CN108699775B - 用于改性有色涂料的流变性的组合物、其用途和有色涂料 - Google Patents

用于改性有色涂料的流变性的组合物、其用途和有色涂料 Download PDF

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CN108699775B
CN108699775B CN201780013967.5A CN201780013967A CN108699775B CN 108699775 B CN108699775 B CN 108699775B CN 201780013967 A CN201780013967 A CN 201780013967A CN 108699775 B CN108699775 B CN 108699775B
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monomer
composition
starch
weight
degraded starch
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CN108699775A (zh
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A·莱波
H·佩拉恩
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Camiro Head Office
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Abstract

本发明涉及一种改性有色涂料的流变性的组合物及其用途。该组合物包含水性聚合物分散体，其包含单体(a)和单体(b)的共聚物，所述单体(a)是至少一种任选取代的苯乙烯，所述单体(b)是至少一种(甲基)丙烯酸C1‑C4烷基酯。该共聚物的粒径D50<100nm。组合物还包含平均分子量Mn<1000g/mol的降解淀粉。

Description

用于改性有色涂料的流变性的组合物、其用途和有色涂料
本发明涉及根据所附独立权利要求的前序部分的用于改性有色涂料(coatingcolour)的流变性的组合物、其用途和有色涂料。
纸或纸板等可涂布有有色涂料。有色涂料通常包含无机矿物颗粒，如碳酸钙或高岭土；粘合剂，如胶乳或淀粉；以及任选的其他添加剂，如流变改性剂。流变改性剂用于改性有色涂料的流动特性，以使有色涂料能够具有良好的保水力(water retention)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无机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。需要能提供良好的保水力并且在低剪切和高剪切下都具有良好的粘度行为的用于有色涂料的流变改性剂。
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。
苯乙烯丙烯酸酯共聚物在制浆和造纸中用于各种目的，如表面施胶组合物或用于增加纸的干强度。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。
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组合物，其在用于有色涂料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。
根据本发明的用于改性有色涂料的流变性的典型组合物包含：
-水性聚合物分散体，其包含以下单体的共聚物：
-单体(a)，其为至少一种任选取代的苯乙烯，和
-单体(b)，其为至少一种(甲基)丙烯酸C1-C4烷基酯，
该共聚物具有D50<100nm的粒径，和
-平均分子量Mn<1000g/mol的降解淀粉。
根据本发明的用于涂布纸或纸板等的典型有色涂料包含无机矿物颗粒和根据本发明的组合物。
根据本发明的组合物的根据本发明的典型用途是作为有色涂料的添加剂用于改善有色涂料的保水力。
现已令人惊讶地发现，当包含苯乙烯丙烯酸酯共聚物的聚合物分散体和平均分子量Mn<1000g/mol的降解淀粉的混合物的组合物作为流变改性剂用于有色涂料中时，该组合物提供了预料不到的改善。该组合物在低剪切和高剪切下均赋予有色涂料优异的保水力和粘度性能。观察到的效果的起源尚未被完全了解。不希望受理论束缚，假定强降解淀粉能够有效地与有色涂料的其他组分形成氢键，并因而保留有色涂料中的水，同时保持低粘度水平。出乎意料的是，淀粉的降解程度对有色涂料的性质具有如此强的积极作用。
根据本发明的一个实施方案，按组合物的总干固体含量计算，组合物中降解淀粉的量为1-70重量％，优选3-60重量％，更优选5-50重量％。
根据本发明的一个实施方案，按组合物的总干固体含量计算，组合物中聚合物分散体的量为30-99重量％，优选40-97重量％，更优选50-95重量％。
根据本发明，降解淀粉的低数均分子量减少了有色涂料的粘度增加。同时，强降解淀粉的使用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，并且强降解淀粉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。根据本发明的一个优选实施方案，该组合物包含降解淀粉，其平均分子量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50-990g/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(Waters Ultrahydrogel 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的常规柱校准。乙二醇用作内标。
适用于本发明的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，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。
可以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的，或者其可以具有净阴离子电荷。具有净阴离子电荷的降解淀粉是优选的。在本申请的上下文中，具有阴离子净电荷的淀粉可以是阴离子的，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，只要降解淀粉的净电荷是阴离子的。阴离子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的阴离子基团的数目，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。
通过加热使降解淀粉溶解到水中，由此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对15重量％的溶液在25℃下测量，溶液形式的降解淀粉的粘度为<15mPas，优选<10mPas。
用于根据本发明的组合物的水性聚合物分散体包含优选通过单体(a)和单体(b)的自由基乳化共聚获得的共聚物，所述单体(a)是至少一种任选取代的苯乙烯，所述单体(b)是至少一种(甲基)丙烯酸C1-C4烷基酯。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。合适的单体(b)可以选自丙烯酸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，聚合物分散体包含通过单体(a)和单体(b)以及至少一种任选的单体(c)共聚获得的共聚物，所述单体(c)是烯键式不饱和的且不同于单体(a)和单体(b)。合适的烯键式不饱和可共聚单体(c)是丙烯酸乙基己酯、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、乙酸乙烯酯或阴离子共聚单体，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是优选的。
按单体(a)、(b)和任选的(c)的总干固体含量计算，单体(a)的量可以是0.1-75重量％，优选5-60重量％，更优选10-55重量％。按单体(a)、(b)和任选的(c)的总干固体含量计算，单体(b)的量可以是25-99.9重量％，优选30-95重量％，更优选35-90重量％。按单体(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％。
根据本发明的一个优选实施方案，聚合物分散体包含通过至少上述单体(a)、(b)和任选的(c)在多糖的存在下发生自由基乳化聚合获得的共聚物。多糖可以是淀粉，或者它可以选自用于获得本发明中使用的苯乙烯丙烯酸酯共聚物的任何含有游离羟基的多糖，例如直链淀粉、支链淀粉、角叉菜胶、纤维素、壳聚糖(chitosan)、几丁质(chitin)、糊精、瓜尔胶(guarane)和其他半乳甘露聚糖、阿拉伯树胶、半纤维素组分和普鲁兰多糖(pullulan)。优选淀粉和糊精作为多糖。
根据本发明的一个优选实施方案，聚合物分散体包含苯乙烯丙烯酸酯共聚物，其通过上述单体(a)、(b)和任选的(c)在淀粉(优选降解淀粉)的存在下发生自由基乳化聚合获得。淀粉可以是任何合适的天然淀粉，如马铃薯、大米、玉米、蜡质玉米、小麦、大麦或木薯淀粉，优选马铃薯淀粉。支链淀粉含量>80％、优选>95％的淀粉是有利的。聚合中使用的淀粉也可以进行改性，例如，阴离子化、阳离子化或降解。
根据本发明的一个优选实施方案，聚合物分散体包含苯乙烯丙烯酸酯共聚物，其通过上述单体(a)、(b)和任选的(c)在强降解淀粉的存在下发生自由基乳化聚合获得。在聚合中使用的降解淀粉可以与用于与聚合物分散体一起形成根据本发明的组合物的降解淀粉相同或不同。根据本发明的一个优选实施方案，在聚合中使用的淀粉是强降解淀粉，其平均分子量为<1000g/mol，优选100-990g/mol，更优选100-790g/mol，甚至更优选为100-490g/mol，有时甚至更优选在100-400g/mol。平均分子量以与本申请前面所述相同的方式测定。在聚合中使用的降解淀粉可以通过使淀粉经受氧化、热、酸或酶促降解而获得，优选氧化降解。
在聚合中使用的降解淀粉可以是非离子性的或具有阴离子净电荷。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；或两性的，即含有带阴离子和阳离子电荷的基团，只要净电荷是阴离子的即可。降解淀粉优选是阴离子性的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。
根据本发明的一个实施方案，当通过在降解淀粉的存在下聚合获得聚合物分散体时，按聚合物分散体的总干固体含量计算，聚合物分散体中降解淀粉的量为9-97重量％，优选12-92重量％，更优选16-83重量％。
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。在采用超大气压下的压力反应器的情况中，温度可以>100℃。在聚合开始时和加入单体之前，按聚合开始时反应混合物的含量计算，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％。
聚合物分散体是通过将已在上文描述的单体单独地或作为混合物和适合于引发聚合的自由基引发剂加入到优选为多糖水溶液、更优选为平均分子量<1000g/mol的降解淀粉溶液中进行聚合而得到的。由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％。单体的量在此是指单体(a)、(b)和任选的(c)的总量，它们在聚合过程中加入到反应混合物中。通常在预定的时间段内加入单体。
在结束添加单体和引发剂后，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，可以调节所得聚合物分散体的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。
基于总分散体的重量，根据本发明获得的聚合物分散体的浓度(即干固体含量)可以为>30重量％，更通常>35％，优选35-60重量％，更优选35-57重量％。
当在聚合中使用降解淀粉时，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，所获得的水性聚合物分散体可以具有≤150mPas的粘度。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。
根据本发明的一个实施方案，聚合物分散体的粒径D50值为<85nm，优选<80nm，更优选<75nm和/或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ZetasizerNano 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。
根据一个优选的实施方案，该组合物是水性聚合物分散体和降解淀粉水溶液的混合物。根据本发明的组合物可以通过在将组合物加入到有色涂料之前将聚合物分散体与降解淀粉混合而形成。或者，聚合物分散体和降解淀粉可以单独地、优选同时加入到有色涂料，由此在有色涂料中形成组合物。优选地，在加入到有色涂料之前，将降解淀粉与聚合物分散体混合以形成组合物。
包含水性聚合物分散体和降解淀粉的组合物可以用作有色涂料添加剂，如流变改性剂。有色涂料可用于涂布纸或纸板等。有色涂料在此理解为浆料，其包含水、粘合剂、无机矿物颗粒和添加剂。可以用于本发明中的合适的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、缎光白(satine white)、硫酸钡、硅酸铝钠、氢氧化铝和它们的任何混合物。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颗粒的粒径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。还可以将该组合物用作有色涂料中的唯一粘合剂。
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，使用转子3或4来测量粘度。
该组合物的用量可以是1-50份，优选1-30份，更优选1-20份。
按最终纸或纸板等的干固体计算，降解淀粉在涂布纸或纸板等中的量可以是0.001-20重量％，优选0.05-15重量％，更优选0.1-10重量％。
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颗粒的量计算的，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：组合物的制备
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。30分钟后，淀粉降解完成。开始化学进料。
单体作为混合物进料：在200分钟内加入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45.6％，粒径为66nm，粘度为148mPas。
在氮气气氛下在另一个具有冷却/加热夹套的1升玻璃反应器中，将148.3g氧化降解的马铃薯淀粉(Perfectamyl A 4692)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1.52g1.0％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，淀粉降解完成，并将其冷却至室温。获得固体含量为28.1％的淀粉溶液。将降解淀粉溶液与聚合物分散体以10:90重量％的比例混合。
实施例2：有色涂料的制备和实验
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克干无机矿物颜料。
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 BDA0001780891530000091
Akademi Gravimetric Water Retention装置测量静态保水力。
有色涂料2以与有色涂料1类似的方式制备，不同的是以4.5份聚合物分散体代替4.5份苯乙烯丁二烯胶乳，并在天然淀粉后加入0.5份降解淀粉。聚合物分散体对应于实施例1中制备的聚合物分散体，并且降解淀粉对应于实施例1中制备的降解淀粉。
有色涂料33以与有色涂料1类似的方式制备，不同的是在天然淀粉后加入0.5份降解淀粉。使用的降解淀粉对应于实施例1中制备的降解淀粉。
有色涂料的组成在表1中给出，得到的测量结果在表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 4.5
聚合物分散体 - 4.5 -
天然淀粉 7 7 7
降解淀粉 - 0.5 0.5
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 23.1
低剪切粘度[mPas] 304 290 290
高剪切粘度[mPas] 37 36 36
保水力[g/m<sup>3</sup>] 68 28 71
从表2可以看出，当向涂料组合物中加入强降解淀粉时，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)

1.一种用于涂布纸或纸板的有色涂料，所述有色涂料包括无机矿物颗粒和用于改变有色涂料的流变性的组合物，其中所述组合物是水性聚合物分散体和降解淀粉水性溶液的混合物，所述组合物包含：
-按所述组合物的总干固体含量计算，30-99重量％的水性聚合物分散体，所述聚合物分散体包含以下单体的共聚物：
-0.1-75重量％的单体(a)，其为至少一种任选取代的苯乙烯，和
-25-99.9重量％的单体(b)，其为至少一种(甲基)丙烯酸C1-C4-烷基酯，其中所述重量％是按单体(a)和(b)的总干固体含量计算的，
其中所述共聚物的粒径D50<100nm，和
-按所述组合物的总干固体含量计算，1-70重量％的降解淀粉，其平均分子量Mn<1000g/mol。
2.根据权利要求1所述的有色涂料，其特征在于按所述组合物的总干固体含量计算，所述组合物中降解淀粉的量为3-60重量％。
3.根据权利要求1所述的有色涂料，其特征在于按所述组合物的总干固体含量计算，所述组合物中聚合物分散体的量为40-97重量％。
4.根据权利要求1所述的有色涂料，其特征在于所述降解淀粉的平均分子量Mn<800g/mol。
5.根据权利要求1所述的有色涂料，其特征在于所述降解淀粉的平均分子量Mn为50-990g/mol。
6.根据权利要求1所述的有色涂料，其特征在于所述降解淀粉是非离子的或者其具有净阴离子电荷。
7.根据权利要求6所述的有色涂料，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。
8.根据权利要求1所述的有色涂料，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。
9.根据权利要求1所述的有色涂料，其特征在于所述单体(b)选自(甲基)丙烯酸丁酯。
10.根据权利要求1所述的有色涂料，其特征在于所述共聚物通过单体(a)和单体(b)以及至少一种单体(c)的共聚获得，所述单体(c)是烯键式不饱和的且不同于单体(a)和单体(b)。
11.根据权利要求10所述的有色涂料，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选自丙烯酸、甲基丙烯酸、衣康酸、马来酸和苯乙烯磺酸。
12.根据权利要求1所述的有色涂料，其特征在于所述共聚物的粒径D50<85nm。
13.根据权利要求1所述的有色涂料，其特征在于包含所述共聚物的聚合物分散体通过至少单体(a)和单体(b)在多糖存在下发生自由基乳化聚合获得。
14.根据权利要求13所述的有色涂料，其特征在于所述多糖是淀粉或糊精。
15.根据权利要求14所述的有色涂料，其特征在于所述多糖是降解淀粉，其平均分子量为100-990g/mol。
16.根据权利要求1所述的有色涂料，其特征在于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、缎光白、硫酸钡、硅酸铝钠、氢氧化铝和它们的任何混合物。
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