CN111572131B - 一种高耐热、高可靠性cem-1覆铜板的制备方法 - Google Patents
一种高耐热、高可靠性cem-1覆铜板的制备方法 Download PDFInfo
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Abstract
本发明属于覆铜板生产技术领域,涉及一种高耐热、高可靠性CEM‑1覆铜板的制备方法。本发明将木浆纤维纸分别浸渍里料一浸树脂和里料二浸树脂,尤其里料二浸树脂中,聚乙烯醇缩甲醛‑聚乙烯醇‑聚丙烯酸共聚物大大提高了层间粘合力,氰酸酯树脂及其改性树脂具有优良的高温力学性能、弯曲强度和拉伸强度,且其具有极低的吸水率、较低的成型收缩率和较好的尺寸稳定性,其耐湿热性、阻燃性、粘结性都很好,与玻纤、碳纤、石英纤维、晶须等增强材料及电子级填料的粘接性能较好。本发明制得的覆铜板板材的耐热性能够达到288℃、60秒以上浮焊不分层、不起泡,耐热性有明显提高;从而显著降低维修焊接时的爆板率,大大提高工作效率。
Description
技术领域
本发明涉及一种覆铜板,尤其涉及一种高耐热、高可靠性CEM-1覆铜板的制备方法,属于覆铜板生产技术领域。
背景技术
2006年7月1日开始实施的欧盟WEEE(废旧电子电气设备)和ROHS(电子电气设备中禁止使用某些有害物质)两大指令中规定,新投放市场的电气电子产品不得含有铅、汞、镉等6种有毒物质,标志着全球电子行业进入无铅焊接时代。典型的无铅回流焊条件温度为245-265℃,维持一分钟;维修焊接温度峰值将达到300℃,维持几秒钟。如果覆铜板的耐热性差,在整机加工中有时就不得不采取降低焊接温度、降低波峰没人板的深度等措施,从而使焊料不能充分接触焊盘,焊料流动性差,造成润湿不良的缺陷,导致整机的质量稳定性降低,且工作效率大大降低。这就要求PCB(环氧印制线路板)板材有更高的热可靠性。
FR-4覆铜板具有较高的耐热性,但其制造成本高,机械加工性差,不可冲孔,而高耐热的CEM-1覆铜板可以克服这些缺点。
发明内容
本发明针对上述现有技术存在的不足,提供一种高耐热、高可靠性CEM-1覆铜板的制备方法。
本发明解决上述技术问题的技术方案如下:一种高耐热、高可靠性CEM-1覆铜板的制备方法,步骤如下:
(1)制备表料树脂:按重量份数计,将10-70份溶剂型环氧树脂、0.1-2份固化及固化促进剂、10-40份溶剂和0.1-30份阻燃剂混合,搅拌均匀;
(2)制备里料一浸树脂:按重量份数计,将30-45份水溶性酚醛树脂、150-200份甲醇、30-50份丙酮和100-150份水混合,搅拌均匀;
(3)制备里料二浸树脂:按重量份数计,将40-50份聚乙烯醇缩甲醛-聚乙烯醇-聚丙烯酸共聚物、10-40份环氧树脂、125-130份溶剂型酚醛树脂、0-50份氰酸酯树脂、10-50份氰酸酯改性树脂、10-50份电子级填料和10-60份阻燃剂混合,搅拌均匀;
(4)将电子级玻璃纤维布浸渍在步骤(1)制得的表料树脂后,经过100-200℃的上胶机,制得表料半固化片;
(5)将木浆纤维纸依次浸渍在步骤(2)的里料一浸树脂和步骤(3)的里料二浸树脂后,经过100-200℃的上胶机,制得里料半固化片;
(6)取若干张步骤(5)制得的里料半固化片叠加在一起,双面各覆有一张步骤(4)所得的表料半固化片,最后在单面表料半固化片或双面表料半固化片上覆有铜箔,得板材;将板材与不锈钢板上下对应叠合,送入真空压机,在100-200℃、70-150kgf/cm2条件下热压90-150min,制得高耐热、高可靠性CEM-1覆铜板。
在上述技术方案的基础上,本发明还可以做如下改进。
进一步,步骤(1)中,所述溶剂型环氧树脂为低溴型环氧树脂与丙酮按重量比1:0.9完全混合溶解而成,其环氧当量为410-420g/eq,含溴量为19-21wt%;
所述固化及固化促进剂为双氰胺、2-甲基咪唑或硅烷偶联剂KH-550中的一种或两种以上;
所述溶剂为DMF、丙酮或丁酮中的一种或两种以上;
所述阻燃剂为氢氧化镁、三氧化二锑或氢氧化铝中的一种或两种以上混合。
进一步,步骤(3)中,所述环氧树脂为含磷环氧树脂、四溴双酚A型环氧树脂或E51中的一种或两种以上混合,其环氧当量为180-450g/eq;
所述溶剂型酚醛树脂为固体酚醛树脂与甲苯、甲醇、丁酮按重量比6:4:2:3混合溶解而成;
所述氰酸酯改性树脂为氰酸酯与环氧树脂、酚醛树脂的共聚改性物;
所述电子级填料为钛白粉或硅微粉中的一种或两种混合,其粒度为D30-200μm;
所述阻燃剂为氢氧化镁或三氧化二锑中的一种或两种混合。
本发明的有益效果是:
本发明将木浆纤维纸分别浸渍里料一浸树脂和里料二浸树脂,尤其里料二浸树脂中,聚乙烯醇缩甲醛-聚乙烯醇-聚丙烯酸共聚物大大提高了层间粘合力,氰酸酯树脂及其改性树脂具有优良的高温力学性能,弯曲强度和拉伸强度都比双官能团环氧树脂高,且其具有极低的吸水率(<1.5%)、较低的成型收缩率和较好的尺寸稳定性,其耐热性好,玻璃化温度在240-260℃,最高能达到400℃,改性后可在170℃固化;氰酸酯树脂及其改性树脂的耐湿热性、阻燃性、粘结性都很好,与玻纤、碳纤、石英纤维、晶须等增强材料及电子级填料的粘接性能较好。本发明制得的覆铜板板材的耐热性能够达到288℃、60秒以上浮焊不分层、不起泡,耐热性有明显提高;从而显著降低维修焊接时的爆板率,大大提高工作效率。
具体实施方式
以下结合实例对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例1
一种高耐热、高可靠性CEM-1覆铜板的制备方法,步骤如下:
(1)制备表料树脂:按重量份数计,将59份溶剂型环氧树脂(低溴型环氧树脂的环氧当量为410g/eq,含溴量为20wt%)、1份固化剂双氰胺、0.1份硅烷偶联剂KH-550、0.1份固化促进剂2-甲基咪唑、19份溶剂DMF和21份阻燃剂氢氧化铝混合,搅拌均匀;
(2)制备里料一浸树脂:按重量份数计,将40份水溶性酚醛树脂、200份甲醇、30份丙酮和100份水混合,搅拌均匀;
(3)制备里料二浸树脂:按重量份数计,将43份聚乙烯醇缩甲醛-聚乙烯醇-聚丙烯酸共聚物、40份E-51环氧树脂、125份溶剂型酚醛树脂、20份氰酸酯改性树脂、10份电子级填料硅微粉和15份电子级填料钛白粉和10份阻燃剂三氧化二锑混合,搅拌均匀;
(4)将电子级玻璃纤维布浸渍在步骤(1)制得的表料树脂后,经过100℃的上胶机,制得表料半固化片;
(5)将木浆纤维纸依次浸渍在步骤(2)的里料一浸树脂和步骤(3)的里料二浸树脂后,经过100℃的上胶机,制得里料半固化片;
(6)取6张步骤(5)制得的里料半固化片叠加在一起,双面各覆有一张步骤(4)所得的表料半固化片,最后在单面表料半固化片上覆有铜箔,铜箔厚度在1OZ,得板材;将板材与不锈钢板上下对应叠合,送入真空压机,在150℃、80kgf/cm2条件下热压100min,制得高耐热、高可靠性CEM-1覆铜板。
对比例1
一种高耐热、高可靠性CEM-1覆铜板的制备方法,步骤如下:
(1)制备表料树脂:按重量份数计,将59份溶剂型环氧树脂(低溴型环氧树脂的环氧当量为410g/eq,含溴量为20wt%)、1份固化剂双氰胺、0.1份硅烷偶联剂KH-550、0.1份固化促进剂2-甲基咪唑、19份溶剂DMF和21份阻燃剂氢氧化铝混合,搅拌均匀;
(2)制备里料一浸树脂:按重量份数计,将40份水溶性酚醛树脂、200份甲醇、30份丙酮和100份水混合,搅拌均匀;
(3)制备里料二浸树脂:按重量份数计,将40份E-51环氧树脂、125份溶剂型酚醛树脂、10份电子级填料硅微粉、15份电子级填料钛白粉和10份阻燃剂三氧化二锑混合,搅拌均匀;
(4)将电子级玻璃纤维布浸渍在步骤(1)制得的表料树脂后,经过100℃的上胶机,制得表料半固化片;
(5)将木浆纤维纸依次浸渍在步骤(2)的里料一浸树脂和步骤(3)的里料二浸树脂后,经过100℃的上胶机,制得里料半固化片;
(6)取6张步骤(5)制得的里料半固化片叠加在一起,双面各覆有一张步骤(4)所得的表料半固化片,最后在单面表料半固化片上覆有铜箔,铜箔厚度在1OZ,得板材;将板材与不锈钢板上下对应叠合,送入真空压机,在150℃、80kgf/cm2条件下热压100min,制得高耐热、高可靠性CEM-1覆铜板。
实施例2
一种高耐热、高可靠性CEM-1覆铜板的制备方法,步骤如下:
(1)制备表料树脂:将40份溶剂型环氧树脂(低溴型环氧树脂的环氧当量为420g/eq,含溴量为20wt%)、1份固化剂双氰胺、0.1份固化促进剂2-甲基咪唑、25份溶剂丙酮和25份阻燃剂氢氧化铝混合,搅拌均匀;
(2)制备里料一浸树脂:按重量份数计,将30份水溶性酚醛树脂、180份甲醇、40份丙酮和120份水混合,搅拌均匀;
(3)制备里料二浸树脂:按重量份数计,将40份聚乙烯醇缩甲醛-聚乙烯醇-聚丙烯酸共聚物、20份四溴双酚A型环氧树脂(环氧当量为410g/eq)、128份溶剂型酚醛树脂、35份氰酸酯改性树脂、15份电子级填料硅微粉、20份电子级填料钛白粉、10份阻燃剂三氧化二锑和8份阻燃剂氢氧化镁混合,搅拌均匀;
(4)将电子级玻璃纤维布浸渍在步骤(1)制得的表料树脂后,经过150℃的上胶机,制得表料半固化片;
(5)将木浆纤维纸依次浸渍在步骤(2)的里料一浸树脂和步骤(3)的里料二浸树脂后,经过150℃的上胶机,制得里料半固化片;
(6)取4张步骤(5)制得的里料半固化片叠加在一起,双面各覆有一张步骤(4)所得的表料半固化片,最后在双面表料半固化片上各覆有铜箔,铜箔厚度为1OZ,得板材;将板材与不锈钢板上下对应叠合,送入真空压机,在120℃、100kgf/cm2条件下热压120min,制得高耐热、高可靠性CEM-1覆铜板。
实施例3
一种高耐热、高可靠性CEM-1覆铜板的制备方法,步骤如下:
(1)制备表料树脂:将55份溶剂型环氧树脂(低溴型环氧树脂的环氧当量为410g/eq,含溴量为20wt%)、1份固化剂双氰胺、0.1份固化促进剂2-甲基咪唑、35份溶剂丁酮、5份阻燃剂氢氧化铝、10份阻燃剂氢氧化镁和5份阻燃剂三氧化二锑混合,搅拌均匀;
(2)制备里料一浸树脂:按重量份数计,将35份水溶性酚醛树脂、200份甲醇、35份丙酮和120份水混合,搅拌均匀;
(3)制备里料二浸树脂:按重量份数计,将45份聚乙烯醇缩甲醛-聚乙烯醇-聚丙烯酸共聚物、30份含磷环氧树脂(环氧当量为410g/eq、含磷量为20wt%)、128份溶剂型酚醛树脂、10份氰酸酯树脂、25份氰酸酯改性树脂、15份电子级填料硅微粉、10份电子级填料钛白粉、15份阻燃剂三氧化二锑和8份阻燃剂氢氧化镁混合,搅拌均匀;
(4)将电子级玻璃纤维布浸渍在步骤(1)制得的表料树脂后,经过180℃的上胶机,制得表料半固化片;
(5)将木浆纤维纸依次浸渍在步骤(2)的里料一浸树脂和步骤(3)的里料二浸树脂后,经过180℃的上胶机,制得里料半固化片;
(6)取6张步骤(5)制得的里料半固化片叠加在一起,双面各覆有一张步骤(4)所得的表料半固化片,最后在单面表料半固化片上覆有铜箔,铜箔厚度为1OZ,得板材;将板材与不锈钢板上下对应叠合,送入真空压机,在180℃、140kgf/cm2条件下热压130min,制得高耐热、高可靠性CEM-1覆铜板。
表1为实施例1-3和对比例1所得样品的各项性能对照表。
表1
由表1可以看出,相比于对比例1,实施例1制备的CEM-1覆铜板,其耐浸焊及分解温度的测试效果均优异很多,证明本发明制备的CEM-1覆铜板具有较高的耐热性及可靠性。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (3)
1.一种高耐热、高可靠性CEM-1覆铜板的制备方法,其特征在于,步骤如下:
(1)制备表料树脂:按重量份数计,将10-70份溶剂型环氧树脂、0.1-2份固化及固化促进剂、10-40份溶剂和0.1-30份阻燃剂混合,搅拌均匀;所述溶剂型环氧树脂为低溴型环氧树脂与丙酮按照重量比1:0.9完全混合溶解而成,其中低溴型环氧树脂的环氧当量为410-420g/eq,含溴量为19-21wt%;
(2)制备里料一浸树脂:按重量份数计,将30-45份水溶性酚醛树脂、150-200份甲醇、30-50份丙酮和100-150份水混合,搅拌均匀;
(3)制备里料二浸树脂:按重量份数计,将40-50份聚乙烯醇缩甲醛-聚乙烯醇-聚丙烯酸共聚物、10-40份环氧树脂、125-130份溶剂型酚醛树脂、0-50份氰酸酯树脂、10-50份氰酸酯改性树脂、10-50份电子级填料和10-60份阻燃剂混合,搅拌均匀;所述环氧树脂为含磷环氧树脂、四溴双酚A型环氧树脂或E51中的一种或两种以上混合,其环氧当量为180-450g/eq;所述氰酸酯改性树脂为氰酸酯与环氧树脂、酚醛树脂的共聚改性物;
(4)将电子级玻璃纤维布浸渍在步骤(1)制得的表料树脂后,经过100-200℃的上胶机,制得表料半固化片;
(5)将木浆纤维纸依次浸渍在步骤(2)的里料一浸树脂和步骤(3)的里料二浸树脂后,经过100-200℃的上胶机,制得里料半固化片;
(6)取若干张步骤(5)制得的里料半固化片叠加在一起,双面各覆有一张步骤(4)所得的表料半固化片,最后在单面表料半固化片或双面表料半固化片上覆有铜箔,得板材;将板材与不锈钢板上下对应叠合,送入真空压机,在100-200℃、70-150kgf/cm²条件下热压90-150min,制得高耐热、高可靠性CEM-1覆铜板。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,所述固化及固化促进剂为双氰胺、2-甲基咪唑和硅烷偶联剂KH-550的混合物;
所述溶剂为DMF、丙酮或丁酮中的一种或两种以上;
所述阻燃剂为氢氧化镁、三氧化二锑或氢氧化铝中的一种或两种以上混合。
3.根据权利要求1所述的制备方法,其特征在于,步骤(3)中,所述溶剂型酚醛树脂为固体酚醛树脂与甲苯、甲醇、丁酮按重量比6:4:2:3混合溶解而成;
所述电子级填料为钛白粉或硅微粉中的一种或两种混合,其粒度为D20-200μm;
所述阻燃剂为氢氧化镁或三氧化二锑中的一种或两种混合。
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