CN108779607B - 水性聚合物分散体、其用途和制备水性聚合物分散体的方法 - Google Patents

水性聚合物分散体、其用途和制备水性聚合物分散体的方法 Download PDF

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CN108779607B
CN108779607B CN201780018443.5A CN201780018443A CN108779607B CN 108779607 B CN108779607 B CN 108779607B CN 201780018443 A CN201780018443 A CN 201780018443A CN 108779607 B CN108779607 B CN 108779607B
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A·莱波
H·佩拉恩
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Abstract

本发明涉及一种水性聚合物分散体，其在40％固体含量下具有≤150mPas的粘度，并且包含粒径D50小于85nm的聚合物颗粒。该聚合物分散体可通过在包含平均分子量Mn<1000g/mol的降解淀粉的反应混合物中由至少单体(a)和单体(b)的自由基乳化共聚获得，其中单体(a)是至少一种任选取代的苯乙烯，单体(b)是至少一种(甲基)丙烯酸C1‑C4烷基酯。本发明还涉及该聚合物分散体的用途及其制备方法。

Description

水性聚合物分散体、其用途和制备水性聚合物分散体的方法
本发明涉及根据所附独立权利要求的前序部分的水性聚合物分散体、其用途和制备水性聚合物分散体的方法。
淀粉接枝共聚物分散体用于纸浆和造纸。它们可用于各种目的，例如用于表面施胶组合物或用于提高纸的干强度。例如，US 6,426,381公开了可用于表面施胶的苯乙烯/(甲基)丙烯酸酯共聚物。水性聚合物分散体通过烯键式不饱和单体在淀粉的存在下共聚而获得。使用的淀粉是降解淀粉，并且具有500至10,000的平均分子量Mn。
在施加在纸或纸板等的表面上的有色涂料中使用流变改性剂。有色涂料通常是包含无机矿物颗粒、水、天然和/或合成聚合物粘合剂和流变改性剂的组合物。流变改性剂用于改变有色涂料的流动特性。流变改性剂使有色涂料能够具有良好的保水力(waterretention)和粘度行为。有色涂料的保水力描述了有色涂料保持水相与有色涂料的矿物颗粒接触的能力。保水力能够实现在计量刮刀下形成均匀的流体压力、良好的运行性能和光滑的涂层表面。如果有色涂料的保水力太低，则有色涂料的水太快地被原纸吸附，并且涂料太快地沉积在纸表面上。
已知使用淀粉、羧甲基纤维素、聚乙烯醇或合成增稠剂作为流变改性剂。它们改善了有色涂料的保水力，但同时也增加了有色涂料的粘度。因此，它们只能以有限的量使用，并且保水力的改善必须与涂料粘度增加引起的问题相均衡。因此，需要一种能提供良好的保水力并具有良好的粘度行为的流变改性剂。
本发明的一个目的是最小化或甚至消除现有技术中存在的缺点。
本发明的一个目的还在于提供一种水性聚合物分散体，其在用于有色涂料中时提供最佳的保水力和粘度行为。
这些目的通过具有下文在独立权利要求的特征部分中呈现的特征的方法和设置来实现。在从属权利要求中描述了本发明的一些优选实施方案。
根据本发明的典型水性聚合物分散体在40％固体含量下具有≤150mPas的粘度，并且包含粒径D50小于85nm的聚合物颗粒，该聚合物分散体通过在包含平均分子量Mn<1000g/mol的降解淀粉的反应混合物中由至少单体(a)和单体(b)的自由基乳化共聚获得，其中：
-单体(a)是至少一种任选取代的苯乙烯，和
-单体(b)是至少一种(甲基)丙烯酸C1-C4烷基酯。
用于制备根据本发明的水性聚合物分散体的根据本发明的典型方法包括在包含平均分子量Mn<1000g/mol的降解淀粉的反应混合物中至少单体(a)和单体(b)的自由基乳化共聚，其中：
-单体(a)是至少一种任选取代的苯乙烯，和
-单体(b)是至少一种(甲基)丙烯酸C1-C4烷基酯。
水性聚合物分散体的根据本发明的典型用途是作为有色涂料中的保水改性剂用于改善有色涂料的保水力。
现已令人惊讶地发现，当自由基乳化共聚在平均分子量Mn<1000g/mol的降解淀粉的存在下进行时，得到的聚合物分散体具有高固体含量但具有低粘度，这在工业规模上生产分散体是有利的。此外，获得的聚合物分散体在作为流变改性剂用于有色涂料中时表现出预料不到的改善。其在低剪切和高剪切下均为有色涂料提供优异的保水力和粘度性能。观察到的效果的来源尚未被完全了解。不希望受理论束缚，假定强降解淀粉能够有效地形成氢键，并保留有色涂料中的水，同时在低剪切率和高剪切率下提供低粘度。出乎意料的是，淀粉的降解程度对聚合物分散体的性质及其与其他有色涂料组分的相容性具有如此强的积极作用。
在反应混合物中进行通过使用接枝-连接水溶性氧化还原体系作为自由基引发剂的聚合，所述反应混合物包含淀粉和至少单体(a)和(b)。
通过使用Brookfield LVDV粘度计及转子18以及使用转子的最高可行转速在25℃下在40重量％的固体含量下测量，水性聚合物分散体的粘度≤150mPas。优选地，通过使用Brookfield LVDV粘度计及转子18，在25℃下在40重量％的固体含量下测量，水性聚合物分散体的粘度范围为1-150mPas，优选5-100mPas，更优选5-70mPas，甚至更优选5-49mPas。
降解淀粉的低数均分子量降低了聚合物分散体在涂料组合物中增加粘度的效果，同时还增加了水在有色涂料组合物中的保留。这改善了有色涂料特别是在刮刀涂布中的行为以及有色涂料在涂布刮刀处的运行性能。有色涂料在刮刀压力下不经受粘度增加，并且聚合物分散体有助于在涂层中最佳地保留水，从而提供平滑且无缺陷的涂层结果。此外，降解淀粉的低平均分子量Mn确保分散体中聚合物颗粒的粒径保持很小。根据本发明的一个优选实施方案，降解淀粉的平均分子量Mn<1000g/mol，优选<800g/mol，更优选<500g/mol。降解淀粉的平均分子量Mn可以为100-990g/mol，优选100-790g/mol，更优选100-490g/mol，甚至更优选100-400g/mol。淀粉的平均分子量Mn可以例如通过使用尺寸排阻色谱法(SEC)使用以下设备和程序测定：Viscotek GPCmax TDA 302SEC设备，包括三个柱(WatersUltrahydrogel 2000、500和120)和一个保护柱的柱组。洗脱液是在35℃下流速为0.8ml/min的含2.5％(v/v)乙腈的0.1M NaNO3水溶液。进样体积为50μL，样品浓度为2mg/ml。来自示差折光率检测器的信号用于采用聚丙烯酸钠标准物的常规柱校准。乙二醇用作内标。
降解淀粉可以通过使淀粉经受氧化降解、热降解、酸降解、水解降解或酶促降解来获得。目前优选氧化降解。可以使用次氯酸盐、过氧二硫酸盐、过氧化氢或它们的混合物作为氧化剂。根据一个实施方案，用次氯酸盐降解淀粉以改善淀粉的溶解性质，在此之后，例如在随后的共聚之前不久，进行进一步降解，例如采用过氧化氢。在这种情况下，基于所用的淀粉，过氧化氢(按100％计算)以0.3至5.0重量％的浓度使用。过氧化氢的确切量取决于待被降解的淀粉的最终分子量。
用于本发明的降解淀粉可以是任何合适的降解天然淀粉，如马铃薯、大米、玉米、蜡质玉米、小麦、大麦或木薯淀粉。支链淀粉含量>80％、优选>95％的淀粉是有利的。
降解淀粉可以是非离子性的或者具有阴离子净电荷。具有阴离子净电荷的淀粉可以是阴离子性的，即仅含有带阴离子电荷的基团，或者是两性的，即含有带阴离子和阳离子电荷的基团，只要淀粉的净电荷是阴离子性的。降解淀粉优选是阴离子性或具有净阴离子电荷的两性的。阴离子性或两性淀粉包含阴离子基团，如羧酸根或磷酸根基团。取代度DS表示淀粉中每个葡萄糖单元平均带电荷基团的数目，通常为0.01-0.20。根据本发明的一个优选实施方案，降解淀粉是降解的阴离子马铃薯或木薯淀粉。
还可以使用化学改性的淀粉，如羟乙基淀粉或羟丙基淀粉。
在聚合之前，通过加热使降解淀粉溶解到水中，并获得降解淀粉的水溶液。根据本发明的一个实施方案，采用Brookfield LVDV粘度计及转子18以60rpm在25℃下对15重量％的溶液测量，溶液形式的降解淀粉的粘度为<15mPas，优选<10mPas。在加入单体和形成反应混合物之前测量淀粉溶液的粘度。
在聚合开始之前，可以将降解淀粉溶液加热至高于其谷蛋白化温度的值。通常，聚合过程的聚合步骤在30-100℃的温度范围内进行，优选在70-98℃的温度范围内进行。在采用超大气压的压力反应器的情况下，温度可以>100℃。
根据本发明的一个实施方案，按照聚合开始时反应混合物的含量计算，在聚合开始时和加入单体之前，反应混合物中降解淀粉的量为5-60重量％，优选10-45重量％，更优选11-35重量％。如此处定义的淀粉量为获得的苯乙烯和丙烯酸酯的共聚物颗粒提供了最佳的粒径，以及为获得的聚合物分散体提供最佳的稳定性。
聚合通过将单体单独地或作为混合物以及适合于引发聚合的自由基引发剂加入到包含平均分子量Mn<1000g/mol的降解淀粉的水性淀粉溶液进行，所述单体在下文更详细地描述。因此形成用于聚合的反应混合物。聚合过程通常在不存在氧气的情况下进行，优选在惰性气体气氛中进行，例如在氮气下进行。根据本发明的一个实施方案，按照反应混合物的总干固体含量计算，反应混合物中单体的总量为10-92重量％，优选20-90重量％，更优选35-88重量％。单体的量在此是指在聚合过程中加入到反应混合物中的单体(a)、(b)和任选的(c)的总量。通常在预定的时间段内将单体加入到包含水性淀粉溶液的反应混合物。
聚合可以通过不间歇给料方法(a feed process)和间歇给料方法(a batchprocess)进行。在搅拌釜级联或流动管中的连续聚合方法也是可能的。在优选的进料方法中，将单体和自由基引发剂在搅拌反应器中均匀计量加入到降解淀粉溶液中。在整个制备和聚合过程中，保持借助于任何合适的搅拌或混合单元彻底混合，使得加入的单体和其他组分尽可能快速地均匀分布。
按照单体(a)、(b)和任选的单体(c)的总干固体含量计算，单体(a)的量为0.1-75重量％，优选5-60重量％，更优选10-55重量％。根据一个优选的实施方案，单体(a)选自苯乙烯、取代的苯乙烯如α-甲基苯乙烯或乙烯基甲苯，及其任何混合物。
按照单体(a)、(b)和任选的单体(c)的总干固体含量计算，单体(b)的量为25-99.9重量％，优选30-95重量％，更优选35-90重量％。合适的单体(b)是(甲基)丙烯酸C1-C4烷基酯，其选自丙烯酸C1-C4烷基酯、甲基丙烯酸C1-C4烷基酯或它们的混合物，例如丙烯酸正丁酯、异丁酯、叔丁酯或2-丁酯和相应的甲基丙烯酸丁酯；丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯或甲基丙烯酸丙酯。根据本发明的一个优选实施方案，单体(b)选自(甲基)丙烯酸丁酯。它可包含例如至少两种异构的丙烯酸丁酯的混合物。更优选地，单体组分(b)是丙烯酸正丁酯、丙烯酸叔丁酯或丙烯酸正丁酯和丙烯酸叔丁酯的混合物。对于两种单体(b)的混合物，混合比可以为1:99至99:1，有时为10:90至90:10。
根据本发明的一个实施方案，反应混合物还包含至少一种单体(c)，其是烯键式不饱和的并且不同于单体(a)和(b)。合适的其他烯键式不饱和可共聚单体(c)选自丙烯酸乙基己酯、丙烯酸十八烷基酯、甲基丙烯酸十八烷基酯、丙烯酸和甲基丙烯酸与具有多于四个C原子的醇的酯，以及丙烯腈、甲基丙烯腈、丙烯酰胺、乙酸乙烯酯和阴离子共聚单体，如丙烯酸、甲基丙烯酸、衣康酸、马来酸或苯乙烯磺酸。丙烯酸和苯乙烯磺酸优选用作单体(c)。
按照单体(a)、(b)和(c)的总干固体含量计算，任选的单体(c)的量可以为0.1-15重量％，优选0.1-10重量％，更优选0.1-7重量％。
用于聚合的引发剂是常规的自由基引发剂，优选过氧化合物或偶氮化合物。这些的实例是过氧化氢；过氧二硫酸钠、钾和铵；二叔丁基过氧化物；过氧化二苯甲酰；偶氮二异丁腈；2,2'-偶氮二(2-甲基丁腈)；2,2'-偶氮二(2,4-二甲基戊腈)和2,2'-偶氮二(2-脒基丙烷)二氢氯化物。优选地，引发剂是水溶性的，即在23℃下具有>1重量％的水溶解度。过氧化氢、过氧二硫酸钾和过氧二硫酸铵是有利的。
上述自由基引发剂也可以在常规还原剂的存在下使用，因此形成所谓的氧化还原引发剂体系，其适合用作引发剂。常规还原剂的实例是例如亚硫酸钠、亚硫酸氢钠、焦亚硫酸钠、亚硫酸氢钠、连二亚硫酸钠、甲醛合次硫酸钠、抗坏血酸和羟基甲烷亚磺酸的钠盐。
优选地，还原剂作为溶液引入。它可以在单体和引发剂的进料过程中连续地或定期地引入。定期引入是优选的。
自由基引发剂(尤其是过氧化氢)也可以与重金属盐(如铈(IV)、锰或铁(II)盐)组合，得到适合用作水溶性引发剂体系的氧化还原体系，提供高接枝产率。根据本发明的一个实施方案，使用过氧化氢和铁(II)盐的组合作为接枝连接水溶性氧化还原体系是特别优选的。接枝产率在此理解为在聚合结束后与淀粉化学偶联的聚合物的比例。
可以进行聚合以使在聚合之前将氧化还原体系的重金属盐(例如铁(II)盐)加入到淀粉溶液，同时将过氧化氢与单体同时但分开加入。根据本发明的一个实施方案，基于总分散体，铁(II)盐通常以0.1-200mg/l Fe(II)离子、优选1-45mg/l Fe(II)离子、更优选2–18mg/l Fe(II)离子的浓度使用。优选地，铁(II)的量尽可能地小，以便避免最终分散体和制备的纸中的颜色问题。过氧化氢(按100％计算)以基于单体0.2至3.0重量％的浓度加入。该量是任选用于淀粉降解的过氧化氢的量以外的。
由自由基引发剂、还原剂和重金属盐组成的三元引发剂体系也适合用于聚合。在聚合之前，可以首先将还原剂与铁(II)盐一起引入。
在加入单体和引发剂结束后，通常使反应混合物继续反应一段时间以完成聚合。反应时间通常为0.5至10小时，优选0.75至5小时。在这一随后的反应时间之后，可以再次加入一定量的引发剂，以尽可能地使仍然存在于反应混合物中的残留单体聚合。
在聚合后，通过加入合适的碱，如碱金属氢氧化物和碱金属乙酸盐，优选氢氧化钠溶液、氢氧化钾溶液或氨，可以调节得到的聚合物分散体的pH。由此优选建立4-7的pH值。此外，还可以加入缓冲物质以在整个储存时间内稳定pH。
可以在聚合中使用阴离子或非离子低分子量乳化剂，如烷基磺酸钠、十二烷基硫酸钠、十二烷基苯磺酸钠、磺基琥珀酸酯、脂肪醇聚乙二醇醚、烷基芳基聚乙二醇醚等，以便改善分散效果，但聚合反应因此在不存在乳化剂的情况下进行。因此，聚合有利地不含乳化剂。
获得的接枝聚合物的分子量可以通过伴随使用链转移剂或调节剂来调节，如正十二烷基硫醇、叔十二烷基硫醇、正丁基硫醇、叔丁基硫醇等。
基于总分散体的重量，根据本发明的获得的聚合物分散体的浓度(即干固体含量)通常为>30重量％，更通常>35％，优选35-60重量％，更优选35-57重量％。
根据本发明的一个实施方案，聚合物分散体的粒径D50值为<80nm，优选<75nm和D99值为<160nm，优选<150nm，更优选<130nm，有时甚至<115nm。典型的聚合物分散体的D50值为45-85nm，优选45-80nm，更优选45-75nm，有时甚至为45-70nm。典型的聚合物分散体的D90值为70-160nm，优选90-140nm，更优选100-135nm。通过使用Zetasizer Nano ZS,Malvern测量所有粒径。D50和D90值是指基于体积分布的第50百分位数和第90百分位数的相应值。
水性聚合物分散体作为流变改性剂用于有色涂料添加剂中。有色涂料在此理解为浆料，其包含水、无机矿物颗粒和添加剂，如粘合剂和流变改性剂。有色涂料可用于涂布纸或纸板等。
可以用于本发明中的合适的无机矿物质是碳酸钙、高岭土、煅烧高岭土、滑石、二氧化钛、石膏、白垩、沙白(satine white)、硫酸钡、硅酸铝钠、氢氧化铝或它们的任何混合物。碳酸钙可以是研磨碳酸钙(GCC)或沉淀碳酸钙(PCC)或它们的混合物。优选地，无机矿物质是碳酸钙。在涂料组合物中使用的无机矿物质的粒径D50通常在<5μm的范围内。
可以用于本发明的典型粘合剂是淀粉和/或合成粘合剂。可用作天然粘合剂的淀粉可以是天然淀粉或改性淀粉，例如降解淀粉或取代淀粉。典型的合成粘合剂是基于丁二烯、苯乙烯、乙酸乙烯酯、丙烯酸丁酯和丙烯酸单体的胶乳聚合物。可以用于本发明的典型合成胶乳粘合剂是本领域已知的胶乳，如苯乙烯丁二烯(SB)、苯乙烯丙烯酸酯(SA)或聚乙酸乙烯酯(PVAc)胶乳。优选地，胶乳粘合剂是苯乙烯丁二烯(SB)胶乳。合成胶乳粘合剂的粒径为约0.1-0.2μm。
有色涂料中合成粘合剂的量为0.1-50份，优选1-25份，更优选1-20份。
根据本发明的组合物可与天然和/或合成粘合剂一起使用。还可以将该聚合物分散体用作涂料组合物中的唯一粘合剂。
根据本发明的聚合物分散体在有色涂料中的量可以为0.1-50份，优选1-25份，更优选1-20份。
通常，根据本发明的有色涂料具有50-74％、优选60-72％、更优选65-71％的固体含量和<3500、通常为100-2000mPas的低剪切粘度。使用DV-II型Brookfield粘度计，以100rpm的速度，并使用转子3或4来测量粘度。
按照本领域的惯例，涂料组分的量以份数给出。该量是相对于涂料组合物中无机矿物颜料的量计算的，并且所有的量均以干活性物质计算和给出。
实验
在以下非限制性实施例中说明本发明的一些实施方案。
实施例1：聚合物分散体A的制备
在氮气气氛下将148.0g氧化降解的马铃薯淀粉(Perfectamyl A 4692)在具有冷却/加热夹套的1升玻璃反应器中在搅拌下分散于276g去矿质水中。通过在60分钟内将混合物加热至95℃来溶解淀粉。淀粉溶解后，用硫酸将pH调节至2。混合5分钟后，将1.52g 1.0％强度的硫酸亚铁(II)七水合物水溶液加入到反应器中。5分钟后，加入7.27g 30％强度的过氧化氢。120分钟后，淀粉降解完全。开始化学进料。
单体作为混合物进料：在200分钟内加入147.8g丙烯酸正丁酯和苯乙烯(1:1重量)的混合物。在205min内，将16.2g 8％过氧化氢溶液与单体进料同时进料。反应器温度在进料期间保持在95℃，15分钟后进行后聚合反应。然后将混合物冷却至60℃并向反应器中加入0.4g 70％强度的叔丁基过氧化氢溶液。将温度在60℃下再保持60分钟。此后，冷却至40℃，加入1.5g 10％强度的乙二胺四乙酸钠盐(EDTA-Na)溶液，然后用50％强度的氢氧化钠溶液调节pH至6.2并冷却至室温。使用100μm滤布进行过滤。获得细分的分散体，其固体含量为46.3％，粒径为73nm，粘度为64mPas。
实施例2：聚合物分散体B的制备
在氮气气氛下将70.4g氧化降解的马铃薯淀粉(Perfectamyl A 4692)在具有冷却/加热夹套的1升玻璃反应器中在搅拌下分散于266g去矿质水中。通过在60分钟内将混合物加热至95℃来溶解淀粉。淀粉溶解后，用硫酸将pH调节至2。混合5分钟后，将2.17g 1.0％强度的硫酸亚铁(II)七水合物水溶液加入到反应器中。5分钟后，加入3.47g 30％强度的过氧化氢。120分钟后，淀粉降解完全。开始化学进料。
单体作为混合物进料：在200分钟内进料210.8g丙烯酸正丁酯和苯乙烯(1:1重量)的混合物。在205min内，将41.0g 4.5％过氧化氢溶液与单体进料同时进料。反应器温度在进料期间保持在95℃，15分钟后进行后聚合反应。然后将混合物冷却至60℃并向反应器中加入0.57g 70％强度的叔丁基过氧化氢溶液。将温度在60℃下再保持60分钟。此后，冷却至40℃，加入2.2g 10％强度的乙二胺四乙酸钠盐(EDTA-Na)溶液，然后用50％强度的氢氧化钠溶液调节pH至6.2并冷却至室温。使用100μm滤布进行过滤。得到细分的分散体，其固体含量为46.1％，粒径为74nm，粘度为53mPas。
实施例3：有色涂料的制备和涂布实验
使用以下用于有色涂料的步骤来制备有色涂料1：
将100份研磨碳酸钙(GCC)(75％，粒径<2μm)和4.5份苯乙烯-丁二烯胶乳混合在一起。将7份蒸煮过的天然淀粉(固体含量为28重量％)加入到GCC和胶乳的混合物中。加入水以获得目标固体含量为60重量％的有色涂料。通过使用10％氢氧化钠将有色涂料的pH调节至pH 9.2。有色涂料批量大小为500克干颜料。使用DV-II型Brookfield粘度计，使用转子3以100rpm的速度对制备的有色涂料测量低剪切粘度。使用Hercules Hi-Shear DV-10旋转粘度计测量高剪切粘度。使用
Figure BDA0001804526270000091
Akademi Gravimetric Water Retention装置测量静态保水力。
有色涂料2和3以与有色涂料1类似的方式制备，不同的是在有色涂料2和3中用4.5份实施例1和2的聚合物分散体替代4.5份苯乙烯丁二烯胶乳，如表1中所示。
有色涂料的组成在表1中给出，获得的测量结果在表2中给出。
表1实施例1中使用的有色涂料组成。
有色涂料1 有色涂料2 有色涂料3
GCC 100 100 100
苯乙烯丁二烯胶乳 4.5
聚合物分散体A 4.5
聚合物分散体B 4.5
天然淀粉 7 7 7
表2实施例1中研究的有色涂料的测量结果。
性质 有色涂料1 有色涂料2 有色涂料3
pH 9.2 9.2 9.2
固体含量[重量％] 60 60 60
温度[℃] 23.1 23.1 23.5
低剪切粘度[mPas] 304 341 325
高剪切粘度[mPas] 37 38 37
保水力[g/m<sup>3</sup>] 68 46 48
从表2可以看出，当使用根据本发明的聚合物分散体替代苯乙烯-丁二烯胶乳时，有色涂料的静态保水力得到改善，而有色涂料的高剪切粘度没有增加。
即使参考目前似乎是最实用和优选的实施方案描述了本发明，但应理解，本发明不应限于上述实施方案，而是本发明旨在也涵盖所附权利要求范围内的不同修改和等同技术方案。

Claims (16)

1.水性聚合物分散体作为有色涂料中的保水改性剂用于改善包含无机矿物颗粒的有色涂料的保水力的用途，所述水性聚合物分散体在40％固体含量下具有≤150mPas的粘度，并且包含粒径D50小于85nm的聚合物颗粒，该聚合物分散体通过在包含平均分子量Mn<1000g/mol的降解淀粉的反应混合物中由至少单体(a)和单体(b)的自由基乳化共聚获得，其中：
-单体(a)是至少一种任选取代的苯乙烯，和
-单体(b)是至少一种(甲基)丙烯酸C1-C4烷基酯。
2.根据权利要求1所述的用途，其特征在于在40重量％固体含量下测量，所述水性聚合物分散体的粘度为1-150mPas。
3.根据权利要求1或2所述的用途，其特征在于所述降解淀粉的平均分子量Mn<800g/mol。
4.根据权利要求1所述的用途，其特征在于所述降解淀粉的平均分子量Mn可以为100-990g/mol。
5.根据权利要求1所述的用途，其特征在于所述降解淀粉是非离子的或者具有阴离子净电荷。
6.根据权利要求1所述的用途，其特征在于所述降解淀粉是降解的阴离子马铃薯或木薯淀粉。
7.根据权利要求1所述的用途，其特征在于在聚合开始时所述反应混合物中降解淀粉的量为5-60重量％。
8.根据权利要求1所述的用途，其特征在于所述反应混合物还包含至少一种单体(c)，其是烯键式不饱和的且不同于单体(a)和单体(b)。
9.根据要求8所述的用途，其特征在于所述单体(c)选自丙烯酸乙基己酯；丙烯酸十八烷基酯；甲基丙烯酸十八烷基酯；丙烯酸和甲基丙烯酸与具有多于四个C原子的醇的酯；丙烯腈；甲基丙烯腈；丙烯酰胺；乙酸乙烯酯；和阴离子共聚单体，所述阴离子共聚单体由丙烯酸、甲基丙烯酸、衣康酸、马来酸和苯乙烯磺酸组成。
10.根据权利要求1所述的用途，其特征在于按照所述反应混合物的总干固体含量计算，所述反应混合物中的单体总量为10-92重量％。
11.根据权利要求1所述的用途，其特征在于按单体(a)、(b)和任选的(c)的总干固体含量计算，单体(a)的量为0.1-75重量％。
12.根据权利要求1所述的用途，其特征在于按照单体(a)、(b)和任选的(c)的总干固体含量计算，单体(b)的量为25-99.9重量％。
13.根据权利要求1所述的用途，其特征在于所述单体(a)选自苯乙烯、取代的苯乙烯，及其任何混合物，和/或所述单体(b)选自(甲基)丙烯酸丁酯。
14.根据权利要求1所述的用途，其特征在于所述聚合物分散体包含粒径D50为45-85nm的聚合物颗粒。
15.根据权利要求1所述的用途，其特征在于所述有色涂料包含无机矿物颗粒，所述无机矿物颗粒选自碳酸钙、高岭土、煅烧高岭土、滑石、二氧化钛、石膏、白垩、沙白、硫酸钡、硅酸铝钠、氢氧化铝或它们的任何混合物。
16.根据权利要求1或15所述的用途，其特征在于所述有色涂料中聚合物分散体的量为0.1-50份。
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