CN102257218A - 有色涂料组合物以及涂布有该组合物的纸或纸板 - Google Patents
有色涂料组合物以及涂布有该组合物的纸或纸板 Download PDFInfo
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- CN102257218A CN102257218A CN2009801512216A CN200980151221A CN102257218A CN 102257218 A CN102257218 A CN 102257218A CN 2009801512216 A CN2009801512216 A CN 2009801512216A CN 200980151221 A CN200980151221 A CN 200980151221A CN 102257218 A CN102257218 A CN 102257218A
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- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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Abstract
本发明涉及用于纸和/或纸板的有色涂料组合物,其包含颜料、任选已知的用于涂料组合物的添加剂以及包含平均粒度≤100nm的苯乙烯丙烯酸酯共聚物的粘合剂替代品。本发明还涉及用根据本发明的有色涂料组合物涂布的纸或纸板。
Description
本发明涉及有色涂料组合物(coating colour composition)以及根据所附权利要求的前序部分所述的纸或纸板。本发明还涉及苯乙烯丙烯酸酯共聚物的用途。
为了改善纸和纸板的强度、适印性和外观(如光滑度和光泽度)以及其它性能,将纸和纸板涂布以不同的有色涂料。常规的涂料组合物主要包括涂料和粘合剂,以及可能的其它添加剂,例如共粘合剂(co-binders)、防腐剂、分散剂、消泡剂、润滑剂、硬化剂和荧光增白剂。
涂料组合物中粘合剂的作用是使颜料颗粒彼此结合并与原纸结合。粘合剂还可以影响涂料组合物的流变性质。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聚合物。这样的聚合物分散体通常称为胶乳粘合剂,且其粒径为约0.1-0.2μm。作为胶乳粘合剂的合成化合物的价格相对较高。因此,使涂料组合物中粘合剂的量最小化而不损害组合物和所得的被涂布的纸的性质是有利的。
苯乙烯/丙烯酸酯共聚物作为表面上浆剂(surface sizing agents)是已知的。例如,US 6,426,381公开了能够用于表面上浆的苯乙烯/(甲基)丙烯酸酯共聚物。
JP 58/115196公开了水溶性纸强度增强剂,其是通过苯乙烯和丙烯酸酯在淀粉存在下的接枝共聚而制备的。据称,该增强剂改善纸的强度和上浆程度。
本发明一目的是提供有色涂料组合物,其可以使现有技术中的缺点最小化甚至消除。
另一目的是提供有色涂料组合物,其改善被涂布的纸或纸板的强度性质。
本发明的另一目的是提供有色涂料组合物,其中可以降低粘合剂的量而不损害被涂布的纸的强度性质。
通过具有独立权利要求特征部分给出的特征的方法和设置实现了这些目的。
本发明的典型的用于纸和/或纸板的有色涂料组合物包括
-颜料,
-任选已知的用于涂料组合物的添加剂,以及
-粘合剂替代品,其包含平均粒度≤100nm的苯乙烯丙烯酸酯共聚物替代品。
本发明的典型的纸或纸板被本发明的有色涂料组合物涂布。
令人惊奇地发现,通过使用包含粒度小且定义明确的苯乙烯和丙烯酸酯的共聚物的粘合剂替代品,可以全部或部分地代替有色涂料组合物中所用的常规胶乳粘合剂,并且同时获得具有改善的强度特性的被涂布的纸。还可以降低常规粘合剂的量而不会显著损害被涂布的纸的强度。当粘合剂替代品被用作涂料组合物中的主粘合剂或唯一粘合剂时,可以获得具有明显增强的表面强度特性的被涂布的纸。另一方面,当使用粘合剂替代品来部分代替常规粘合剂时,发现可以很容易将粘合剂总量降低20-30%,而不损害纸的强度性质。降低粘合剂总量自然降低了与之相关的成本。
令人惊奇地,苯乙烯丙烯酸酯共聚物的小粒度对获得的被涂布的纸的强度性质有影响。不期望受理论所限,推测该影响归因于增加的表面积。
用作粘合剂替代品的苯乙烯丙烯酸酯共聚物可通过烯键不饱和单体的共聚反应获得。适当的苯乙烯单体为苯乙烯和取代的苯乙烯,例如α-甲基苯乙烯或乙烯基甲苯或它们的混合物,且适当的丙烯酸酯单体为C1-C4烷基丙烯酸酯,C1-C4烷基甲基丙烯酸酯或它们的混合物(如正丁基丙烯酸酯、异丁基丙烯酸酯、叔丁基丙烯酸酯或2-丁基丙烯酸酯以及相应的丁基甲基丙烯酸酯)、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,优选至少两种异构化丁基丙烯酸酯的混合物,尤其优选正丁基丙烯酸酯和甲基丙烯酸甲酯的混合物。根据本发明一最优选的实施方式,在聚合物反应中使用正丁基丙烯酸酯和叔丁基丙烯酸酯的混合物。对于两种单体的混合物,混合比例可以是10∶90至90∶10。
优选地,粘合剂替代品是包含淀粉的苯乙烯丙烯酸酯共聚物。可以如US 6,426,381所述,即通过烯键不饱和单体在淀粉存在下的自由基乳液共聚反应获得苯乙烯丙烯酸酯共聚物。淀粉可以是任何适当的天然淀粉,例如马铃薯、大米、玉米、蜡质玉米(waxy corn)、小麦、大麦或木薯淀粉,优选马铃薯淀粉。支链淀粉含量为>80%(优选>95%)的淀粉是有利的。也可以对淀粉进行修饰,例如阴离子化、阳离子化或降解。阴离子化的淀粉包含阴离子基团,例如羧酸根或磷酸根基团,而阳离子化的淀粉包含阳离子基团,例如季铵盐基团。表示淀粉中平均每个葡萄糖单元上阴离子/阳离子基团的数目的取代度(DS)通常为0.01-0.20。同时包含阴离子和阳离子基团的两性淀粉也可以用于制备苯乙烯丙烯酸酯共聚物。降解淀粉是通过对淀粉进行氧化、热、酸或酶降解而获得的,优选氧化降解。次氯酸盐、过二硫酸盐、过氧化氢或它们的混合物可以用作氧化剂。降解淀粉通常的平均分子量(Mn)为500-10000,其可以通过已知的凝胶色谱法测定。固有粘度通常为0.05至0.12dl/g,其通过例如已知的粘度测定法测定。
根据本发明一实施方式,可以使用任何其它含有游离羟基的多糖(例如直链淀粉、支链淀粉、角叉菜、纤维素、脱乙酰壳多糖、甲壳质、糊精、瓜耳胶(瓜拉纳,guarane)和其它半乳甘露聚糖、阿拉伯树胶、半纤维素成分和普鲁兰多糖)代替淀粉来获得用于本发明的苯乙烯丙烯酸酯共聚物。在列出的多糖中,更优选糊精,即苯乙烯丙烯酸酯共聚物包含糊精。
粘合剂替代品可以以固含量为10-50%(优选为20-50%,更优选为21-29%,最优选为35-40%)的水性聚合物分散体的形式使用。高的固含量是有利的,因为可以使涂料组合物中的水量最小化。
根据本发明一实施方式,水性分散体形式的粘合剂替代品的平均粒度为至少20nm,优选为至少25nm,更优选为30nm,还更优选为35nm,最优选至少40nm,且小于90nm,优选小于80nm,更优选小于70nm,还更优选小于60,最优选小于50nm。通常,粘合剂替代品的平均粒度为<100nm。根据本发明一实施方式,水性分散体形式的粘合剂替代品的平均粒度为20-100,优选为30-80nm,更优选为40-70nm,最优选为60-70。可以通过光子相关谱法(photon correlation spectroscopy),使用例如MalvernZetamaster装置,测定粘合剂替代品的平均粒度。
根据本发明一实施方式,除了粘合剂替代品之外,涂料组合物还包含胶乳粘合剂。可用于本发明的典型的合成胶乳粘合剂是本领域已知的胶乳,例如苯乙烯丁二烯(SB)胶乳、苯乙烯丙烯酸酯(SA)胶乳或聚乙酸乙烯酯(PVAc)胶乳。优选的胶乳粘合剂是苯乙烯丁二烯(SB)胶乳。胶乳粘合剂可被考虑作为涂料组合物的主粘合剂,其量通过使用本发明的粘合剂替代品而降低。
根据本发明一实施方式,除了粘合剂替代品和可能的主粘合剂之外,涂料组合物还可以包含淀粉粘合剂,该淀粉可以是阴离子的或阳离子的。
可用于本发明的典型颜料是碳酸钙、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、氢氧化铝或它们的任意混合物。碳酸钙可以是重质碳酸钙(GCC)或沉淀碳酸钙(PCC)或它们的混合物。颜料优选为碳酸钙。涂料组合物中所用的颜料的粒度D50通常为<5μm。
在本申请中,如本领域中常规的那样,通过给出颜料总量值100,并相对于颜料总量(pph)计算其它成分的量而给出有色涂料混合物的组成。所有成分的比例均以活性物质给出。
根据本发明一实施方式,粘合剂替代品可以与诸如羧甲基纤维素(CMC)、聚乙烯醇(PVOH)、淀粉、酪蛋白或蛋白质等常规共粘合剂一起使用。涂料组合物中共粘合剂的量通常为0.05-3份。在淀粉的情况下,其量可以为0.05-12份,优选为0.1-10份。
还可以向本发明的有色涂料组合物中加入少量的常规添加剂以改善组合物的性质或操纵性或者为其提供期望的功能。可能的添加剂例如是防腐剂、分散剂、消泡剂、润滑剂、硬化剂和荧光增白剂。其它添加剂的量通常为0-3份。
根据本发明一实施方式,有色涂料组合物包含
-100份颜料,
-0-12份粘合剂,优选胶乳粘合剂,
-1.5-9份粘合剂替代品,以及
-0-3份已知的添加剂,
条件是粘合剂与粘合剂替代品的总量为至少5份。
根据本发明另一实施方式,有色涂料组合物包含
-100份颜料,
-4-12份淀粉,
-3-6份粘合剂,优选胶乳粘合剂,
-2-4份粘合剂替代品,以及
-0-3份已知的添加剂。
根据本发明的再另一实施方式,有色涂料包含
-100份颜料,
-4-5份粘合剂,
-2-3份粘合剂替代品,以及
-0-3份已知的添加剂。
可以通过常规方式制备本发明的有色涂料,即将颜料浆与分散体形式的粘合剂替代品以及可能的照例加入的其它添加剂混合。如果除了粘合剂替代品之外还使用常规的粘合剂,则其也照例加入到有色涂料组合物中。由于当使用本发明的粘合剂替代品时可以使用现有的设备和操作,所以不需要对设备进行大规模的改动。
通常,本发明的有色涂料的固含量为60-74%,优选为63-72%,更优选为65-71%,且粘度为<2500,通常为1000-2000mPas。通过使用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。
根据本发明一实施方式,以单涂层或多涂层的形式将有色涂料组合物涂布在纸或纸板表面上。采用的涂布方法包括例如刮涂、棒涂(rod coating)、膜转移涂布或气刷涂布。所涂布的涂料重量通常为5-30g/m2/面。在一层所涂布的涂层中,涂料重量通常为5-16g/m2/面,更通常为6-14g/m2/面,且最通常为8-12g/m2/面。
实施例
以下非限制性实施例说明本发明的某些实施方式。
在阴离子淀粉的存在下制备包含苯乙烯丙烯酸酯共聚物的粘合剂替代品
(一般性描述)
在具有回流冷凝器的2l三口烧瓶中,于持续搅拌下将67g氧化降解的马铃薯淀粉(PerfectamylA 4692)分散在536g去矿物质水中。通过加热至85℃将淀粉溶解,从而连续加入20.0g FeSO4×7H2O(0.72mmol)的1%水溶液和4.0g 35%过氧化氢。
15min后,完成淀粉降解。在85℃下于90分钟内,以恒定的加料速度同时但分别计量供给包含单体的溶液和引发剂溶液。单体溶液包含86.6g苯乙烯、43.3g正丁基丙烯酸酯和43.3g叔丁基丙烯酸酯。引发剂溶液包含4.3g过氧化氢(35%)和127g水。在氮气气氛下进行聚合反应。
计量供给结束10min后,进一步加入0.7g叔丁基过氧化氢用于随后的活化,并继续进行搅拌60min。此后,冷却至室温,经过100μm过滤器进行过滤。用20%氢氧化钠溶液将pH调节至6。
获得固含量为24.9%且浑浊度值A=0.380(1∶10稀释,660nm)的聚合物分散液。通过Malvern Zetamaster测量的平均粒度为61.3nm。
涂布实验
对比实验
使用表1的有色涂料组合物测试商业苯乙烯丁二烯和苯乙烯丙烯酸酯胶乳。制备有色涂料并稀释至固含量为50%,以便用于实验室涂布。对纸样品进行下拉涂布(draw-down coated)。用IGT-仪器(IGT测试系统)测量表面强度。结果总结于表2中。
表1.所用的有色涂料组合物
有色涂料成分 | 份数 |
涂布级重质碳酸钙 | 100 |
粘合剂 | 9 |
流变改性剂 | 0.7 |
表2.使用常规粘度油获得的有色涂料性质和表面强度结果
粘合剂 | SB-胶乳 | SA-胶乳 |
固体(%) | 50.2 | 50.2 |
T(℃) | 23 | 26 |
pH | 9.0 | 9.0 |
Br100(mPas) | 89 | 88 |
Br50(mPas) | 115 | 119 |
涂料重量(g/m2) | 7.9 | 7.8 |
平均IGT-表面强度(m/s): | 0.70 | 0.73 |
两种商业胶乳给出类似的表面强度结果。
实验1
以实验室规模进行实验。粘合剂替代品1包含在阴离子淀粉存在下聚合的苯乙烯丙烯酸酯共聚物,且粘合剂替代品2包含在阳离子淀粉存在下聚合的苯乙烯丙烯酸酯共聚物。根据上文的一般性表示制备粘合剂替代品1。粘合剂替代品1和粘合剂替代品2的固含量分别为24%和25%。在涂料组合物中使用商业苯乙烯丁二烯作为主粘合剂。粘合剂替代品的类型是有色涂料组合物中唯一的变量。使用Diaf实验室溶解器制备有色涂料组合物并稀释至固含量为50%。有色涂料组合物如表1所示。
表1.所用的有色涂料组合物
有色涂料成分 | 份数 |
涂布级重质碳酸钙 | 100 |
总粘合剂(=主粘合剂+粘合剂替代品) | 6-9 |
流变改性剂 | 0.7 |
使用SB胶乳和粘合剂替代品的混合物(4.5+3份)。所有待测有色涂料组合物的固含量为67%且Brookfield 100粘度为约2000mPas或更低。使用模型4的A-GWR装置(制造商:DT-paper science),使用30秒的时间和0.3bar的压力测量静水保留值(static water retention value)。静水保留值与参比的类似。
使用粘合剂替代品为有色涂料组合物赋予类似于参比的高剪切粘度。对纸样品进行下拉涂布。根据标准操作SCAN-P 63:90,用IGT AIC2-5仪器测量被涂布的纸样品的表面强度。表面强度结果示于表2.
表2.表面强度结果
粘合剂/组合物性质 | 参比组合物 | 组合物1 | 组合物2 |
SB-胶乳(份数) | 9 | 4.5 | 4.5 |
粘合剂替代品1(份数) | - | 3 | - |
粘合剂替代品2(份数) | - | - | 3 |
固含量(%) | 49.6 | 50.0 | 50.0 |
涂料重量(g/m2) | 10.8 | 11.0 | 10.1 |
IGT-表面强度(m/s) | 0.86 | 0.84 | 0.80 |
从表2可见,通过使用3份粘合剂替代品,能够使SB-胶乳量减少50%,且被涂布的纸样品仍然显示相同的表面强度性质。
实验2
使用OptiBlade涂布机用粘合剂替代品1进行实验。对原纸进行预涂布,且所涂布的涂料重量为11g/m2。不同的有色涂料组合物示于表3。所有的有色涂料组合物含有相同量的常规有色涂料添加剂(在此未列出)。
表3.使用粘合剂替代品1的测试组合物
组合物/组合物性质 | 组合物3 | 组合物4 | 组合物5 | 组合物6 | 参比组合物 |
涂布GCC(份数) | 100 | 100 | 100 | 100 | 100 |
SB胶乳(份数) | 5 | 5 | 4 | 4 | 9 |
粘合剂替代品1(份数) | 3 | 2 | 3 | 2 | - |
固含量(%) | 69 | 69 | 69 | 69 | 69 |
pH | 9 | 9 | 9 | 9 | 9 |
所有组合物用涂布装置运行均没有任何问题。对于所有组合物,刮刀压力在相同的水平上。参比组合物具有最低的Brookfield粘度。
在Optiload Twinline上对涂布有测试组合物的纸样品进行轧光。轧光速度为800m/min且辊温度为120℃。
然后在Man Roland 300印刷机上使用5-色(B、C、M、B、C)印刷,并以恒定的密度和速度(8000张/h)对涂布的纸样品进行印刷。在表4中给出印刷的纸样品的视觉评价的结果,并如下分级:1=极好,2=良好,3=中等,4=差,5=极差。
表4.印刷的样品的视觉评价
样品名 | 评价 |
参比样品 | 2 |
组合物3 | 3 |
组合物4 | 2 |
组合物5 | 1.5 |
组合物6 | 3.5 |
还分析了纸样品的堆墨性(piling)和拉毛性(picking),且将结果示于表5。分级如下:0=良好;1-3=合适;4=差;5=极差。所有涂布的纸样品具有好的抗堆墨性和合适的拉毛性。所有样品的运行性能也很好。
表5.20℃下的堆积和拣选结果
分析印刷的纸样品,并将来自试验性印刷的平均结果总结于表6。
表6.印刷试验的总结
结果显示,在印刷光泽度、纸光泽度、平滑度、展刷以及在C50%、M50%和C100%上的墨斑中,参比样品和包含粘合剂替代品1的样品之间的差异不显著。在转移测试中,包含4份SB胶乳和2份粘合剂替代品1的具有最低总粘合剂含量的样品比参比样品快得多。
纵向(MD)和横向(CD)的IGT表面强度结果总结于表7。
表7.使用IGT的表面强度结果
从结果可以看出,合成粘合剂含量的总量从9份下降至6份仍然给出可接受的印刷结果。
实验3
测试了粘合剂替代品与淀粉的相容性。用粘合剂替代品1和2进行了实验室测试,粘合剂替代品1包含在阳离子淀粉存在下聚合的苯乙烯丙烯酸酯共聚物,而粘合剂替代品2包含在阴离子淀粉存在下聚合的苯乙烯丙烯酸酯共聚物。粘合剂替代品1的固含量为24%,而粘合剂替代品2的固含量为25%。所用的有色涂料配方如表8所示。
表8.含淀粉的有色涂料组合物
组分 | 份数 |
涂布级重质碳酸钙(GCC) | 100 |
共粘合剂(淀粉) | 10 |
总合成粘合剂(=主粘合剂+粘合剂替代品) | 5-7 |
有色涂料组合物的测试结果总结于表9。组合物A包含粘合剂替代品1,而组合物B包含粘合剂替代品2。
表9.含有淀粉和粘合剂替代品的有色涂料组合物的性质
参比样品 | 组合物A | 组合物B | |
SB胶乳含量 | 7 | 3 | 3 |
粘合剂替代品含量 | - | 2 | 2 |
总粘合剂含量(pph) | 7 | 5 | 5 |
粘合剂替代品固含量(%) | - | 24 | 25 |
有色涂料固含量(%) | 65.3 | 64.8 | 64.1 |
T(℃) | 32 | 31 | 31 |
pH | 9.0 | 9.0 | 9.0 |
Br100(mPas) | 614 | 586 | 930 |
Br50(mPas) | 900 | 820 | 1380 |
WR(g/m2) | 67.7 | 50.3 | 54.5 |
将SB胶乳用作参比,粘合剂替代品1为有色涂料组合物提供类似的粘度。包含粘合剂替代品2的有色涂料组合物具有比参比更高的粘度值。参比样品具有最低的高剪切粘度。粘合剂替代品1为有色涂料组合物提供的粘度比粘合剂替代品2提供的粘度低。对于测试的涂料组合物,所有粘度值均为良好或可接受。
从表9可以看出,本发明的涂料组合物的静水保留(WR)值好于参比组合物。
用测试的涂料组合物对纸样品进行下拉涂布。测定了表面强度,并将结果示于表10。
表10.用中等粘度油测量的包含淀粉和粘合剂替代品的有色涂料组合物的IGT-表面强度
参比 | 组合物A | 组合物B | |
总粘合剂含量(份数) | 7 | 5(3+2) | 5(3+2) |
固含量(%) | 50.0 | 50.0 | 50.0 |
涂料重量(g/m2) | 11.5 | 11.1 | 11.1 |
表面强度(m/s) | 1.09 | 0.97 | 1.17 |
被测有色涂料组合物显示类似的表面强度。
即使参考目前似乎是最可行的和优选的实施方式描述了本发明,应当理解,本发明不应限于上述的实施方式,本发明旨在覆盖所附权利要求范围内的不同修改和等同的技术方案。
Claims (14)
1.用于纸和/或纸板的有色涂料组合物,其包含
-颜料,
-任选已知的用于涂料组合物的添加剂,以及
-粘合剂替代品,其包含平均粒度≤100nm的苯乙烯丙烯酸酯共聚物。
2.根据权利要求1的有色涂料组合物,其特征在于,粘合剂替代品的平均粒度为20-100nm。
3.根据权利要求1或2所述的有色涂料组合物,其特征在于,其还包含胶乳粘合剂。
4.根据权利要求3所述的有色涂料组合物,其特征在于所述胶乳粘合剂是苯乙烯丁二烯胶乳、苯乙烯丙烯酸酯胶乳或聚乙酸乙烯酯胶乳。
5.根据权利要求1所述的有色涂料组合物,其特征在于,所述粘合剂替代品是以下的共聚物:
a)苯乙烯单体或取代的苯乙烯单体,例如α-甲基苯乙烯或乙烯基甲苯或它们的混合物;和
b)选自C1-C4烷基丙烯酸酯、C1-C4烷基甲基丙烯酸酯、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的丙烯酸酯单体。
6.根据权利要求1所述的有色涂料组合物,其特征在于,所述粘合剂替代品是包含淀粉的苯乙烯丙烯酸酯共聚物。
7.根据权利要求1所述的有色涂料组合物,其特征在于,其包含
-100份颜料,
-0-12份粘合剂,
-1.5-9份粘合剂替代品,以及
-0-3份已知的添加剂,
条件是粘合剂与粘合剂替代品的总量为至少5份。
8.根据权利要求1所述的有色涂料组合物,其特征在于,其包含
-100份颜料,
-4-12份淀粉,
-3-6份粘合剂,优选胶乳粘合剂,
-2-4份粘合剂替代品,以及
-0-3份已知的添加剂。
9.根据权利要求1所述的有色涂料组合物,其特征在于,其包含
-100份颜料,
-4-5份粘合剂,
-2-3份粘合剂替代品,以及
-0-3份已知的添加剂。
10.根据前述任一权利要求所述的有色涂料组合物,其特征在于,所述颜料是碳酸钙、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、氢氧化铝或它们的任意混合物。
11.涂布有权利要求1-10中任一项所述的有色涂料组合物的纸或纸板。
12.根据权利要求11所述的纸或纸板,其特征在于,涂布在纸上的涂层的涂料重量为5-30g/m2/纸面。
13.平均粒度≤100nm的苯乙烯丙烯酸酯共聚物作为粘合剂替代品在用于纸或纸板的涂料组合物中的用途。
14.根据权利要求13所述的用途,其特征在于,所述共聚物以固含量为10-50%的水性分散体的形式使用。
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CN108779608A (zh) * | 2016-03-18 | 2018-11-09 | 陶氏环球技术有限责任公司 | 纸涂料组合物和其制备方法 |
CN108699775A (zh) * | 2016-03-22 | 2018-10-23 | 凯米罗总公司 | 用于改性有色涂料的流变性的组合物、其用途和有色涂料 |
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CN108699775B (zh) * | 2016-03-22 | 2021-05-14 | 凯米罗总公司 | 用于改性有色涂料的流变性的组合物、其用途和有色涂料 |
CN111005258A (zh) * | 2019-12-31 | 2020-04-14 | 玖龙纸业(东莞)有限公司 | 一种轻涂牛卡纸及其生产方法 |
CN111005258B (zh) * | 2019-12-31 | 2021-09-17 | 玖龙纸业(东莞)有限公司 | 一种轻涂牛卡纸及其生产方法 |
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CA2670397C (en) | 2017-05-16 |
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EP2370631B1 (en) | 2017-11-08 |
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