CN118234698A - 具有一定孔隙率的聚乙烯醇缩醛类作为陶瓷坯片中的粘结剂的用途 - Google Patents

具有一定孔隙率的聚乙烯醇缩醛类作为陶瓷坯片中的粘结剂的用途 Download PDF

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CN118234698A
CN118234698A CN202280075227.5A CN202280075227A CN118234698A CN 118234698 A CN118234698 A CN 118234698A CN 202280075227 A CN202280075227 A CN 202280075227A CN 118234698 A CN118234698 A CN 118234698A
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polyvinyl acetal
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G·贝克
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Kuraray Europe GmbH
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Abstract

本发明涉及具有一定孔隙率的聚乙烯醇缩醛的粉末在陶瓷坯片中作为粘结剂的用途。该聚乙烯醇缩醛的通过根据说明书的压汞法测量的总孔容积为1.5～5.0ml/g并且所述聚乙烯醇缩醛具有直径的值集中在10～100μm之间的主要孔群。制造了一种悬浮液组合物，其包含一种或多种无机颜料、一种或多种有机溶剂、一种或多种粘结剂、一种或多种增塑剂和一种或多种分散剂，其中所述粘结剂是聚乙烯醇缩醛。一种用于制备陶瓷坯片或陶瓷模塑体的方法，其包含压实聚乙烯醇缩醛和制备包含生产的压实体的悬浮液组合物的步骤。

Description

具有一定孔隙率的聚乙烯醇缩醛类作为陶瓷坯片中的粘结剂 的用途
技术领域
本发明涉及具有一定孔隙率的聚乙烯醇缩醛类作为陶瓷坯片中的粘结剂的用途和使用这种聚乙烯醇缩醛类生产压实体的方法。
背景技术
像用于电子工业的陶瓷电容器的陶瓷材料通常通过烧结包含陶瓷材料的所谓坯片即膜状薄模塑体来生产。为了生产这些坯片，生产金属氧化物、增塑剂、分散剂和粘结剂在有机溶剂中的悬浮液。随后将悬浮液借助于合适的工艺(即刮刀工艺)以所需厚度施加到载体膜上，并且除去溶剂。由此获得的坯片必然没有裂纹，显示平滑的表面，并且仍然具有一定的弹性。
如聚乙烯醇丁醛(PVB)的聚乙烯醇缩醛类经常用作生产陶瓷坯片的粘结剂。为此，DE4 003 198A1描述了用于陶瓷坯膜的流延浆料(casting slip)的生产，其中使用了具有0～2重量％的残余聚乙酸乙烯酯含量的PVB作为粘结剂。
近年来，多层陶瓷电容器(MLCC)在电子工业中变得越来越重要。MLCC由许多并联堆叠在一起并通过端子表面接触的独立电容器构成。由于电子组件的小型化推进，粉末颗粒的尺寸可以小到10nm。因此，生产要求其中使用的陶瓷片的精度增加。
用于制备悬浮液的PVB树脂通常以细粉的形式提供。然而，出于健康和/或安全考虑，这种粉末不能在所有工业环境中使用。因此，PVB粉末在用于某些应用之前被压实以避免这些缺点。
此外，为了满足电子工业的严格要求，PVB树脂必须显示出非常高的纯度。然而，以经济可行的方式将这种聚合物产品洗涤至高纯度并不容易。
因此，本发明的一个目的是提供用于陶瓷坯片的同时具有改善的可洗涤性和改善的可压实性的粘结剂。另一个目的是提供粘结剂，其导致改善的溶解速率、改善的粘附性、改善的处理、改善的断裂伸长率、改善的分散效果、改善的环境、健康和安全影响和/或在陶瓷坯片的生产和使用中具有更好的经济性。
本发明人现在令人惊讶地发现使用具有高的总孔容积的PVB的同时，小的平均孔径的孔解决了这些和其他目标。据信高的总孔容积导致良好的可洗涤性，因为洗涤液可以容易地渗透粉末。同时，总孔容积主要由孔尺寸相对小的孔贡献，这显然导致了改善的可压实性，即，他们可被压缩成具有更低的总孔容积和更高的密度的压实体，其密度通过它的体积或振实密度表示。
因此，本发明的第一方面涉及聚乙烯醇缩醛作为生产陶瓷坯片或陶瓷模塑体的粘结剂的用途，其中聚乙烯醇缩醛的通过根据下述条件的压汞法测量的总孔容积为1.5～5.0ml/g并且所述聚乙烯醇缩醛具有直径的值集中在10～100μm之间的主要孔群。
图1示出根据本发明的两种聚乙烯醇缩醛粉末样品和由所述聚乙烯醇缩醛粉末制备的两种压实体以及目前在电子工业中使用的现有技术的商业压实体的孔隙率法测量的结果。
术语“主要孔群的直径的值集中在……之间”应指使用如下所述的孔隙率法测量绘制的累积孔容积相对于孔径的曲线在给定值之间具有拐点。
优选地，直径的值集中在15～50μm之间，更优选在20～40μm之间。此外，优选直径的值集中在30～80μm之间，更优选在40～60μm之间。
优选地，总孔容积为1.75～4.5ml/g，更优选为2.0～4.0ml/g，甚至更优选为2.0～3.0ml/g并且最优选为2.5～3.0ml/g。
优选地，聚乙烯醇缩醛的通过根据下述压汞法测量的平均孔径等于或小于2.0μm。更优选地，聚乙烯醇缩醛的平均孔径为1.0～1.5μm。
优选地，聚乙烯醇缩醛的通过根据DIN ISO 16014 1:2019-05的凝胶渗透色谱法测量的分子量等于或大于20,000g/mol。
根据DIN ISO 16014 1:2019-05通过凝胶渗透色谱法确定分子量。优选地，分子量为等于或大于40,000g/mol，更优选为50,000g/mol。此外。优选分子量为等于或小于200,000g/mol，更优选为等于或小于175,000g/mol，最优选为等于或小于150,000g/mol并且特别为等于或小于100,000g/mol。
优选地，聚乙烯醇缩醛的缩醛基团单独具有1～7个碳原子，即它们来源于与具有1～7个碳原子的醛的缩合反应。更优选地，它们来源于下述组成的列表中：甲醛，乙醛，正丙醛(丙醛)，正丁醛(丁醛)，异丁醛(2-甲基-1-丙醛、异丁醛)，正戊醛(戊醛)，异戊醛(3-甲基-1-丁醛)，仲戊醛(2-甲基-1-丁醛)，叔戊醛(2,2-二甲基-1-丙醛)，正己醛(己醛)，异己醛(2-甲基-1-戊醛，3-甲基-1-戊醛，4-甲基-1-戊醛)，2,2-二甲基-1-丁醛，2,3-二甲基-1-丁醛，3,3-二甲基-1-丁醛，2-乙基-1-丁醛，正庚醛，2-甲基-1-己醛，3-甲基-1-己醛，4-甲基-1-己醛，5-甲基-1-己醛，2,2-二甲基-1-戊醛，3,3-二甲基-1-戊醛，4,4-二甲基-1-戊醛，2,3-二甲基-1-戊醛，2,4-二甲基-1-戊醛，3,4-二甲基-1-戊醛，2-乙基-1-戊醛，2-乙基-2-甲基-1-丁醛，2-乙基-3-甲基-1-丁醛，3-乙基-2-甲基-1-丁醛，环己醛和苯甲醛。更优选地，它们来源于与异丁醛、乙醛和/或正丁醛的缩合反应。最优选地，聚乙烯醇缩醛是聚乙烯醇缩丁醛或来源于与正丁醛和乙醛的缩合的混合的聚乙烯醇缩醛。
虽然对本发明的本实施方案中使用的聚乙烯醇缩醛类的生产方法没有特别限制，但它们可以通过在酸性条件下将醛添加到聚乙烯醇溶液并且进行缩醛化反应的方法来生产。
优选地，本发明中使用的聚乙烯醇缩醛类的缩醛化程度为50mol％以上且小于90mol％，更优选缩醛化程度的下限为大于60mol％，甚至更优选为大于70mol％，并且最优选为大于80mol％。此外，缩醛化程度的上限更优选为90mol％以下，并且最优选为85mol％以下。
优选地，本发明的聚乙烯醇缩醛类中的乙烯醇单元基于构成树脂的总单体单元的百分比为10～25mol％，更优选为15～20mol％。
聚乙烯醇缩醛的乙烯醇含量和乙酸乙烯酯含量根据DIN ISO 3681(乙酸酯含量)和DIN ISO 53240(PVA含量)确定。
在第二方面，本发明涉及包含一种或多种无机颜料、一种或多种有机溶剂、一种或多种粘结剂、一种或多种增塑剂和一种或多种分散剂的悬浮液组合物，其中粘结剂是上述的聚乙烯醇缩醛。
优选地，缩醛基团具有2～7个碳原子并且来源于与上述相同的醛。最优选地，缩醛基团来源于正丁醛或来源于正丁醛和乙醛的混合物。
无机颜料可以选自顺电或铁电原料的精细研磨的颗粒，并且包括二氧化钛(金红石)，优选通过锌、锆、铌、镁、钽、钴和/或锶的添加剂以及选自MgNb2O6、ZnNb2O6、MgTa2O6、ZnTa2O6、(ZnMg)TiO3、(ZrSn)TiO4、BaTiO3和Ba2Ti9O20的化合物改性。无机颜料的平均粒径优选为约0.01～1μm。
有机溶剂可以选自芳香族化合物，如甲苯和二甲苯；和醇化合物，如乙醇、异丙醇和丁醇，更优选其混合物。最优选地，有机溶剂是乙醇和甲苯的混合物。
适合的分散剂包括鱼油、磷酸酯和在侧链上包含聚氧亚烷基的功能聚合物，如从NOF America Cooperation商购可得的MALIALIMTM系列。
除了根据本发明的粘结剂，悬浮液还可以包含尤其选自其它粘结剂、如聚乙二醇或邻苯二甲酸酯的增塑剂、和/或消泡剂的其它组分，所述其它粘结剂如纤维素树脂、丙烯酸类树脂、乙酸乙烯酯树脂、聚乙烯醇树脂。
悬浮液组合物的生产方法没有特别限制。可以使用各种分散方法，例如，使用介质型研磨机如珠磨机、球磨机、磨碎机、油漆摇拌器和砂磨机的方法，；捏合粉状陶瓷、分散介质、分散剂、粘结剂、增塑剂等的方法；和使用三辊研磨机的方法。使用三辊研磨机，该方法包括将粉状无机颜料和分散剂、粘结剂、增塑剂等一起分散在有机溶剂(混合物)中。混合物通过彼此独立滚动并且彼此相邻且其间有小间隙的第一辊和第二辊之间的小间隙，以被压缩和捏合，随后，混合物通过第二辊和第三辊之间，第三辊滚动并与第二辊相邻，其间的间隙小于第一辊和第二辊之间的间隙，以便被进一步压缩和捏合。
优选地，将粉状陶瓷、分散剂和溶剂(混合物)预混合并分散，使得分散剂吸附在粉状陶瓷上。在第二步骤中，向这样形成的混合物中添加粘结剂，随后，再次进行混合和分散。
通过这些工艺生产的涂布膜的干膜厚度可为0.25～25μm，并且通常为1～15μm。
本发明人现在已经发现，压实体可以有利地由上述聚乙烯醇缩醛类制备。显示出高的总孔容积的PVB粉末同时具有小的平均孔径。高的总孔容积导致粉末更好的可洗涤性，因为更多的洗涤液，通常以软化水(demineralized water)的形式，可以渗透PVB粉末，导致PVB粉末和因此所得的压实体的优越的杂质分布。另一方面，PVB粉末中的小孔显然导致具有更高压缩水平的压实体。
因此，本发明的第三方面涉及使用上述聚乙烯醇缩醛制备压实体的方法。
优选地，压实体通过根据下述方法的压汞法测量的平均孔径为0.01～0.5μm。平均孔径的下限更优选为0.05、0.1或0.15μm。平均孔径的上限更优选为0.4μm，最优选为0.3μm。特别地，平均孔径为0.1～0.3μm。
优选地，压实体根据下述方法测量的体积密度为等于或大于0.50g/ml，更优选为等于或大于0.55g/ml，最优选为等于或大于0.60g/ml并且特别为等于或大于0.65g/ml。
优选地，压实体的中值粒径为0.5～5mm，更优选为1～3mm。使用规定数量的颗粒测量颗粒的尺寸并且通过光学检查在球形的情况下测量颗粒的直径或在非球形的情况下测量颗粒的最长横向轴(longest lateral axis)。
本文使用的术语“压实体”应指在不使用溶剂或熔化粉末的情况下经过压制干粉的压实工艺的压实的聚乙烯醇缩醛粉末。这种压实工艺也称为干法制粒，其与使用溶液或浆料的湿法制粒以及使用聚乙烯醇缩醛材料熔体的挤出工艺相反。
压实体可以通过现有技术中已知的工艺制备，即在没有任何液体溶液的帮助下形成压实体的工艺。如果要压实的成分对水分或热量敏感，这种工艺是优越的。压实用于使粉末致密化并形成压实体。该工艺通常使用段塞工具(slugging tool)或辊式压实机(rollercompactor)进行。段塞法通常会产生“段塞(slugs)”-通常直径为25mm，厚度为10-15mm。将锤式研磨机用于破碎段塞是理想的。压实的材料可以通过分级筛分进一步处理，以达到所需粒径的压实体。
优选地，将辊式压实机用于生产压实体的工艺。在这种装置中，粉末通过两个反向旋转的辊被挤压以形成压缩片。这些片是脆的，并且易于碎成薄片。薄片需要仔细处理，将其破碎以压实，然后可以将它们研磨成所需的尺寸。辊压设备提供了广泛的压力和辊类型，以获得适当的致密度。
本发明的第四方面涉及用于制备陶瓷坯片或陶瓷模塑体的方法，其包含步骤：
a.压实根据上述方法的聚乙烯醇缩醛，和
b.制备包含步骤a中生产的压实体的悬浮液组合物。
实施例
孔隙率法
根据ISO 15901-1:2016，通过压汞孔隙率法，使用孔隙率计设备AutoPore V 9600(从Micromeritics可得)测量总孔容积、中值孔径、平均孔径和体积密度。汞的接触角为130°，并且表面张力为485dynes/cm。使用10s的平衡时间和0.24psia的初始填充压力。测量的压力范围为0.24～33.063psia，其转化成孔径为752～0.00581μm。总孔容积定义为在此范围内测量的累积进入容积。中值孔径(与容积有关)定义为孔径，其中50％的孔容积小于或大于该值。平均孔径假设为完美的圆柱形孔，并且定义为“4×孔容积/孔面积”。体积密度定义为测量室的填充压力为0.24psia时的密度。在此压力下，汞仅会嵌入而不会渗透样品。
聚乙烯醇缩醛类的合成
聚乙烯醇缩丁醛(PVB 1)
将100重量份粘度为19mPas(在20℃下根据DIN 53015在8w/w％的水溶液中测量)和水解程度为98mol％的聚乙烯醇溶解在加热到90℃的1000重量份的水中。在40℃的温度下，添加65重量份的正丁醛，并且在5℃的温度下，在搅拌中，添加250重量份的20％盐酸。将混合物加热到40℃。在聚乙烯醇缩丁醛(PVB)沉淀之后，在该温度下搅拌混合物48h。冷却到室温之后分离PVB，用水洗涤至中性，并且干燥。获得具有12.7质量％(19.1mol％)的聚乙烯醇含量和2.3质量％(1.8mol％)的聚乙酸乙烯酯含量的PVB。
混合的聚乙烯醇缩醛(PVB 2)
将100重量份粘度为50mPas(在20℃下根据DIN 53015在8w/w％的水溶液中测量)和水解程度为99mol％的聚乙烯醇溶解在加热到90℃的1000重量份的水中。在40℃的温度下，添加200重量份的20％盐酸，并且在12℃的温度下，在搅拌中，先添加22重量份的乙醛再添加30重量份的正丁醛。将混合物加热到40℃。在聚乙烯醇缩丁醛(PVB)沉淀之后，在该温度下搅拌混合物48h。冷却到室温之后分离PVB，用水洗涤至中性，并且干燥。获得具有12.5质量％(18.8mol％)的聚乙烯醇含量和1.7质量％(1.3mol％)的聚乙酸乙烯酯含量的PVB。
压实工艺-PVB压实体1和2
聚乙烯醇缩丁醛粉末在两个反向旋转、水冷的辊之间，使用辊式压实机以15kN/cm的线压力在45℃的温度下牵拉(draw)。然后将得到的0.5～1.0cm的厚片破碎，随后借助造粒机进一步减小尺寸，并且最后通过分级筛分处理以获得中值粒径为1～3mm的压实体。

Claims (14)

1.聚乙烯醇缩醛作为粘结剂用于生产陶瓷坯片或陶瓷模塑体的用途，其中所述聚乙烯醇缩醛的通过根据说明书的压汞法测量的总孔容积为1.5～5.0ml/g并且所述聚乙烯醇缩醛具有直径的值集中在10～100μm之间的主要孔群。
2.根据权利要求1所述的用途，其中所述通过根据说明书的压汞法测量的总孔容积为2.0～3.5ml/g。
3.根据权利要求1或2所述的用途，其中所述通过根据说明书的压汞法测量的总孔容积为2.5～3.0ml/g。
4.根据上述权利要求中任一项所述的用途，其中所述直径的值集中在15～50μm之间。
5.根据上述权利要求中任一项所述的用途，其中所述聚乙烯醇缩醛的通过根据说明书的压汞法测量的平均孔径为等于或小于2.0μm。
6.根据上述权利要求中任一项所述的用途，其中所述聚乙烯醇缩醛的通过根据说明书的压汞法测量的平均孔径为1.1～1.5μm。
7.根据上述权利要求中任一项所述的用途，其中所述聚乙烯醇缩醛是聚乙烯醇缩丁醛或来源于正丁醛和乙醛的混合的聚乙烯醇缩醛。
8.一种悬浮液组合物，其包含一种或多种无机颜料、一种或多种有机溶剂、一种或多种粘结剂、一种或多种增塑剂和一种或多种分散剂，其中所述粘结剂是根据权利要求1至7中任一项所述的聚乙烯醇缩醛。
9.一种用于制备陶瓷坯片或陶瓷模塑体的方法，其包含步骤：
a.压实根据权利要求1至7中任一项所述的聚乙烯醇缩醛，
b.制备包含步骤a中生产的压实体的悬浮液组合物。
10.根据权利要求9所述的方法，其中所述压实体的根据说明书测量的体积密度为等于或大于0.55g/ml。
11.根据权利要求9或10所述的方法，其中所述压实体的总孔容积为0.25ml/g～0.75ml/g。
12.一种使用根据权利要求1至7中任一项所述的聚乙烯醇缩醛用于制备压实体的方法。
13.根据权利要求12所述的方法，其中所述压实体的根据说明书测量的体积密度为等于或大于0.55g/ml。
14.根据权利要求12或13所述的方法，其中所述压实体的总孔容积为0.25ml/g～0.75ml/g。
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