CN108779362B - 水基阻挡涂层 - Google Patents
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Abstract
本文提供一种适合于用作阻挡涂层的水基阻挡涂料组合物,所述组合物包含(A):(i)(A)总重量40至95wt%在(d)0至40%wt%分子量Mn为500至10,000的降解淀粉存在下,可通过自由基(共)聚合含下述组分的烯键式不饱和单体共混物获得的水性聚合物组合物:(a)0至70wt%至少一种任选取代的苯乙烯,(b)最多100wt%至少一种(甲基)丙烯酸C1‑C4‑烷酯,(c)0至10wt%其他烯键式不饱和可共聚单体,其中(a)+(b)+(c)+(d)之和为100%;(ii)(A)总重量2至55wt%任选地与(i)的组分一起聚合的聚乙烯醇(PVA);(iii)(A)总重量2至30wt%的增塑剂;(iv)(A)总重量5至30wt%含任选地以与松香的混合物形式的C16‑C18链烯基烯酮二聚体的组合物,其中C16‑C18链烯基烯酮二聚体:松香之比为100:0至25:75;(v)(A)总重量5至20wt%的胶凝剂;和(B):填料。
Description
技术领域
本发明涉及纸张和纸板的阻挡涂层,尤其形成阻挡涂层用的水基阻挡涂料组合物,和阻挡涂布纸张与纸板的方法。
背景技术
水基阻挡涂层中的主要成分是聚合物。影响聚合物阻挡性能的因素一般地为结晶度,取向,分子结构和极性,以及大气条件。另外,在基底上形成无针孔膜的能力是关键的。
分散体的成膜是指当干燥时聚合物粒子的聚结。成膜从水蒸发和填充聚合物粒子进行到因毛细力导致的这些粒子的变形,和最后到聚合物分子跨越粒子边界相互扩散。当旨在无针孔的阻挡层时,良好且均匀的膜是关键的。
当折叠时,龟裂成为现有技术的阻挡涂层应用中最大的问题,从而导致阻挡性能的损失。
发明内容
本发明的目的因此是提供水基阻挡涂料组合物和用于阻挡涂布纸张与纸板的方法,用本发明的水基涂料组合物的一层或多层涂布的物体,和本发明的水基阻挡涂料组合物用于在纸张或纸板上形成油脂阻挡层的用途。
为了克服上述问题,通过特征在于独立权利要求中描述的组合物和方法,实现本发明的目的。本发明的优选实施方案公开于从属权利要求中。
本发明基于下述理念:提供一种水基阻挡涂料组合物,除了可由烯键式不饱和单体共混物获得的水性聚合物组合物(i)以外,它还包含:(ii)(A)的总重量2至55wt%的聚乙烯醇(PVA);(iii)(A)的总重量0至30wt%的增塑剂;(iv)(A)的总重量0至30wt%的包含C16-C18链烯基烯酮二聚体,任选地作为与松香的混合物形式的组合物;(v)(A)总重量0至20wt%的胶凝剂。本发明组合物的优点是,提供当折叠时抗龟裂的阻挡涂层,尤其油脂阻挡涂层。
附图说明
以下通过优选实施方案,参考附图更加详细地描述本发明,其中:
图1示出了第一组皱褶试验图像;
图2示出了第二组皱褶试验图像;
图3示出了第三组皱褶试验图像。
具体实施方式
本文提供一种水基阻挡涂料组合物,其包含:
(A):
(i)(A)总重量40至95wt%在(d)0至40%wt%分子量Mn为500至10,000的降解淀粉存在下,可通过自由基乳液(共)聚合含下述组分的第一烯键式不饱和单体共混物获得的水性聚合物组合物:
(a)0至70wt%至少一种任选取代的苯乙烯,
(b)最多100wt%至少一种(甲基)丙烯酸C1-C4-烷酯,
(c)0至10wt%其他烯键式不饱和可共聚单体,
其中(a)+(b)+(c)+(d)之和为100%;
(ii)(A)总重量2至55wt%任选地与(i)的组分一起聚合的聚乙烯醇(PVA);
(iii)(A)总重量0至30wt%的增塑剂;
(iv)(A)总重量0至30wt%含任选地为与松香的混合物形式的C16-C18链烯基烯酮二聚体的组合物,其中C16-C18链烯基烯酮二聚体:松香之比为100:0至25:75;
(v)(A)总重量0至20wt%的胶凝剂;
和
任选地(B):填料。
该水性聚合物组合物(A)不需要包含苯乙烯。然而,(a)组单体的用量优选为20至60%,更优选30至60wt%。合适的(a)组单体的实例包括苯乙烯和取代苯乙烯,例如α-甲基苯乙烯,乙烯基甲苯,乙基乙烯基甲苯,氯甲基苯乙烯,及其混合物。
(b)组单体的用量可以是最高到100wt%,当水性聚合物组合物在不存在淀粉(d)和苯乙烯(a)的情况下聚合时。然而,(b)组单体的用量优选80至30%,更优选60至30wt%。合适的(b)组单体的实例包括丙烯酸C1-C4-烷酯,甲基丙烯酸C1-C4-烷酯或其混合物,例如丙烯酸正丁酯,丙烯酸异丁酯,丙烯酸叔丁酯,和丙烯酸2-丁酯,和相应的甲基丙烯酸丁酯类,甲基丙烯酸正丁酯,甲基丙烯酸异丁酯,甲基丙烯酸叔丁酯,和甲基丙烯酸2-丁酯,和此外,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。至少两种异构丙烯酸丁酯的混合物是可能的,可能地混合比为10:90至90:10。优选的(b)组单体是丙烯酸正丁酯。
合适的(c)组单体是进一步的烯键式不饱和单体,例如丙烯酸乙基己酯,丙烯酸硬脂酯,甲基丙烯酸硬脂酯,以及丙烯酸和甲基丙烯酸与具有大于4个碳原子的醇的进一步的酯,和此外,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,例如丙烯酸,甲基丙烯酸,苯乙烯磺酸。尤其优选的(c)组单体是丙烯酸和苯乙烯磺酸。然而,优选(c)组单体的用量为0wt%。
淀粉(d)可视需要在聚合段中存在。天然淀粉,例如土豆,小麦,玉米,大米或木薯淀粉合适作为淀粉,优选土豆淀粉。优选使用具有大于或等于80%的高支链淀粉含量的淀粉类型。尤其优选支链淀粉含量>95%的土豆淀粉。也可使用化学改性淀粉,例如羟乙基-或羟丙基-淀粉,或含有阴离子基团的淀粉,例如淀粉磷酸盐,或含有季铵基的阳离子淀粉,优选其取代度DS=0.01-0.2。取代度DS表示相对于每一葡萄糖单元,在淀粉内平均包含的阳离子基团的数量。尤其优选含有季铵基和阴离子基团,例如羧酸根和/或磷酸根基团二者,且也可任选地化学改性,例如羟基烷基化或烷基酯化的两性淀粉。可通过对所述淀粉类型进行氧化,热,酸或酶降解,获得根据本发明使用的淀粉(d)。优选淀粉的氧化降解。在建立淀粉的所需分子量之后优选使用的氧化剂,例如高氯酸盐,过氧二硫酸盐或过氧化氢,或其组合对于降解适合。尤其优选为了改进淀粉的溶解性能通常进行的用高氯酸盐降解淀粉,和例如在后续的接枝共聚之前立即可进行的例如用过氧化氢进一步降解。在这一情况下,以0.3至5.0wt%的浓度使用过氧化氢(以100%形式计算),基于所使用的淀粉。过氧化氢的用量取决于淀粉要降解的分子量。
按照这一方式降解的淀粉(d)的平均分子量Mn优选为500至10,000,结果是一方面确保乳液聚合物的良好分散,和另一方面,避免聚合批料的过早交联和沉淀。在例如通过已知方法用右旋糖酐标准物校正之后,可容易地通过凝胶渗透色谱分析测定降解淀粉的平均分子量。例如在"Methods in Carbohydrate Chemistry",第IV卷,Academic Press NewYork and Frankfurt,1964,第127页中描述的测粘度方法也适合于表征。所测定的特性粘度因此优选为0.05至0.12dl/g。
选择聚合物组合物的单体,以便所得(共)聚合物的玻璃化转变温度优选为-40℃至50℃,优选-10℃至30℃。
尤其优选用含过氧化氢和金属离子的氧化还原体系聚合。可通过添加油溶性、几乎不水溶的自由基引发剂,继续聚合。优选在添加第二淀粉批次期间连续添加油溶性、几乎不水溶的自由基引发剂以供在用水溶性氧化还原体系聚合之后后续活化,并由其完成聚合。
组合物(A)的总浓度典型地为10至50wt%,优选20至45wt%。在(A)中水性聚合物组合物(i)的用量优选为(A)总重量的40至95wt%。
可通过一起聚合所述组分,即通过在聚乙烯醇(PVA)(ii)存在下,聚合组分(i),获得(i)和(ii)的混合物。当通过一起聚合PVA(ii)与(i)的组分,获得(i)和(ii)的混合物时,(i):(ii)之比优选为45:55至60:40,更优选1:1。进一步当通过一起聚合PVA(ii)与(i)的组分获得(i)和(ii)的混合物时,在(A)中(i)的用量优选为(A)总重量的45至60wt%。
在一个实例中,在(d)0至40wt%分子量Mn为500至10,000的降解淀粉,和(e)接枝-连接的水溶性氧化还原体系作为自由基乳液共聚用自由基引发剂存在下,通过自由基共聚含(a)0至60wt%至少一种任选取代的苯乙烯,(b)最多100wt%至少一种(甲基)丙烯酸C1-C4-烷酯,和(c)0至10wt%其他烯键式不饱和可共聚单体的烯键式不饱和单体和(ii),获得(i)和(ii)的混合物,其中(a)+(b)+(c)+(d)+(ii)之和为100%。
当通过一起聚合所述组分,获得组分(i)和(ii)的混合物时,不需要在组合物中包括淀粉。因此,在一个特别的实例中,(d)的用量为0wt%。
或者可通过共混,添加PVA(ii)到水性聚合物组合物(i)中。也可通过共混,添加其他添加剂到配方中。当通过共混添加(ii)时,淀粉(d)的用量优选为20至40wt%。当通过共混添加PVA(ii)到(i)中时,在(A)中(i)的用量优选为(A)总重量的50至95wt%,更优选在(A)中(i)的用量为(A)总重量的50至95wt%,甚至更优选(i)的用量为(A)总重量的75至85%。
PVA等级的选择影响阻挡性能。较少水解的等级得到较好的氧气阻挡性能,而更多水解的等级改进水蒸气和油的阻挡性能。优选地,PVA选自分子量小于或等于50000的完全或部分水解的等级的组。
当通过一起聚合PVA(ii)与(i)的组分获得(i)和(ii)的混合物时,在(A)中PVA(ii)的用量优选为(A)总重量的40至55wt%。当通过一起聚合PVA(ii)与(i)的组分,获得(i)和(ii)的混合物时,最优选(i)的用量为(A)总重量的45至60wt%,和(ii)的用量为(A)总重量的40至55wt%。
当通过共混添加PVA(ii)到(i)中时,在(A)中PVA(ii)的用量优选为(A)总重量的2至20,更优选5至15wt%。当通过共混添加PVA(ii)到(i)中时,最优选(i)的用量为(A)总重量的75至85%,和在(A)中PVA(ii)的用量为2至20。
为了获得可接受的性能,不要求存在组分(iii),尤其在一起聚合组分(i)和(ii)的情况下。因此,在本发明的一个方面中,组分(ii)的用量为0%。当没有一起聚合组分(i)和(ii)和/或在聚合物中存在淀粉(d)时,组分(iii)的用量优选为(A)总重量的2至30%,更优选3至10wt%。
合适的(iii)组增塑剂的实例是选自甘油,聚乙二醇(PEG),山梨醇及其混合物中的那些。优选使用增塑剂,因为它们的存在增加淀粉的可变形性。
在水基涂料组合物中还优选存在含任选地以与松香的混合物形式的C16-C18链烯基烯酮二聚体的组合物,因为它增加涂层的疏水性并减少与水的相互作用。这些表面施胶剂足够稳定地在这类配方中使用。该组合物典型地由任选地以与松香的混合物形式的C16-C18链烯基烯酮二聚体和淀粉组成。在组合物(iv)中C16-C18链烯基烯酮二聚体的用量典型地为6至20%,优选为组合物(iv)总重量的12至18wt%。在组合物(iv)中松香的用量典型地为组合物(iv)总重量的15至30wt%。当以与松香的混合物形式提供C16-C18链烯基烯酮二聚体时,C16-C18链烯基烯酮二聚体:松香之比优选为8:2至2:8,更优选1:1。组合物(iv)的用量优选为(A)总重量的0至15wt%,更优选5至12wt%。
也可在水基涂料组合物中包括有胶凝剂(v),以调节流变学性能,作为水溶性化合物改进成膜,和/或桥连到淀粉分子上并降低脆度。胶凝剂典型地或者是蛋白质或者是藻酸盐。(v)组的胶凝剂的合适实例是选自玉米,玉米蛋白,乳清,酪蛋白,大豆蛋白,羧甲基纤维素和麸质中的那些。优选地,胶凝剂(iv)是麸质。优选地,(v)的用量为(A)总重量的5至20wt%,更优选10至18wt%。
水基阻挡涂料组合物可任选地包含填料(B)。当水基阻挡涂料组合物用作物体上的预涂层时,典型地存在填料。当水基阻挡涂料组合物用作面涂层时,典型地不存在(B)。填料(B)优选是滑石或高岭土,或其混合物,因为它们作为高度板状颜料产生曲折路径以供湿气,油,油脂和氧气透过。当存在(B)时,(A):(B)之比优选为2:5至1:1。
本文还提供阻挡涂布物体,优选纸张或纸板的方法,该方法包括施加本文定义的水基涂料组合物到所述物体的至少一部分表面上。视需要,在施加本发明的水基涂料组合物到表面上之前,待涂布的表面可以用常规涂料组合物预涂布。
在一个实例中,所述方法包括施加第一水基涂料组合物到物体的至少一部分表面上,获得预涂布的物体,其中所述第一水基涂料组合物包括(B),然后施加权利要求1-15任何一项中要求保护的第二水基组合物到预涂布的物体的至少预涂布的表面上,获得面涂布的物体,其中所述第二水基涂料组合物不含(B)。第一水基涂料组合物优选包含0wt%(iv)和第二水基涂料组合物优选包含大于0wt%的(iv)。
在另一实例中,所述方法包括施加第一水基预涂布组合物到物体的至少一部分表面上,获得预涂布的物体,其中所述第一水基预涂布组合物包含在(d)0至40wt%分子量Mn为500至10,000的降解淀粉存在下,通过自由基(共)聚合含下述组分的烯键式不饱和单体共混物可获得的水性聚合物组合物:
(a)0至70wt%至少一种任选取代的苯乙烯,
(b)最多100wt%至少一种(甲基)丙烯酸C1-C4-烷酯,
(c)0至10wt%其他烯键式不饱和可共聚单体,
其中(a)+(b)+(c)+(d)之和为100%;
和(B),
然后施加本文定义的水基组合物到预涂布的物体的至少预涂布的表面上,以获得面涂布的物体,其中所述水基涂料组合物不含(B)。
在这一实例中,该方法可进一步包括在施加本文定义的水基组合物到物体的进一步预涂布的表面上之前,施加第二水基预涂布组合物到该物体的至少一部分该表面上,获得进一步预涂布的物体,所述第二水基预涂布组合物包含在(d)0至40wt%分子量Mn为500至10,000的降解淀粉存在下,可通过自由基(共)聚合含下述组分的烯键式不饱和单体共混物获得的水性聚合物组合物:
(a)0至70wt%至少一种任选取代的苯乙烯,
(b)最多100wt%至少一种(甲基)丙烯酸C1-C4-烷酯,
(c)0至10wt%其他烯键式不饱和可共聚单体,
其中(a)+(b)+(c)+(d)之和为100%;
(A)总重量的0至30wt%的增塑剂;
(A)总重量的0至20wt%的胶凝剂。
本文还提供用一层或多层本文定义的水基涂料组合物层涂布的物体。
本文讨论的物体优选是纸张或纸板,尤其食品包装。
特别地本文提供本文定义的水基阻挡涂料组合物在纸张或纸板上形成油脂阻挡层的用途。
实施例
制备例
在下述实施例中解释聚合物基础组分,例如组分(i),或组分(i)+(ii)的混合物的制备。然后以所示用量共混在表1中所示的其余组分与这些聚合物基础组分(base)。
聚合物基础组分实施例1
在搅拌下,在具有冷却/加热夹套的1L玻璃反应器内,在氮气气氛下,在232.12g软化水中分散80.17g氧化降解的土豆淀粉(Perfectamyl A 4692)。通过加热混合物到95℃并在95℃下蒸煮60分钟,使淀粉溶解。在淀粉溶解完全之后,在该反应器内添加在小量水中溶解的0.02g七水合硫酸亚铁(II)水溶液。在15分钟之后,添加3.83g 30%浓度的过氧化氢。在120分钟之后,淀粉降解完全。然后开始化学品进料。在250分钟期间进料151.45g丙烯酸正丁酯和81.55g苯乙烯。在255分钟期间使40.75g 8%过氧化氢溶液与该单体原料同时进料。在进料期间,在95℃下保持反应器温度,和在后聚合之后保持15分钟。然后冷却混合物到60℃,并逐滴添加0.63g 70%浓度的氢过氧化叔丁基溶液到反应器内。在60℃下保持温度另外60分钟。之后,进行冷却到40℃,并添加0.5g乙二胺四乙酸钠盐(EDTA-Na)溶液,接着用50%浓度的氢氧化钠溶液调节pH到6,并冷却到室温。使用100μm滤布,进行过滤。获得固含量为50%和Tg 0℃的微细分的分散体。
聚合物基础组分实施例2
在具有冷却/加热夹套的1L玻璃反应器内称取613.73g水和108.31g聚乙烯醇。加热夹套到95℃。在反应器内保持氮气气氛并在反应当中继续搅拌。在夹套达到其目标温度之后,开始在反应器内的化学品进料。添加0.0084g硫酸铁。在250分钟内,使由54.2g苯乙烯和54.2g丙烯酸正丁酯组成的单体原料与0.43g十六烯基琥珀酸酐和18.94g 8%浓度的过氧化氢一起进料。在进料期间,反应器内温度保持在95℃下,并且在进料终止之后保持15分钟。然后在15分钟期间添加42.4g 70%浓度的氢过氧化叔丁基溶液到反应器内。在95℃下保持该温度另外60分钟。之后进行冷却到室温,并用50%浓度的氢氧化钠溶液调节pH到6.2。使用100μm滤布进行过滤。获得固含量为24.5%和Tg 23℃的微细分的分散体。
实施例1
表1示出了当皱褶和折叠时,针对龟裂测试的一组阻挡涂料配方。各组分的用量以组合物总重量的wt%给出。
表1.所测试的阻挡涂料配方
Ref | 1 | 2 | 3 | 4 | 5 | 6 | |
聚合物基础组分1(淀粉)Tg 23℃ | 98 | 80.6 | 80.6 | 80.6 | 80.6 | 80.6 | |
聚合物基础组分2(PVA)Tg 23℃ | 100 | ||||||
AKD/松香50:50组合物 | 8.1 | 8.1 | 8.1 | ||||
AKD/松香25:75组合物 | 8.1 | ||||||
AKD/松香75:25组合物 | 8.1 | ||||||
甘油 | 2 | 3.2 | 3.2 | 3.2 | |||
聚乙二醇300 | 3.2 | ||||||
聚乙二醇4000 | 3.2 | ||||||
PVA Mw 47000 | 8.1 | 8.1 | 8.1 | 8.1 | 8.1 |
在130g/m2衬板上进行所有涂布试验。使用光滑棒,刮涂涂布样品,并使用IR干燥器干燥。使用Cyklos GBM 450皱褶单元,进行皱褶试验。在图1中示出了实施例1的每一组合物的皱褶试验图像。通常从反面拍摄样品,并且在起皱线内观察任何渗透的染料。
对于阻挡试验来说,所使用的基底是基重为130g/m2的衬板。使用Er ichsen片材涂布机,在衬里的光滑侧(2涂层重量)上进行涂布,并用带凹槽的棒计量。在实验室烘箱内在105℃下干燥充足的时间。配方2,3,和4的水蒸气和油脂阻挡性能如表2中所示。
■阻挡性能:
■氧气(ASTM D3985;23℃/50%相对湿度&80%相对湿度)
■水蒸气(ASTM E-96,D3985&F1927;23℃/50%相对湿度)
■水(ISO 535,EN 20535&TAPPI T 441;Cobb 300s)
■油脂和油
■KIT试验,3次平行
■在40℃下的橄榄油(ISO 16235-2&TAPPI 507cm-99)
表2.配方2,3,和4的水蒸气和油脂阻挡性能
实施例2.具有不同的预涂层和面涂层的双重涂布的样品
表3和4示出了第二组测试的涂料配方,使用针对当皱褶和折叠时测试的单独的预涂层和面涂层的双重涂层。各组分的用量以组合物总重量的wt%给出。
表3.预涂布配方
表4.面涂层配方
T1 | T2 | T3 | |
苯乙烯丙烯酸酯(淀粉)Tg 23 | 76 | 54.5 | |
苯乙烯丙烯酸酯(淀粉)Tg 10 | 78.2 | ||
完全水解的PVA Mw 47000 | 9.1 | 10 | |
PEG 300 | 3.6 | 4 | |
AKD组合物,阴离子 | 9.1 | 10 | 9.1 |
甘油 | 22.7 | ||
麸质 | 13.6 |
在130g/m2衬板上进行所有涂布试验。使用光滑棒,刮涂涂布样品,并使用红外干燥器干燥。使用Cyklos GBM 450皱褶单元,进行皱褶试验。在图2中示出了具有实施例2的所指涂层的双层涂层样品的皱褶试验图像。
实施例3.具有不同预涂层的三重涂布的样品
表5至7示出了第三组测试的涂料配方,使用当皱褶和折叠时针对龟裂测试的单独的预涂层和面涂层的三层涂层,以组合物总重量wt%形式给出了各组分的用量。
表5.预涂层配方
表6.中间涂层配方
表7.面涂层配方
G10 | |
聚合物基础组分1(淀粉)Tg 23℃ | 50 |
甘油 | 30 |
麸质 | 18 |
PVA | 2 |
AKD组合物,阴离子 | 10 |
在130g/m2衬板上进行所有涂布试验。使用光滑棒,刮涂涂布样品,并使用红外干燥器干燥。使用Cyklos GBM 450皱褶单元,进行皱褶试验。在图3中示出了具有实施例3的所指涂层的三次涂布样品的皱褶试验图像。在这一试验中,从着色的顶部侧拍摄照片。
对于本领域技术人员来说,显而易见的是,由于技术进步,可按照各种方式实施本发明的概念。本发明及其实施方案并不受限于以上描述的实施例,而是可在权利要求的范围内变化。
Claims (31)
1.一种阻挡涂布物体的方法,该方法包括通过如下来将水基涂料组合物施加到所述物体的至少一部分表面上,
将第一水基涂料组合物施加到该物体的至少一部分表面上,获得预涂布的物体,其中所述第一水基涂料组合物包含(A)和(B),然后将第二水基涂料组合物施加到该预涂布的物体的至少预涂布的表面上,获得面涂布的物体,其中所述第二水基涂料组合物包含(A)但不包含(B),
其中,所述第一水基涂料组合物包含:
(A):
(i)(A)的总重量40至95wt%的水性聚合物组合物,该水性聚合物组合物通过在(d)0至40wt%分子量Mn为500至10,000的降解淀粉存在下,自由基共聚含下述组分的烯键式不饱和单体共混物而获得:
(a)0至70wt%至少一种任选取代的苯乙烯,
(b)最多100wt%至少一种(甲基)丙烯酸Cl-C4-烷酯,
(c)0至10wt%其他烯键式不饱和可共聚单体,
其中(a)+(b)+(c)+(d)之和为100%;
(ii)(A)的总重量2至55wt%的任选地与(i)的组分一起聚合的聚乙烯醇PVA;
(iii)(A)的总重量的2至30wt%的增塑剂;
(iv)(A)的总重量5至30wt%的组合物,所述组合物含任选地以与松香的混合物形式的C16-C18链烯基烯酮二聚体,其中C16-C18链烯基烯酮二聚体:松香之比为100:0至2:8;
(v)(A)的总重量的5至20wt%的胶凝剂;和
(B):填料,其中(A):(B)之比为2:5至1:1。
2.权利要求1的方法,其中(i)+(ii)+(iii)+(iv)+(v)之和为100%。
3.权利要求1或2的方法,其中PVA(ii)选自由分子量等于或小于50000的完全或部分水解的等级组成的组。
4.权利要求1或2的方法,其中增塑剂(iii)选自甘油、聚乙二醇(PEG)、山梨醇及其混合物。
5.权利要求1或2的方法,其中胶凝剂(v)是蛋白质或藻酸盐。
6.权利要求1或2的方法,其中胶凝剂(v)选自玉米、玉米蛋白、乳清、酪蛋白、大豆蛋白、羧甲基纤维素和麸质。
7.权利要求6的方法,其中胶凝剂(v)是麸质。
8.权利要求1或2的方法,其中填料(B)是滑石或高岭土。
9.权利要求1或2的方法,其中在(d)0至40wt%分子量Mn为500至10,000的降解淀粉和(e)接枝-连接的水溶性氧化还原体系作为自由基乳液共聚用自由基引发剂存在下,通过自由基共聚含下述组分的烯键式不饱和单体共混物,获得水性聚合物组合物(i):
(a)0至70wt%至少一种任选取代的苯乙烯,
(b)最多100wt%至少一种(甲基)丙烯酸Cl-C4-烷酯,和
(c)0至10wt%其他烯键式不饱和可共聚单体,
其中(a)+(b)+(c)+(d)之和为100%。
10.权利要求1或2的方法,其中通过一起聚合PVA(ii)和(i)中的所述组分,获得(i)和(ii)的混合物。
11.权利要求10的方法,其中在(d)0至40wt%分子量Mn为500至10,000的降解淀粉和(e)接枝-连接的水溶性氧化还原体系作为自由基乳液共聚用自由基引发剂存在下,通过自由基乳液共聚含下述组分的烯键式不饱和单体,获得(i)和(ii)的混合物:
(a)0至60wt%至少一种任选取代的苯乙烯,
(b)最多100wt%至少一种(甲基)丙烯酸Cl-C4-烷酯,和(c)0至10wt%其他烯键式不饱和可共聚单体,和
(ii)。
12.权利要求11的方法,其中降解淀粉(d)的用量为0wt%。
13.权利要求11-12任何一项的方法,其中(i):(ii)之比为45:55至60:40。
14.权利要求11-12任何一项的方法,其中(i)的用量为(A)的总重量的45至60wt%,和(ii)的用量为(A)的总重量的40至55wt%。
15.权利要求1的方法,其中通过共混(i)和(ii),获得(i)和(ii)的混合物。
16.权利要求15的方法,其中(i)的用量为(A)的总重量的50至95wt%,和(ii)的用量为(A)的总重量的2至20wt%。
17.权利要求15或16的方法,其中降解淀粉(d)的用量为20至40wt%。
18.权利要求17的方法,其中组分(iv)的用量为(A)的总重量的5至15wt%。
19.权利要求1或2的方法,其中(iv)中的链烯基烯酮二聚体:松香(iv)之比为8:2至2:8。
20.权利要求1或2的方法,其中(iv)中的链烯基烯酮二聚体:松香(iv)之比为100:0至25:75。
21.权利要求1或2的方法,其中聚合物的玻璃化转变温度(Tg)为-40℃至50℃。
22.权利要求21的方法,其中聚合物的玻璃化转变温度(Tg)为-10℃至30℃。
23.权利要求1或2的方法,其中(a)的用量为20至60wt%。
24.权利要求23的方法,其中(a)的用量30至60wt%。
25.权利要求1或2的方法,其中单体组分(b)是丙烯酸正丁酯。
26.权利要求1或2的方法,其中所述物体是纸张或纸板。
27.权利要求1或2的方法,其中所述物体是食品包装。
28.涂布有两层或多层的水基涂料组合物的物体,使得将权利要求1-27任何一项中的第一水基涂料组合物施加到该物体的至少一部分表面上,获得预涂布的物体,其中所述第一水基涂料组合物包含(A)和(B),然后将权利要求1-27任何一项中的第二水基涂料组合物施加到预涂布的物体的至少预涂布的表面上,获得面涂布的物体,其中所述第二水基涂料组合物包含(A)但不包含(B)。
29.权利要求28的物体,其中所述物体是纸张或纸板。
30.权利要求28的物体,其中所述物体是食品包装。
31.水基涂料组合物用于在纸张或纸板上形成油脂阻挡物的用途,包括将权利要求1-27任何一项中的第一水基涂料组合物施加到该物体的至少一部分表面上,获得预涂布的物体,其中所述第一水基涂料组合物包含(A)和(B),然后将权利要求1-27任何一项中的第二水基涂料组合物施加到预涂布的物体的至少预涂布的表面上,获得面涂布的物体,其中所述第二水基涂料组合物包含(A)但不包含(B)。
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