CN118234697A - 压实的聚乙烯醇缩醛类作为陶瓷坯片的粘结剂的用途 - Google Patents

压实的聚乙烯醇缩醛类作为陶瓷坯片的粘结剂的用途 Download PDF

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CN118234697A
CN118234697A CN202280075118.3A CN202280075118A CN118234697A CN 118234697 A CN118234697 A CN 118234697A CN 202280075118 A CN202280075118 A CN 202280075118A CN 118234697 A CN118234697 A CN 118234697A
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polyvinyl acetal
compact
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F·玛弥
M·弗兰克
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Kuraray Europe GmbH
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Abstract

公开了包含聚乙烯醇缩醛的压实体作为用于生产陶瓷坯片或陶瓷模塑体的粘结剂的用途，其中，当根据DIN ISO 16014‑l:2019‑05通过凝胶渗透色谱法测量时，聚乙烯醇缩醛具有等于或大于50,000g/mol的分子量。还公开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，其中所述粘结剂是压实体。

Description

压实的聚乙烯醇缩醛类作为陶瓷坯片的粘结剂的用途
本发明涉及聚乙烯醇缩醛类的压实粉末作为陶瓷坯片的粘结剂的用途。
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。随后将该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。由此获得的坯片必须没有裂纹，显示平滑的表面，并且仍然具有一定的弹性。
如聚乙烯醇缩丁醛(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浇注浆的生产，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。此外，在生产工艺中，陶瓷坯片的多层堆叠通常被卷绕成卷。为了避免分层，单个坯片必须在粘合和断裂伸长率方面具有优异的性能。
为了实现这些目标，优选具有高分子量即具有高聚合度的PVB，因为这种PVB导致悬浮液具有足够高的粘度。然而，与短链PVB相比，高分子量PVB具有低的溶解速率，导致制备悬浮液所需的时间整体增加。
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。根据粉末的颗粒尺寸，颗粒很容易被吸入处理材料的员工的肺部。此外，粉末形式的材料在火焰点燃后通常表现出***风险。
为了解决这些问题，已经引入颗粒形式的PVB。例如，US20080203593A1描述了用作用于陶瓷坯片的粘结剂的PVB颗粒的生产。
然而，由于挤出机使用的升高的温度和高剪切力，使用熔融挤出生产这种颗粒会导致PVB部分分解。此外，颗粒比相应的粉末溶解得慢得多。因为高分子量PVB在溶解速率方面已经较低，不鼓励在陶瓷工业中以颗粒形式使用这种PVB。
因此，本发明的一个目的是提供用于陶瓷坯片的具有改善的溶解速率的粘结剂。另一个目的是提供粘结剂，其导致改善的粘附性、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压实的PVB解决了这些和其他目标。
因此，本发明的第一方面涉及包含聚乙烯醇缩醛的压实体作为用于生产陶瓷坯片或陶瓷模塑体的粘结剂的用途，其中，当根据DIN ISO 16014-l:2019-05通过凝胶渗透色谱法测量时，聚乙烯醇缩醛具有等于或大于50,000g/mol的分子量。
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60,000g/mol，更优选为70,000g/mol。此外优选地，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。此外，优选分子量为50,000～150,000g/mol，更优选为60,000～125,000g/mol。
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。
优选地，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。
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由此进行缩醛化反应的方法来生产。聚乙烯醇缩醛类也可以商购得到，例如，从Kuraray Europe GmbH可得的聚乙烯醇缩醛类。
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％、大于70mol％。此外，缩醛化程度的上限更优选为90mol％以下、85mol％以下、80mol％以下和75。
优选地，本发明的聚乙烯醇缩醛类的乙烯醇单元基于构成树脂的总单体单元的百分比为10～50mol％，更优选为15～35mol％。
聚乙烯醇缩醛类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。
优选地，压实体具有0.5～5mm的中值粒径，更优选为2～4mm。使用规定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。
在第二方面，本发明涉及一种悬浮液组合物，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，其中所述粘结剂是包含如上所述的聚乙烯醇缩醛的压实体。
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。
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。可以使用多种分散方法，例如，使用介质型磨机的方法，如珠磨机、球磨机、磨碎机、油漆摇拌器和砂磨机；捏合粉状陶瓷、分散介质、分散剂、粘结剂、增塑剂等的方法；和使用三辊磨机的方法。使用三辊磨机，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。
通过这些方法生产的涂膜的干膜厚度可为0.25～25微米，并且通常为1～15微米。
压实体可以通过现有技术中已知的干法制粒工艺制备，即在没有任何液体溶液的帮助下形成颗粒的工艺。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。将锤式磨机用于破碎段塞以产生最终压实体是理想的。
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。这些片很脆，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，以获得适当的致密化。
实施例
实施例1-PVB压实体1
聚乙烯醇缩丁醛粉末(B 75H，具有100,000g/mol+/-10,000g/mol的分子量)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℃的温度下牵引(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，以获得中值粒径为1～3mm的压实体。
PVB粉末vs.PVB压实体的溶解行为
将10gPVB粉末或压实体分别与90g溶剂混合物(乙醇和甲苯的1:1混合物)混合。对于溶解过程，使用旋转和倾斜混合器(供应商：IKA，型号：Kipp-/Rollenmischer,digital,6)。在规定时间段(0h、3h、6h、18h和24h)后，停止混合器，并且取出1g上清液并且借助烘箱蒸发溶剂来确定固体含量。使用数字精密天平进行分析。
溶解速率以[％]计
结果：
压实体1在3小时后已经完全溶解。在另一方面，相应的粉末材料需要大于6小时的溶解时间才能完全溶解。
PVB粉末和PVB压实体的溶液中的颗粒计数
除了使用从Kuraray Europe GmbH商购得到的B 30HH，具有35,000g/mol+/-10,000g/mol的分子量的PVB以外，如上述压实体1所述制备压实体2。
使用倾斜/旋转混合器将2gPVB粉末或压实体分别溶解在98g溶剂混合物(乙醇和甲苯的1:1混合物)中。在24小时后，采集50mL样品并且使用Soliton GmbH的AccusizerTM780通过激光聚焦的单颗粒测量进行分析。仅计数尺寸在2-500μm范围内的颗粒。
结果：
尺寸为2～500μm的残余颗粒可以是陶瓷坯片生产中的主要问题并且因此必需最小化其存在于粘结剂溶液中的量。虽然关于压实体1的压实工艺仅示出颗粒尺寸的适度增加，但是压实具有低分子量的PVB材料(压实体2)惊讶地导致从粉末至压实体的颗粒计数的高得多的增加。

Claims (8)

1.包含聚乙烯醇缩醛的压实体作为用于生产陶瓷坯片或陶瓷模塑体的粘结剂的用途，其中，当根据DINISO 16014-l:2019-05通过凝胶渗透色谱法测量时，所述聚乙烯醇缩醛具有等于或大于50,000g/mol的分子量。
2.根据权利要求1所述的用途，其中所述聚乙烯醇缩醛是聚乙烯醇缩丁醛。
3.根据权利要求1或2所述的用途，其中，当根据DIN ISO 160141:2019-05通过凝胶渗透色谱法测量时，所述聚乙烯醇缩醛具有等于或大于50,000g/mol且等于或小于150,000g/mol的分子量。
4.根据权利要求1至3中任一项所述的用途，其中所述压实体具有1～5mm的中值粒径。
5.一种悬浮液组合物，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4中任一项所述的压实体。
6.一种压实体，其包含当根据DINISO 16014 1:2019-05通过凝胶渗透色谱法测量时具有等于或大于50,000g/mol的分子量的聚乙烯醇缩醛。
7.根据权利要求6所述的压实体，其具有1～5mm的中值粒径。
8.一种制备根据权利要求7所述的压实体的方法，其包含使用辊磨机压实聚乙烯醇缩醛粉末的步骤。
CN202280075118.3A 2021-11-18 2022-11-17 压实的聚乙烯醇缩醛类作为陶瓷坯片的粘结剂的用途 Pending CN118234697A (zh)

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