剂。
政府法规和市场运作不断趋向用于涂料配制物的零挥发性有机化合物(VOC)。因此,不含挥发性溶剂和聚结剂的水性配制物已在行业内变得越来越受欢迎。尽管如此,油漆特性已由于这种巨大的改变而损害;尤其为开放时间,所述开放时间为在其期间新施用的漆膜可二次加工而不留刷痕的时间段。在溶剂型系统中,开放时间为约30至45分钟;在典型的水性配制物中,开放时间为大约3至5分钟。因此,本领域中需要寻找一种用于水性配制物的添加剂,所述添加剂使开放时间延长超过目前可用的添加剂而不降低最终涂料的其它特性,如膜粘合和粘聚强度、硬度、耐粘连性、早期耐起泡性、耐擦洗性、耐污染性以及耐损性。
发明内容
在第一方面,本发明通过提供包含中和的多阶段聚合物颗粒的水分散体的组合物来满足本领域的需要,所述中和的多阶段聚合物颗粒包含a)第一阶段,按所述第一阶段的重量计,所述第一阶段包含:i)10至50重量%的羧酸单体的钠、钾、锂或第一季铵盐的结构单元,其中第一季铵盐的共轭碱的沸点为至少150℃;和ii)50至70重量%的非离子烯键式不饱和单体的结构单元;和b)Tg不高于25℃的第二阶段;其中第一阶段与第二阶段的比率在1:3.2至1:6的范围内。
在第二方面,本发明为涂料组合物,所述涂料组合物包含中和的多阶段聚合物颗粒的水分散体、粘结剂和流变改性剂,其中多阶段聚合物颗粒包含a)第一阶段,按所述第一阶段的重量计,所述第一阶段包含:i)10至50重量%的羧酸单体的钠、钾、锂或第一季铵盐的结构单元,其中第一季铵盐的共轭碱的沸点为至少150℃;和ii)50至70重量%的非离子烯键式不饱和单体的结构单元;和b)Tg不高于25℃的第二阶段;其中第一阶段与第二阶段的比率在1:3.2至1:6的范围内;其中按所述涂料组合物的重量计,多阶段聚合物颗粒的浓度在0.1至10重量%的范围内。
具体实施方式
在第一方面,本发明为包含中和的多阶段聚合物颗粒的水分散体的组合物,所述中和的多阶段聚合物颗粒包含a)第一阶段,按所述第一阶段的重量计,所述第一阶段包含:i)10至50重量%的羧酸单体的钠、钾、锂或第一季铵盐的结构单元,其中第一季铵盐的共轭碱的沸点为至少150℃;和ii)50至70重量%的非离子烯键式不饱和单体的结构单元;和b)Tg不高于25℃的第二阶段;其中第一阶段与第二阶段的比率在1:3.2至1:6的范围内。
中和的多阶段聚合物颗粒的特征在于中和的第一阶段部分(核),优选地羧酸官能化核的盐,和具有如通过福克斯(Fox)方程式计算的不高于25℃的Tg的第二阶段部分(壳)。本文中使用的词语“核”和“壳”是为了方便描述聚合过程的第一和最后阶段(或者如果聚合物颗粒在两个阶段中生成那么为第一和第二阶段)。因此,最终中和的聚合物颗粒可以但不必具有核-壳形态。
中和的多阶段聚合物颗粒通过使碱可溶胀的聚合物颗粒的水分散体与碱(其为LiOH、NaOH、KOH或沸点为至少150℃的胺)接触来制备。沸点为至少150℃的胺的实例包括2-氨基-2-甲基-1-丙醇(可作为AMP 95中和剂商购)和正丁基二乙醇胺(可作为Vantex T中和剂商购)。碱可溶胀的聚合物颗粒的分散体可通过许多技术中的任一种来制备,包括本领域熟知的技术。(参见US 4,468,498;US 5,326,843;和US 9,340,685)。举例来说,核可通过单阶段或多阶段过程来生产,任选地在如正十二烷基硫醇或巯基乙醇的链转移剂的存在下生产。核也可由种子过程来制备。接着将核用于在一个或多个额外的阶段中制备碱可溶胀的聚合物颗粒。
碱的浓度足以中和碱可溶胀的聚合物颗粒的核。如本文所用,“中和”意指核的pH升高至比用于制备酸官能化核的酸单体的pKa高至少1.5个单位的pH。举例来说,如果使用甲基丙烯酸(pKa=4.65)制备酸官能化核,那么将碱可溶胀的分散体的pH调节至至少6.15,优选地至少6.5,更优选地至少7,并且最优选地至少8。优选地,相对于碱可溶胀的聚合物颗粒的酸含量,碱的添加量为至少30%化学计量,更优选地至少50%化学计量,并且最优选地至少化学计量。
按核的重量计,中和的多阶段聚合物颗粒的中和的核包含10,优选地20,更优选地30,更优选地35,并且最优选地38重量%至50,优选地至45,并且更优选地至42重量%的羧酸单体的锂、钠、钾或第一季铵盐的结构单元。如本文所用,术语“结构单元”是指所述单体在聚合后的残余物。举例来说,甲基丙烯酸钠的结构单元如下说明:
甲基丙烯酸钠的结构单元
核还优选地包含50,更优选地55,并且最优选地58重量%至优选地70,更优选地至65,并且最优选地至62重量%的非离子烯键式不饱和单体的结构单元。
羧酸官能化单体的盐的实例包括甲基丙烯酸、丙烯酸和衣康酸的锂盐、钠盐和钾盐,优选丙烯酸和甲基丙烯酸的锂盐、钠盐和钾盐。非离子烯键式不饱和单体的实例包括一种或多种C1-C10丙烯酸烷酯和甲基丙烯酸酯,如甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯和丙烯酸2-乙基己酯;以及苯乙烯。甲基丙烯酸甲酯和甲基丙烯酸丁酯为优选的非离子烯键式不饱和单体。
中和的核还可包含多烯键式不饱和单体的结构单元,如乙二醇二(甲基)丙烯酸酯、烯丙基(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯,或二乙烯基苯。如果存在,那么按核的重量计,多烯键式不饱和单体的结构单元优选地在0.1,更优选地0.3重量%至10,更优选地至3重量%的范围内。
第二阶段(壳)的Tg优选地不高于20℃,并且更优选地不高于15℃。优选地,壳包含一种或多种Tg>50℃的单体(即一种或多种高Tg单体)的结构单元,如甲基丙烯酸甲酯(Tg=105℃)或苯乙烯(Tg=100℃)或其组合,以及至少一种Tg低于10℃的单体(即一种或多种一种低Tg单体)的结构单元,如丙烯酸乙酯(Tg=-23℃)、丙烯酸丁酯(Tg=-53℃),或丙烯酸2-乙基己酯(Tg=-52℃)或其组合。壳优选地另外包含酸单体的锂、钠、钾或第一季铵盐的结构单元,所述酸单体为优选地羧酸单体,优选地甲基丙烯酸(Tg=228℃)或丙烯酸(Tg=101℃)。(所述Tg是指如由聚合物属性数据库(Polymer Properties Database)2015报告的对应均聚物的那些。)
优选地,按壳的重量计,所述壳中高Tg单体的结构单元(优选地甲基丙烯酸甲酯或苯乙烯,更优选地甲基丙烯酸甲酯)的浓度在40,更优选地42,并且最优选地44重量%至优选地60,更优选地至55,更优选地至50,并且最优选地至48重量%的范围内。
优选地,按壳的重量计,所述壳中低Tg单体的结构单元的浓度在38,更优选地45,更优选地48重量%,并且最优选地50重量%至优选地59,更优选地至57,并且最优选地至54重量%的范围内。低Tg单体优选地为丙烯酸丁酯。
优选地,按壳的重量计,所述壳中羧酸单体的盐的结构单元的浓度在0.2,更优选地0.4重量%至优选地5,更优选地至4,并且最优选地至3重量%的范围内。
优选地,中和的多阶段聚合物颗粒基本上不含NH4 +或第二季铵盐抗衡离子,其中第二季铵盐的共轭酸为沸点低于150℃,优选地低于120℃的胺。如本文所用,术语“基本上不含NH4 +或第二季铵盐抗衡离子”意指中和的多阶段聚合物颗粒的NH4 +或低沸点季铵盐抗衡离子的浓度小于20,优选地小于10,并且最优选地小于5摩尔当量/100摩尔当量的锂、钠、钾或沸点为至少150℃的胺的第一季铵阳离子。最优选地,中和的多阶段聚合物颗粒不含NH4 +或第二季铵盐抗衡离子,其中第二季铵盐的共轭酸为沸点低于120℃的胺。优选地,按多阶段聚合物颗粒的重量计,所述多阶段聚合物颗粒中羧酸铵的结构单元的浓度小于5,更优选地小于2,更优选地小于1,并且最优选地小于0.5重量%。
在中和之前,核的平均直径优选地在80nm,更优选地100nm,最优选地110nm至优选地500nm,更优选地至400nm,并且最优选地至350nm的范围内,如通过BI-90PlusBrookhaven颗粒分析仪测量。在中和后,中和的多阶段聚合物颗粒的粒度优选地在250nm至700nm的范围内;核的尺寸优选地在120nm,更优选地140nm至优选地400nm,更优选地至350nm的范围内,如通过Brookhaven BI-90Plus颗粒分析仪测量。
在本发明的第一方面,组合物的挥发性有机物含量(VOC)小于250g/L,更优选地小于200g/L,更优选地小于150g/L,并且最优选地小于50g/L。除水外的以g/L为单位的VOC如通过下式进行计算:
其中H2Od和VOC1d分别指水的密度和VOC1的密度。
多阶段中和的聚合物颗粒的水分散体可用作涂料配制物中的开放时间添加剂。因此,在另一方面,本发明为涂料组合物,其包含中和的多阶段聚合物颗粒的水分散体、粘结剂和流变改性剂,其中按所述涂料组合物的重量计,多阶段聚合物颗粒的浓度在0.1至5重量%的范围内。
如本文所用,“粘结剂”聚合物颗粒在暴露于碱时表现出小于10nm的粒度增加。这些聚合物颗粒(粘结剂固体)的平均直径优选地在70nm,更优选地100nm至600nm,更优选地至500nm的范围内,如通过Brookhaven BI-90Plus颗粒分析仪测定。按粘结剂固体的重量计,所述粘结剂固体的特征还在于包含小于5重量%,优选地小于4重量%,并且最优选地小于3重量%的酸单体的结构单元。
粘结剂有利地通过一种或多种烯键式不饱和单体的水乳液聚合来制备,所述一种或多种烯键式不饱和单体的实例包括苯乙烯、乙酸乙烯酯、丙烯酰胺、甲基丙烯酰胺、丙烯腈和丙烯酸或甲基丙烯酸的C1-C10烷基酯,包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯。按涂料配制物的重量计,所述涂料配制物中粘结剂聚合物颗粒的浓度优选地在3,更优选地6至优选地40,更优选地至30重量%的范围内。
如本文所用,术语“流变改性剂”是指水溶性或水分散性缔合流变改性剂,如疏水改性的环氧乙烷氨基甲酸酯聚合物(HEUR)、疏水改性的碱可溶胀的乳液(HASE)和苯乙烯-马来酸酐三元共聚物(SMAT),以及非缔合流变改性剂,如碱可溶胀的乳液(ASE)。按涂料组合物的重量计,流变改性剂的浓度优选地在0.3至2重量%的范围内。
中和的多阶段聚合物颗粒的水分散体、粘结剂和流变改性剂可以任何顺序组合以获得本发明的涂料组合物。替代地,碱可溶胀的聚合物颗粒的分散体可以任何顺序与粘结剂和流变改性剂组合,然后中和碱可溶胀的分散体,以形成多阶段中和的聚合物颗粒。碱可溶胀的聚合物颗粒可以在不任何另外添加碱的情况下得到中和(因为组合物的碱性已经足以中和并且溶胀聚合物颗粒的核);然而,优选在涂料配制物中后添加碱以将其调节至期望pH,这通常为在引入碱可溶胀的聚合物颗粒之前的配制物的pH。
按涂料组合物的重量计,所述涂料组合物中中和的多阶段聚合物颗粒的浓度在0.1,优选地0.2,并且更优选地0.5重量%至10,优选地至5,更优选地至4,并且最优选地至3重量%的范围内。在这些相对低的浓度下,令人惊讶地发现,在涂料配制物中没有发生明显的粘度改变,其中在将碱可溶胀的聚合物颗粒的分散体与涂料配制物的其它组分组合时完成中和。尽管US 4,468,498教导某些包封的碱可溶胀的聚合物颗粒在涂料配制物中作为增稠剂为有效的,但与在中和之前涂料组合物的粘度相较,在中和后本发明的油漆配制物的粘度改变小于10%,优选地小于5%,并且更优选地小于2%。
因此,本发明的多阶段中和的聚合物颗粒的分散体虽然适用作涂料组合物的开放时间添加剂,但在预期的浓度下不适用作增稠剂;有意地将碱可溶胀的聚合物颗粒的浓度维持在不产生组合物明显增稠的水平。
本发明的涂料组合物有利地另外包含任何或所有下列组分:分散剂、颜料、消泡剂、表面活性剂、溶剂、增量剂、聚结剂、杀生物剂、不透明聚合物和着色剂。组合物为VOC小于50g/L的低挥发性有机物含量(VOC)组合物。
实例
制备碱可溶胀的聚合物
A.制备第1阶段(核)
如下制备第一阶段(核,60MMA/40MAA):5L四颈圆底烧瓶(釜)配备有浆式搅拌器、温度计、N2入口和回流冷凝器。将去离子水(1760g)添加到釜中并且在N2下加热至86℃。通过将去离子水(720g)、十二烷基苯磺酸钠(SDS,5.2g,23%活性)、甲基丙烯酸甲酯(780.0g)和甲基丙烯酸(10.0g)混合来制备单体乳液(ME1)。取出一部分ME1(164.0g)并且放在一边的一个单独的容器中。向剩余的ME1中添加SDS(50.0g,23%活性)和甲基丙烯酸(510.0g)。当釜温达到86℃时,将去离子水(160.0g)和SDS(5.0g,23%活性)的混合物添加到釜中,然后添加最初取出的ME1并且放在一边。接着将过硫酸钠(5.5g)于去离子水(40.0g)中的混合物添加到釜中。釜的温度降至约76℃,接着使其在15分钟的保持期内升至85℃。接着将剩余的ME1在85℃下经2小时进料至釜中。在完成ME1进料之后,将分散体保持在85℃下持续15分钟,之后将分散体冷却至25℃并且过滤以去除任何凝结物。过滤后的分散体具有2.9的pH、31.7%的固含量和152nm的平均粒度。
B.制备具有1:5核-壳比率和含40%甲基丙烯酸的核的碱可溶胀的聚合物颗粒的分散体
向配备有浆式搅拌器、温度计、N2入口和回流冷凝器的5L四颈圆底烧瓶(釜)中添加DI水(500g)并且在N2下加热至86℃。通过将DI水193g、SDS(14.3g,23%活性)、丙烯酸丁酯(655.2g)、甲基丙烯酸甲酯(585.9g)和甲基丙烯酸(18.9g)混合来制备单体乳液(ME2)。当釜温达到86℃时,将部分A(795.0g)的分散体添加到釜中并且将温度调节至60℃。接着将0.1%硫酸铁(II)于水(20g)中的溶液与和DI水(45g)混合的异抗坏血酸(0.6g)溶液一起添加到釜中。将过硫酸钠(3.8g)于DI水(90g)和亚硫酸氢钠(2.5g)于DI水(90g)中的共进料溶液以0.7克/分钟的速率添加到釜中。在开始添加共进料溶液三分钟后,以2克/分钟的速率添加ME2。在开始添加ME2十分钟后,进料速率增加至4g/m。再过十分钟后,ME2进料速率增加至8克/分钟。再过十分钟后,ME进料速率增加至16克/分钟。在整个ME2的添加过程中,釜的温度保持在59-61℃。在完成ME2的添加之后,共进料再过量进料二十分钟。在完成共进料添加后,将釜的内容物冷却至室温并且过滤以去除任何凝结物。过滤后的分散体具有2.1的pH、47.5%的固含量和275nm的平均粒度,如通过BI-90Plus Brookhaven颗粒分析仪测量。
碱可溶胀的聚合物在三个单独的实验中用两种不同的碱2-氨基-2-甲基-1-丙醇和NaOH进行溶胀,如下:将中和碱添加到聚合物分散体中以制备最终固含量为25%的分散体。在室温下添加中和碱,机械混合10分钟。测量添加完成一小时后的pH值>7。通过将溶胀的颗粒分散体添加到表1中所述的油漆配制物中来制备油漆配制物。
表1-具有开放时间添加剂的油漆配制物
材料名称 | 磅 | 加仑 |
RHOPLEX<sup>TM</sup> HG-706粘结剂 | 525.7 | 59.37 |
BYK-024消泡剂 | 1.0 | 0.1 |
丙二醇 | 4.3 | 0.5 |
TRITON<sup>TM</sup> X-100表面活性剂 | 4.4 | 0.5 |
水 | 16.7 | 2.0 |
KATHON<sup>TM</sup> LX 1.5%杀生物剂 | 1.5 | 0.2 |
TAMOL<sup>TM</sup> 2002分散剂 | 2.0 | 0.2 |
氨(28%) | 1.0 | 0.1 |
Ti-纯R-746TiO<sub>2</sub> | 285.0 | 14.7 |
水 | 20.0 | 2.4 |
TEXANOL聚结剂 | 7.9 | 1.0 |
ACRYSOL<sup>TM</sup> RM-2020E流变改性剂 | 20.0 | 2.3 |
ACRYSOL<sup>TM</sup> RM-725流变改性剂 | 3.0 | 0.4 |
BYK-024消泡剂 | 2.0 | 0.2 |
溶胀的颗粒(25%固体) | 95.5 | 11.4 |
水 | 38.7 | 4.63 |
总计 | 1030 | 100 |
RHOPLEX、TRITON、KATHON、TAMOL和ACRYSOL均为陶氏化学公司(The Dow ChemicalCompany)或其附属公司的商标。
使用顶置式混合器配制油漆样品。调节流变改性剂和水量以使Stormer粘度为95KU并且ICI粘度为1.3。将样品平衡过夜,然后评估开放时间。
开放时间根据ASTM-D7488测量。测试在恒温/恒湿室(72℉,50%RH)下进行。使用具有5密耳间隙的刮涂棒将油漆沉积在黑色乙烯基擦洗记录纸上。通过使用两个木制施加器在湿油漆中制作平行标记,立即对膜进行评分。接着使用涂有底漆的1"尼龙刷以定时间隔刷洗膜的区段。使膜干燥过夜。由至少三名读者构成的小组在视觉上检查面板,并且将没有示出刻痕标记迹象的最后一个十字刷区段记录为开放时间。对于每种涂料,通过NaOH和2-氨基-2-甲基-1-丙醇中和的样品的测量开放时间为9分钟,相比之下,由相同的油漆配制物但没有开放时间添加剂制备的涂料的开放时间为6分钟。
Claims (10)
1.一种组合物,其包含中和的多阶段聚合物颗粒的水分散体,所述中和的多阶段聚合物颗粒包含a)第一阶段,按所述第一阶段的重量计,所述第一阶段包含:i)20至50重量%的羧酸单体的钠、钾、锂或第一季铵盐的结构单元,其中所述第一季铵盐的共轭碱的沸点为至少150℃;和ii)50至80重量%的非离子烯键式不饱和单体的结构单元;和b)Tg不高于25℃的第二阶段;其中所述第一阶段与所述第二阶段的比率在1:3.2至1:6的范围内。
2.根据权利要求1所述的组合物,其中所述第一阶段包含30至50重量%的羧酸单体的钠、钾或锂盐的结构单元和50至70重量%的非离子烯键式不饱和单体的结构单元。
3.根据权利要求2所述的组合物,其中所述多阶段聚合物颗粒的所述第一阶段包含:
a1)35至45重量%的甲基丙烯酸或丙烯酸的钠、钾或锂盐的结构单元;和
b1)55至65重量%的甲基丙烯酸甲酯的结构单元;
其中所述多阶段聚合物颗粒的所述第二阶段包含:
a2)40至60重量%的苯乙烯或甲基丙烯酸甲酯的结构单元;
b2)38至59重量%的至少一种选自由以下组成的组的单体的结构单元:丙烯酸乙酯、丙烯酸丁酯和丙烯酸2-乙基己酯;和
c2)0.2至5重量%的羧酸单体的锂、钠或钾盐的结构单元;
其中所述第二阶段的所述Tg低于20℃。
4.根据权利要求1至3中任一项所述的组合物,其中所述多阶段聚合物颗粒基本上不包含NH4 +或第二季铵盐抗衡离子,其中所述第二季铵盐的共轭酸为沸点低于120℃的胺。
5.根据权利要求1至3中任一项所述的组合物,其中按所述多阶段聚合物颗粒的重量计,所述多阶段聚合物颗粒包含小于0.2重量%的羧酸铵的结构单元,其中所述组合物的VOC小于50g/L。
6.根据权利要求1至3中任一项所述的组合物,其中所述多阶段聚合物颗粒的粒度为250nm至700nm。
7.一种涂料组合物,其包含中和的多阶段聚合物颗粒的水分散体、粘结剂和流变改性剂,其中所述多阶段聚合物颗粒包含a)第一阶段,按所述第一阶段的重量计,所述第一阶段包含:i)30至50重量%的羧酸单体的钠、钾、锂或季铵盐的结构单元,其中所述季铵盐的共轭碱的沸点为至少150℃;和ii)50至70重量%的非离子烯键式不饱和单体的结构单元;和b)Tg不高于25℃的第二阶段;其中所述第一阶段与所述第二阶段的比率在1:3.2至1:6的范围内;其中按所述涂料组合物的重量计,所述多阶段聚合物颗粒的浓度在0.1至10重量%的范围内。
8.根据权利要求7所述的组合物,其中按所述涂料组合物的重量计,所述多阶段聚合物颗粒的所述浓度在0.1至5重量%的范围内;其中所述多阶段聚合物颗粒的所述第一阶段包含:
a1)35至45重量%的甲基丙烯酸或丙烯酸的钠、钾或锂盐的结构单元;和
b1)55至65重量%的甲基丙烯酸甲酯的结构单元;
其中所述第二阶段包含:
a2)40至60重量%的苯乙烯或甲基丙烯酸甲酯的结构单元;
b2)38至59重量%的至少一种选自由以下组成的组的单体的结构单元:丙烯酸乙酯、丙烯酸丁酯和丙烯酸2-乙基己酯;和
c2)0.2至5重量%的羧酸单体的锂、钠或钾盐的结构单元;
其中所述第二阶段的所述Tg低于20℃。
9.根据权利要求7或8中任一项所述的组合物,所述组合物另外包含至少一种选自由以下组成的组的组分:分散剂、颜料、消泡剂、表面活性剂、溶剂、增量剂、聚结剂、杀生物剂、不透明聚合物和着色剂,其中所述多阶段聚合物颗粒的粒度为250nm至700nm。
10.根据权利要求9所述的组合物,所述组合物的VOC小于50g/L。
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US5326843A (en) | 1993-10-04 | 1994-07-05 | Rohm And Haas Company | Method for making an alkali-soluble emulsion copolymer |
US7825173B2 (en) * | 2005-04-29 | 2010-11-02 | E.I. Du Pont De Nemours And Company | Process for the production of aqueous binder latices |
CN104513533B (zh) | 2013-09-30 | 2018-11-06 | 罗门哈斯公司 | Hase流变改性剂vae乳液共聚物组合物 |
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2018
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- 2018-02-26 CA CA3059205A patent/CA3059205A1/en active Pending
- 2018-02-26 BR BR112019019463A patent/BR112019019463A2/pt not_active Application Discontinuation
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- 2018-02-26 EP EP18708893.5A patent/EP3606970B1/en active Active
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US4468498A (en) * | 1980-06-12 | 1984-08-28 | Rohm And Haas Company | Sequential heteropolymer dispersion and a particulate materal obtainable therefrom, useful in coating compositions as a thickening and/or opacifying agent |
US4863973A (en) * | 1987-07-30 | 1989-09-05 | Tioxide Group Plc | Polymeric particles and their preparation |
CN1090290A (zh) * | 1992-09-03 | 1994-08-03 | 罗姆和哈斯公司 | 具有碱溶性和碱不溶性段的多段聚合物 |
US20080058473A1 (en) * | 2006-08-31 | 2008-03-06 | Yakov Freidzon | Latex for low VOC paint having improved block resistance, open time and water-softening resistance |
CN103140518A (zh) * | 2010-09-23 | 2013-06-05 | 巴斯夫欧洲公司 | 制造自粘制品用的压敏胶粘剂水性分散体的多阶段制备方法 |
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US20200102412A1 (en) | 2020-04-02 |
EP3606970B1 (en) | 2021-05-05 |
WO2018186946A1 (en) | 2018-10-11 |
AU2018249305A1 (en) | 2019-11-14 |
CA3059205A1 (en) | 2018-10-11 |
MX2019011642A (es) | 2019-12-05 |
EP3606970A1 (en) | 2020-02-12 |
BR112019019463A2 (pt) | 2020-04-22 |
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