CN112175174B - 液晶聚合物、积层材料、液晶聚合物溶液与液晶聚合物薄膜的形成方法 - Google Patents
液晶聚合物、积层材料、液晶聚合物溶液与液晶聚合物薄膜的形成方法 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及液晶聚合物。
背景技术
近年来液晶聚合物(LCP)应用蓬勃发展,在许多高值化及高端应用领域可看到LCP的相关产品,其中又以LCP薄膜发展最受瞩目。因其具有低吸湿、低介电常数及低介电损失的特性,且随着4G/5G高速传输的时代来临,目前应用于手持行动通讯软性铜箔基板(FCCL)的聚酰亚胺薄膜(PI膜)将不敷使用,LCP膜有潜力取而代之。然而传统LCP材料具有高分子排列顺向性,在押出成膜和吹塑成膜过程中,会由于LCP高度结晶顺向性,造成MD/TD两方向结晶度差异,使MD方向强度高,而TD方向易破裂,造就LCP热制膜加工技术具有高门槛设备与技术。
综上所述,目前亟需新的可溶LCP组成作为溶液型的膜级LCP,以应用于FCCL产品。
发明内容
本发明一实施例提供的液晶聚合物,由下列重复单元组成:10mol%至35mol%的(1)10mol%至35mol%的(2)/>10mol%至50mol%的(3)/>与10mol%至40mol%的(4a)/>10mol%至40mol%的(4b)/>或上述的组合,其中AR1、AR2、AR3与AR4各自为AR5或AR5-Z-AR6,AR5与AR6各自为/>/> 或上述的组合,且Z为-O-、/> 或C1-5的烷撑基;其中X与Y各自为H、C1-5的烷基、CF3或/>其中R2为H、CH3、CH(CH3)2、C(CH3)3、CF3、OCH3或/>n=1~4;以及其中R1为C1-5的烷撑基。
本发明一实施例提供的积层材料,包括:支撑物;以及液晶聚合物薄膜,位于支撑物上,其中液晶聚合物薄膜包含上述的液晶聚合物。
本发明一实施例提供的液晶聚合物溶液,包括:100重量份的溶剂;以及0.01至100重量份上述的液晶聚合物。
本发明一实施例提供的液晶聚合物薄膜的形成方法,包括:将上述液晶聚合物溶液涂布于支撑物上,以及移除溶剂,以形成液晶聚合物薄膜在支撑物上。
具体实施方式
本发明一实施例提供的液晶聚合物,由下列重复单元组成:10mol%至35mol%的(1)10mol%至35mol%的(2)/>10mol%至50mol%的(3)/>与10mol%至40mol%的(4a)/>10mol%至40mol%的(4b)/>或上述的组合。举例来说,可取/> 与/>进行反应以形成液晶聚合物。另一方面,可取/> 与进行反应以形成液晶聚合物。在其他实施例中,可取 与进行反应以形成液晶聚合物。/>与的摩尔比例为1∶1,若/>与/>的摩尔比例大于1或小于1,则过多的/>或/>无法进行共聚反应。
上述的AR1、AR2、AR3与AR4各自为AR5或AR5-Z-AR6,AR5与AR6各自为/>或上述的组合,且Z为-O-、/> 或C1-5的烷撑基;其中X与Y各自为H、C1-5的烷基、CF3或/>其中R2为H、CH3、CH(CH3)2、C(CH3)3、CF3、OCH3或/>n=1~4;以及其中R1为C1-5的烷撑基。在液晶聚合物中,若(1)/>的比例过低,以或/>为例,则结晶性变差;以为例,则溶解度变差。若(1)/>的比例过高,以/>或/>为例,则溶解度变差;以为例,则结晶性变差。若(2)/>的比例过低,以/>为例,则溶解度下降。若(2)/>的比例过高,以为例,则结晶性变差。若(3)/>的比例过低,以或/>为例,则结晶性变差。若(3)/>的比例过高,以/>或/>为例,则溶解度变差。若(4a)(4b)/>或上述的组合的比例过低,以 为例,则溶解度变差。若(4a)(4b)/>或上述的组合的比例过高,以或/>为例,则介电特性变差、结晶性变差或导致无法顺利聚合。
在一些实施例中,所述液晶聚合物由下列重复单元组成:15mol%至35mol%的(1)15mol%至35mol%的(2)/>15mol%至35mol%的(3)与10mol%至40mol%的(4a)/>10mol%至40mol%的(4b)/>或上述的组合。AR1、AR2、AR3与AR4各自的定义同上述,在此不再赘述。
在一些实施例中,液晶聚合物的重量平均分子量(Mw)介于1,000g/mol至1,000,000g/mol之间。若液晶聚合物的重量平均分子量过低,则成膜性变差。若液晶聚合物的重量平均分子量过高,则溶解度变差。
生产本发明的液晶聚合物的方法并不特别加以限定,举例来说,可以将含有羟基或是胺基的单体先与一过量的脂肪酸酐酰化以取得一酰化化合物,而酰化化合物与含有羧酸的单体进行转酯作用以形成液晶聚合物。也可以通过预先酰化好的酰化化合物与含有羧酸的单体进行转酯作用以形成液晶聚合物。
在酰化反应中的脂肪酸酐的含量例如是羟基与胺基当量的1.0~1.2倍。酰化反应的条件可以在130至180摄氏度进行5分钟至10小时,例如在140至160摄氏度进行10分钟至3小时。
用于本发明的酰化反应中的脂肪酸酐并不特别加以限定,其可以包括,例如,醋酸酐、丙酸酐、丁酸酐、异丁酸酐、戊酸酐、特戊酸酐、2-乙基己酸酐、单氯醋酸酐、二氯醋酸酐、三氯醋酸酐、单溴醋酸酐、二溴醋酸酐、三溴醋酸酐、单氟醋酸酐、二氟醋酸酐、三氟醋酸酐、戊二酸酐、顺丁烯二酸酐、琥珀酸酐、β-溴丙酸酐、类似物或上述的组合。在一些实施例中脂肪酸酐可为醋酸酐、丙酸酐、丁酸酐或异丁酸酐。
在酰化反应以及转酯反应中也可以加入一催化剂。而所加入的催化剂可以是已知的用于聚酯的聚合反应的催化剂,其例如是包括金属盐催化剂,例如是醋酸镁、醋酸锡、四丁基钛酸盐、醋酸铅、醋酸钾、三氧化锑或类似物,或是有机催化剂,可为含有两个或以上氮原子的杂环化合物,例如是N,N’-二甲基胺基吡啶、N-甲基咪唑、吡唑或类似物。
在酰化反应以及转酯反应中也可以加入一添加物,而所加入的添加物的实例包括已知的结合试剂、抗沉淀试剂、UV吸收剂、热稳定剂、抗氧化剂或上述的组合。
生产芳香液晶聚合物的方法,可利用批次式设备、连续式设备或类似设备。
上述液晶聚合物可溶于溶剂以形成液晶聚合物溶液。溶剂与液晶聚合物的重量比可为100∶0.01至100∶100。举例来说,液晶聚合物溶液可包含100重量份的溶剂以及0.01至100重量份的液晶聚合物。在一实施例中,液晶聚合物溶液包含100重量份的溶剂以及1至70重量份的液晶聚合物。在另一实施例中,液晶聚合物溶液包含100重量份的溶剂以及1至10重量份的液晶聚合物。若液晶聚合物的比例过低,则涂布成膜时不易得到较厚的膜。若液晶聚合物的比例过高,则粘度太高,不易进行涂布工艺。所述的液晶聚合物与前述类似,在此不赘述。举例来说,溶剂可为卤素溶剂(例如1-氯丁烷、氯苯、1,1-二氯乙烷、氯仿或1,1,2,2-四氯乙烷)、醚类溶剂(例如二乙基醚、四氢呋喃或1,4-二氧六环)、酮类溶剂(例如丙酮或环己酮)、酯类溶剂(例如醋酸乙酯)、内酯溶剂(例如γ-丙烯酸正丁酯)、碳酸酯溶剂(例如是乙烯基碳酸酯或丙烯基碳酸酯)、胺类溶剂(例如三乙基胺或吡啶)、腈类溶剂(例如乙腈)、酰胺溶剂(例如N,N′-二甲基甲酰胺、N,N′-二甲基乙酰胺、四甲基脲或N-甲基吡咯啶酮)、硝基溶剂(例如硝基甲烷或硝基苯)、硫化物溶剂(例如二甲基亚砜或丁二烷砜)、磷化物溶剂(例如六甲基磷酸胺或三正丁基磷化物)、链烷烃、烯烃、醇、醛、芳香烃、萜烯烃、氢化烃、杂环化合物或上述的组合。液晶聚合物溶液可进一步包含其他树脂,例如可将非液晶聚合物的至少一种树脂添加至该液体组成物中,该树脂可包含热塑性树脂或热固性树脂。热塑性树脂可为聚丙烯、聚酰胺、聚酯(即,非液晶聚烯丙基酯(polyallylate))、聚苯硫醚、聚醚酮、聚碳酸酯、聚醚砜、聚苯醚、聚醚酰亚胺、氟树脂、以甲基丙烯酸缩水甘油酯和聚乙烯的共聚物为代表的弹性体或其改性产物。热固性树脂可为酚醛树脂、环氧树脂、聚酰亚胺树脂或氰酸酯树脂。此外,在使用其他树脂的情况下,其他树脂可溶解于液晶聚合物所用的溶剂中。此外,液晶聚合物溶液可进一步包含其他添加剂,用以提升尺寸稳定性、机械特性、导热性、介电特性、热稳定性、光稳定性、耐老化性、涂布适性与成膜性。添加剂可包括无机填料(如二氧化硅、氧化铝、氧化钛、氧化锆、含水硅酸铝、碳酸钙、磷酸钙、钛酸钡、钛酸锶、氢氧化铝),有机填料(如环氧树脂粉末、三聚氰胺树脂粉末、聚脲树脂粉末、苯代三聚氰胺甲醛树脂粉末、苯乙烯树脂粉末、氟树脂粉末或氟树脂分散液)、抗氧化剂、热稳定剂、紫外线吸收剂、光安定剂、抗老化剂、增韧剂、扩链剂、塑化剂、交联剂、涂料油墨添加助剂(如消泡剂、流平剂、润湿分散剂、增稠剂、摇变性控制剂、密着促进剂、偶联剂)或上述的组合。
液晶聚合物薄膜可以利用下列方式制成。首先将上述液晶聚合物溶液涂布在支撑物上以使其平坦及均匀,其可利用任何涂布方法如滚轮涂布、浸泡涂布、喷洒涂布、旋转涂布、帘幕涂布、槽涂布或屏幕涂布。所述支撑物可为铜箔、玻璃、铝箔或其他合适的支撑物。在涂布之后,将溶剂移除以形成液晶聚合物薄膜在支撑物上。之后可视应用需求选择是否进一步移除支撑物,且移除支撑物的方法可为蚀刻或剥离。
移除溶剂的方法并不特别加以限定,例如利用蒸发法。而蒸发溶剂的方式可以利用加热、减压或通风等方式。在上述方法中,可利用加热蒸发方式,其优点为产率高与易于操作。另一方面,可在通风条件下加热以蒸发溶剂。在通风条件下加热的方法包括先在60~200摄氏度进行干燥约10分钟至2小时,之后再在200~400摄氏度进行热处理约30分钟至10小时。
以上述的方法所制得的液晶聚合物薄膜的厚度并不加以限定,例如可为1~100微米。
本发明一实施例提供的积层材料,包括支撑物以及位于支撑物上的液晶聚合物薄膜,支撑物可为铜箔、玻璃、铝箔或其他合适的支撑物。在一些实施例中,积层材料包括铜箔以及位于铜箔上的液晶聚合物薄膜。在铜箔与液晶聚合物薄膜之间可进一步包含粘着剂层,以提升铜箔与液晶聚合物薄膜之间的附着能力。当此积层材料被应用于印刷电路板时,一些具有优异电性的粘着剂如氟素树脂的导入能够减少印刷电路板产品的传输损耗。此积层材料可以进一步制成双面铜箔的积层材料,举例来说,可将上述单面铜箔的积层材料在液晶聚酯薄膜面进行对贴,通过热压成型,形成上下两层为铜箔,而中间层为液晶聚合物薄膜的双面铜箔积层材料。
本发明实施例将适量的(4a)(4b)/>或上述的组合导入液晶聚合物中,搭配适量的(1)/>(2)与(3)/>可有效增加液晶聚合物的溶解度、热性质(例如:热裂解温度(Td)、玻璃转移温度(Tg)、熔点(Tm))、降低液晶聚合物的薄膜的介电常数与降低液晶聚合物的薄膜的介电损耗。
为让本发明的上述内容和其他目的、特征和优点能更明显易懂,下文特举出优选实施例,作详细说明如下:
比较例1
取81.75g的4-胺基酚(0.75mol),155.25g的4-羟基苯甲酸(1.125mol)、70.5g的6-羟基-2-萘甲酸(0.375mol)、124.5g的间苯二甲酸(0.75mol)与306g的醋酸酐(3.0mol)混合后,在氮气下加热混合物至150℃反应3小时,接着升温至320℃反应1小时,之后温度维持320℃同时缓步抽真空反应至理想粘度,达理想粘度后用氮气破真空并利用氮气压力挤出产物。产物的重量平均分子量(Mw)为4,183g/mol,测量方法为凝胶渗透层析法(GPC)。产物的热裂解温度Td为398℃,Td的测量方法为热重分析仪(TGA)。将产物溶于N-甲基-2-吡咯烷酮(NMP)以形成8wt%固含量的溶液,经涂布于铜箔上、干燥并在200℃-300℃进行热处理之后可取得贴附于铜箔的液晶聚酯薄膜(厚25微米)。使用蚀刻液将铜箔移除后可取得此液晶聚酯薄膜,此薄膜的玻璃转换温度Tg为180℃、熔点Tm为293℃,Tg与Tm的测量方法为差示扫描量热法(DSC)。此薄膜的介电常数Dk为3.78,而介电损耗Df为0.009。Dk与Df的测量方法为共振腔法@10GHz。
实施例1
取51.75g的4-羟基苯甲酸(0.375mol)、70.5g的6-羟基-2-萘甲酸(0.375mol)、124.5g的间苯二甲酸(0.75mol)、102.75g的4-胺基苯甲酸(0.75mol)、82.5g的对苯二酚(0.75mol)与306g的醋酸酐(3.0mol)混合后,在氮气下加热混合物至150℃反应3小时,接着升温至320℃反应1小时,之后温度维持320℃同时缓步抽真空,反应至理想粘度,达理想粘度后用氮气破真空并利用氮气压力挤出产物。产物的重量平均分子量(Mw)为13,997g/mol(测量方法为凝胶渗透层析法(GPC))。产物的Td为455℃,Td的测量方法为热重分析仪(TGA)。将产物溶于NMP以形成8wt%固含量的溶液,经涂布于铜箔上、干燥并在200℃-300℃进行热处理之后可取得贴附于铜箔的液晶聚合物薄膜(厚25微米)。使用蚀刻液将铜箔移除后可取得此液晶聚合物薄膜。此薄膜的玻璃转换温度Tg为173℃,Tg的测量方法为差示扫描量热法(DSC)。此薄膜的Dk为3.58,而Df为0.0076。Dk与Df的测量方法为共振腔法@10GHz。
实施例2
取48.3g的4-羟基苯甲酸(0.35mol)、65.8g的6-羟基-2-萘甲酸(0.35mol)、116.2g的间苯二甲酸(0.7mol)、95.9g的4-胺基苯甲酸(0.7mol)、130.2g的4,4′-联苯酚(0.7mol)与286g的醋酸酐(2.8mol)混合后,在氮气下加热混合物至150℃反应3小时,接着升温至320℃反应1小时,之后温度维持320℃同时缓步抽真空,反应至理想粘度,达理想粘度后用氮气破真空并利用氮气压力挤出产物。产物的重量平均分子量(Mw)为84,878g/mol(测量方法为凝胶渗透层析法(GPC))。产物的Td为469℃,上述Td的测量方法为热重分析仪(TGA)。将产物溶于NMP以形成8wt%固含量的溶液,经涂布于铜箔上、干燥并在200℃-300℃进行热处理之后可取得贴附于铜箔的液晶聚合物薄膜(厚25微米)。使用蚀刻液将铜箔移除后可取得此液晶聚合物薄膜。此薄膜的玻璃转换温度(Tg)为181℃、熔点(Tm)为296℃,Tg与Tm的测量方法为差示扫描量热法(DSC)。此薄膜的Dk为3.59,而Df为0.007。Dk与Df的测量方法为共振腔法@10GHz。
实施例3
取131.6g的6-羟基-2-萘甲酸(0.7mol)、116.2g的间苯二甲酸(0.7mol)、95.9g的4-胺基苯甲酸(0.7mol)、130.2g的4,4′-联苯酚(0.7mol)与286g的醋酸酐(2.8mol)混合后,在氮气下加热混合物至150℃反应3小时,接着升温至320℃反应1小时,之后温度维持320℃同时缓步抽真空,反应至理想粘度,达理想粘度后用氮气破真空并利用氮气压力挤出产物。产物的重量平均分子量(Mw)为16,841g/mol(测量方法为凝胶渗透层析法(GPC))。产物的Td为457℃,上述Td的测量方法为热重分析仪(TGA)。将产物溶于NMP以形成8wt%固含量的溶液,经涂布于铜箔上、干燥并在200℃-300℃进行热处理之后可取得贴附于铜箔的液晶聚合物薄膜(厚25微米)。使用蚀刻液将铜箔移除后可取得此液晶聚合物薄膜。此薄膜的玻璃转换温度(Tg)为183℃、熔点(Tm)为315℃,Tg与Tm的测量方法为差示扫描量热法(DSC)。此薄膜的Dk为3.58,而Df为0.0042。Dk与Df的测量方法为共振腔法@10GHz。由比较例1与实施例1-3可知,导入4-胺基苯甲酸所形成的液晶聚合物具有较佳的热稳定性与较低的介电常数与介电损耗。
比较例2
取237g的6-羟基-2-萘甲酸(1.26mol)、116g的间苯二甲酸0.7mol)、20g的4-胺基苯甲酸(0.14mol)、130g的4,4′-联苯酚(0.7mol)与286g的醋酸酐(2.8mol)混合后,在氮气下加热混合物至150℃反应3小时,接着升温至320℃反应1小时,之后温度维持320℃同时缓步抽真空,反应至理想粘度,达理想粘度后用氮气破真空并利用氮气压力挤出产物。产物的Td为456℃,上述Td的测量方法为热重分析仪(TGA)。此产物无法溶于NMP中,无法进行溶液涂布成薄膜也无法进行GPC分析。
比较例3
取26g的6-羟基-2-萘甲酸(0.14mol)、116g的间苯二甲酸(0.7mol)、173g的4-胺基苯甲酸(1.26mol)、130g的4,4′-联苯酚(0.7mol)与286g的醋酸酐(2.8mol)混合后,在氮气下加热混合物至150℃反应3小时,接着升温至320℃反应1小时,之后温度维持320℃同时缓步抽真空,反应途中发现有产物析出现象,使反应无法继续进行与顺利下料。
实施例4
取131.6g的6-羟基-2-萘甲酸(0.7mol)、116g的间苯二甲酸(0.7mol)、106g的4-胺基甲基苯甲酸(0.7mol)、175g的双酚芴(0.5mol)、37.2g的4,4′-联苯酚(0.2mol)与286g的醋酸酐(2.8mol)混合后,在氮气下加热混合物至150℃反应3小时,接着升温至320℃反应1小时,之后温度维持320℃同时缓步抽真空,反应至理想粘度,达理想粘度后用氮气破真空并利用氮气压力挤出产物。产物的重量平均分子量为5728g/mol(测量方法为GPC)。产物的Td为358℃,上述Td的测量方法为热重分析仪(TGA)。将此产物可溶于NMP以形成40wt%固含量的溶液,由此可见,导入4-胺基甲基苯甲酸所形成的液晶聚合物具有高溶解度,有利于生产薄膜厚度较厚的液晶聚合物薄膜。在上述反应中,4-胺基甲基苯甲酸的结构为而双酚芴的结构为/>
应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (17)
6.如权利要求1的液晶聚合物,其中该液晶聚合物的重量平均分子量(Mw)介于1,000至1,000,000之间。
7.一种积层材料,包括:
一支撑物;以及
一液晶聚合物薄膜,位于该支撑物上,其中该液晶聚合物薄膜包含权利要求1至6中任一项的液晶聚合物。
8.如权利要求7的积层材料,其中该液晶聚合物薄膜的厚度为1微米至100微米。
9.如权利要求7的积层材料,其中该支撑物包括铜箔、玻璃或铝箔。
10.如权利要求7的积层材料,还包括一粘着剂层配置于该支撑物与该液晶聚合物薄膜之间。
11.一种液晶聚合物溶液,包括:
100重量份的溶剂;以及
0.01至100重量份权利要求1至6中任一项的液晶聚合物。
12.如权利要求11的液晶聚合物溶液,其中该溶剂包括卤素溶剂、醚类溶剂、酮类溶剂、酯类溶剂、碳酸酯溶剂、胺类溶剂、腈类溶剂、酰胺溶剂、硝基溶剂、硫化物溶剂、磷化物溶剂、链烷烃、烯烃、醇、醛、芳香烃、萜烯烃、氢化烃、杂环化合物或上述的组合。
13.如权利要求11的液晶聚合物溶液,还包括一其他树脂,且该其他树脂包含热塑性树脂或热固性树脂。
14.如权利要求11的液晶聚合物溶液,包括一添加剂,且该添加剂包含无机填料、有机填料、抗氧化剂、紫外线吸收剂、热稳定剂、光安定剂、抗老化剂、增韧剂、扩链剂、塑化剂、交联剂、涂料油墨添加助剂或上述的组合。
15.一种液晶聚合物薄膜的形成方法,包括:
将权利要求11至14中任一项的液晶聚合物溶液涂布于一支撑物上;以及
移除该溶剂,以形成一液晶聚合物薄膜在该支撑物上。
16.如权利要求15的液晶聚合物薄膜的形成方法,其中该支撑物包括铜箔、玻璃或铝箔。
17.如权利要求15的液晶聚合物薄膜的形成方法,还包括:
在形成该液晶聚合物薄膜在该支撑物上之后,移除该支撑物。
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EP3763766B1 (en) | 2022-08-31 |
CN112175174A (zh) | 2021-01-05 |
EP3763766A1 (en) | 2021-01-13 |
US20210002554A1 (en) | 2021-01-07 |
JP2021036025A (ja) | 2021-03-04 |
US11866632B2 (en) | 2024-01-09 |
JP7130703B2 (ja) | 2022-09-05 |
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