CN118234763A - 具有改善的残留颗粒尺寸分布的聚乙烯醇缩醛类 - Google Patents

具有改善的残留颗粒尺寸分布的聚乙烯醇缩醛类 Download PDF

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CN118234763A
CN118234763A CN202280075140.8A CN202280075140A CN118234763A CN 118234763 A CN118234763 A CN 118234763A CN 202280075140 A CN202280075140 A CN 202280075140A CN 118234763 A CN118234763 A CN 118234763A
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F·玛弥
C·简森
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Abstract

本发明涉及具有改善的残留颗粒尺寸的聚乙烯醇缩醛类，生产这种聚乙烯醇缩醛类的方法和将它们用作生产陶瓷坯片的粘结剂的用途。

Description

具有改善的残留颗粒尺寸分布的聚乙烯醇缩醛类
本发明涉及具有改善的残留颗粒尺寸分布的聚乙烯醇缩醛类，生产这种聚乙烯醇缩醛类的方法和将它们用作生产用于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用于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％的残留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，例如金属氧化物颗粒的粉末颗粒的尺寸可在纳米范围内。残留颗粒，即未溶解于用于制成生产坯片所需的悬浮液的溶剂(混合物)的颗粒，其与金属氧化物颗粒的尺寸相同，因为它们难以选择性地除去，所以是主要关注点，并且因此会导致在坯片烧结之后的陶瓷层中的缺陷。
此外，低纳米范围内的残留颗粒造成了另外的问题，它们倾向于堵塞用于过滤粘结剂溶液的网版，因此由于需要更经常地更换或清洁网版，使得该工艺经济性降低。另外，即使网版的部分堵塞也会导致过滤工艺中的高背压。此外，由于溶液中聚合物颗粒溶胀的软行为，聚合物颗粒通常难以过滤。
因此，本发明的一个目的是提供具有关于残留颗粒的改善的性质的用作用于陶瓷坯片的粘结剂的聚乙烯醇缩醛以及生产这种聚乙烯醇缩醛的方法。进一步的目的是提供这种粘结剂，其导致改善的溶解速率、粘附性、改善的处理、改善的断裂伸长率、改善的拉伸强度、改善的分散效果、改善的环境、健康和安全影响和/或陶瓷坯片的生产和使用中具有更好的经济性。
现在本发明人已经令人惊讶地发现2～5μm范围内的颗粒的一个主要来源是包含在最终的聚乙烯醇缩醛粉末中的痕量的氯化钠。因为氯化钠不溶于用于制备粘结剂溶液和生产坯片中使用的悬浮液的有机溶剂，其留作残留颗粒。聚乙烯醇缩醛通常通过聚乙烯醇和醛在酸的存在下转化为相应的缩醛的缩醛化过程来生产。在这方面经常使用盐酸。在将聚乙烯醇缩醛沉淀之后，用水清洗粗产物以除去酸至中性并且随后干燥清洗的产物。
工业园区中使用的普通水可能包含相当大量的氯离子。例如，2020年德国Hoechst工业园区的自来水中的氯化物含量的上限为250mg/l。结果，即使用水彻底清洗聚乙烯醇缩醛以除去残留的盐酸，也会导致最终产物具有相当高的氯化物含量，因为清洗的水本身包含氯离子。然后，这种氯化物含量会导致残留颗粒的含量更高，尤其在临界低纳米范围内。
因此，本发明的第一方面涉及生产聚乙烯醇缩醛粉末的方法，其包含以下步骤
a.在酸的存在下将聚乙烯醇与醛反应以制备聚乙烯醇缩醛，
b.将步骤a中获得的聚乙烯醇缩醛沉淀，
c.用包含水的清洗液清洗步骤b中获得的沉淀物，和
d.将步骤c的经清洗的沉淀物干燥，
其中步骤c中的清洗液包含等于或小于100mg/l的氯离子。
根据ASTM D512-04通过硝酸银滴定法(测试方法B)测量清洗液中的氯化物含量。
优选地，步骤c中的清洗液包含等于或小于80mg/l，更优选为小于75，甚至更优选为小于50，最优选为小于30并且特别为小于20mg/l的氯离子。此外优选地，清洗液包含0.1～10mg/l之间的氯离子。
清洗液可以是水和例如像甲醇、乙醇或异丙醇的醇的水溶性溶剂的混合物。优选地，清洗液基本上由水组成。
可以使用的酸是已知用于聚乙烯醇缩醛类的制造过程的那些。例如盐酸、硫酸、硝酸或这些酸的混合物。优选地，酸是盐酸。
可以通过本领域已知的任何方法减少清洗液的氯化物含量。除去氯化物的机理主要包括化学沉淀、吸附、氧化和膜分离。在化学沉淀中，通过形成CuCl、AgCl、BiOCl和弗里德尔盐(Friedel's salt)除去氯化物。用于除去氯化物的吸附剂主要包括离子交换剂、双金属氧化物和碳系电极。用于除去氯化物的氧化包含基于臭氧、电化学和基于硫酸根的氧化。用于除去氯化物的膜分离包括扩散透析、纳滤、反渗透和电渗析。优选地，通过化学沉淀、反渗透、吸附和/或氧化减少清洗液中的氯化物的量。
使用清洗液，特别是具有低的氯化物含量的水导致最终的聚乙烯醇缩醛粉末具有低的氯化物含量。因此，在本发明的一个实施方案中，聚乙烯醇缩醛粉末包含等于或小于25ppm的氯化物，更优选为小于20ppm，甚至更优选为小于15ppm，最优选为小于10ppm并且特别为小于5ppm的氯化物。
优选地，当根据DIN ISO 16014 1:2019-05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20,000g/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40,000g/mol，更优选为50,000g/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。
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生产聚乙烯醇缩醛的方法没有特别限制，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因此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％，最优选为大于80mol％。此外，缩醛化程度的上限更优选为90mol％以下，最优选为85mol％以下。
优选地，本发明的聚乙烯醇缩醛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，如甲醇、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0.25～25μm，并且通常为1～15μm。
本发明的第三方面涉及将在创造性的方法中获得的聚乙烯醇缩醛粉末作为用于生产陶瓷坯片或陶瓷模塑体的粘结剂的用途。
本发明的第四方面涉及聚乙烯醇缩醛，其具有颗粒尺寸为2～500μm的颗粒的残留颗粒计数为等于或小于500个/ml，并且具有颗粒尺寸为2～5μm的颗粒的残留颗粒计数除以颗粒尺寸为2～20μm的颗粒的残留颗粒计数的比率为等于或小于0.8，其中残留颗粒计数如说明书中所述在甲苯和乙醇的1:1混合物中的2重量％的溶液中测量。优选地，比率为等于或小于0.75，更优选为等于或小于0.70，甚至更优选为等于或小于0.65，最优选为等于或小于0.60并且特别为等于或小于0.50。
此外优选地，颗粒尺寸为2～500μm的颗粒的残留颗粒计数为等于或小于450个/ml，更优选为等于或小于400个/ml，甚至更优选为等于或小于350个/ml，最优选为等于或小于300个/ml。
这种具有总体低量残留颗粒，特别是具有在2～5μm的临界范围内的低残留颗粒比率的聚乙烯醇缩醛特别适用于生产陶瓷坯片。
实施例
聚乙烯醇缩醛的合成
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，在搅拌的同时，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，用具有9.4mg/的氯化物含量的水清洗至中性，并且干燥。获得具有12.7重量％(19.1mol％)的聚乙烯醇含量和2.3重量％(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，在搅拌的同时，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，用具有9.4mg/的氯化物含量的水清洗至中性，并且干燥。获得具有12.5重量％(18.8mol％)的聚乙烯醇含量和1.7重量％(1.3mol％)的聚乙酸乙烯酯含量的PVB。
聚乙烯醇缩丁醛(PVB 3)
将100重量份粘度为26mPas(在20℃下根据DIN 53015在4w/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1075重量份的水中。在40℃的温度下，添加57重量份的正丁醛，并且在10℃的温度下，在搅拌的同时，添加75重量份的20％盐酸。将混合物加热到70℃在聚乙烯醇缩丁醛(PVB)沉淀之后在该温度下搅拌1h。冷却到室温之后分离PVB，用具有9.4mg/l的氯化物含量的水清洗至中性，并且干燥。获得具有20.0重量％(28.8mol％)的聚乙烯醇含量和1.4重量％(1mol％)的聚乙酸乙烯酯含量的PVB。
颗粒尺寸分布的测量
使用倾斜/旋转混合器将2g PVB3的粉末溶解于98g溶剂混合物(乙醇和甲苯的1:1混合物)中。24小时之后，取出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。

Claims (13)

1.一种生产聚乙烯醇缩醛粉末的方法，其包含以下步骤：
a.在酸的存在下将聚乙烯醇与醛反应以制备所述聚乙烯醇缩醛，
b.将步骤a中获得的所述聚乙烯醇缩醛沉淀，
c.用包含水的清洗液清洗所述步骤b中获得的沉淀物，和
d.将所述步骤c的经清洗的沉淀物干燥，
其中所述步骤c中的清洗液包含等于或小于100mg/l的氯离子。
2.根据权利要求1所述的方法，其中所述步骤c中的清洗液包含等于或小于30mg/l的氯离子。
3.根据权利要求1或2所述的方法，其中所述步骤c中的清洗液包含等于或小于10mg/l的氯离子。
4.根据上述权利要求中任一项所述的方法，其中所述清洗液基本上由水组成。
5.根据上述权利要求中任一项所述的方法，其中所述醛是正丁醛和/乙醛，并且所述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缩合的混合的聚乙烯醇缩醛。
6.根据上述权利要求中任一项所述的方法，其中所述酸是盐酸。
7.根据上述权利要求中任一项所述的方法，其中通过化学沉淀、反渗透、吸附和/或氧化减少所述清洗液中氯化物的量。
8.根据上述权利要求中任一项所述的方法，其中所述聚乙烯醇缩醛粉末包含等于或小于25ppm的氯化物。
9.根据上述权利要求中任一项所述的方法，其中所述聚乙烯醇缩醛粉末包含等于或小于10ppm的氯化物。
10.将根据权利要求1至9中任一项所述的方法中获得的聚乙烯醇缩醛作为用于生产陶瓷坯片或陶瓷模塑体的粘结剂的用途。
11.一种聚乙烯醇缩醛，其具有颗粒尺寸为2～500μm的颗粒的残留颗粒计数为等于或小于500个/ml，并且具有颗粒尺寸为2～5μm的颗粒的残留颗粒计数除以颗粒尺寸为2～20μm的颗粒的残留颗粒计数的比率为等于或小于0.8，其中所述残留颗粒计数如说明书中所述在甲苯和乙醇的1:1混合物中的2重量％的溶液中测量。
12.根据权利要求11所述的聚乙烯醇缩醛，其中所述比率为等于或小于0.75。
13.将根据权利要求11或12所述的聚乙烯醇缩醛作为用于生产陶瓷坯片或陶瓷模塑体的粘结剂的用途。
CN202280075140.8A 2021-11-18 2022-11-17 具有改善的残留颗粒尺寸分布的聚乙烯醇缩醛类 Pending CN118234763A (zh)

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