CN114953646A - 一种用于mini LED背板的覆铜板的制备方法及覆铜板 - Google Patents

一种用于mini LED背板的覆铜板的制备方法及覆铜板 Download PDF

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CN114953646A
CN114953646A CN202210649879.7A CN202210649879A CN114953646A CN 114953646 A CN114953646 A CN 114953646A CN 202210649879 A CN202210649879 A CN 202210649879A CN 114953646 A CN114953646 A CN 114953646A
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resin
copper
plate
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李凌云
杨永亮
刘政
郑宝林
栾好帅
徐凤
史晓杰
姜晓亮
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SHANDONG JINBAO ELECTRONICS CO Ltd
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Abstract

本发明公开了一种用于mini LED背板的覆铜板的制备方法，包括步骤：(1)制备胶液；(2)将电子级玻璃纤维布浸渍在步骤(1)制得的树脂后，经过100‑200℃的上胶机，制得半固化片；(3)取若干张步骤(2)制得的半固化片叠加在一起，双面各覆有一张铜箔，得板材；将板材与不锈钢板上下对应叠合，送入真空压机，经过热压，制得用于mini LED背板的覆铜板。本发明还提供了由上述制备方法制备得到的覆铜板。本发明采用抗紫外线型环氧树脂、BT树脂和SMA树脂为主体树脂，Tg≥220℃，Z轴CTE≤15ppm/℃，耐热性方面：T288>120min，耐热性更好，尺寸稳定性更好，且抗紫外线，耐辐射，反射率高。

Description

一种用于mini LED背板的覆铜板的制备方法及覆铜板
技术领域
本发明涉及覆铜板生产技术领域领域，特别涉及一种用于mini LED背板的覆铜板的制备方法及覆铜板。
背景技术
作为全球电子最具有发展潜力的国家之一，我国在电视、显示器、可穿戴设备、车载显示等终端需求旺盛的驱动下，Mini LED行业有望在未来几年迎来快速增长期。在MiniLED轻薄化的前提下，显示和背光效果的高要求对PCB背板的厚度均匀性、平整性、对准度等加工精度都提出了新的挑战，再加上PCB背板上有大量的LED芯片和驱动IC，这就需要背板的Tg点要高，而PCB背板在Mini LED加工过程中需要受到各种外力，保持背板的厚度均匀性、尺寸稳定性等非常重要。现阶段，用于mini LED背板的覆铜板也必须解决这些问题。
在专利CN 114085636 A中公布了一种以酚醛环氧树脂、酯环族环氧树脂和苯并恶嗪树脂为主体树脂的树脂组合物，制备的环氧玻璃布基覆铜箔板可达到Tg≥150℃；Z轴CTE≤3.0％；耐热性方面：TD≥400℃，T288＞60min。
发明内容
本发明针对上述现有技术存在的不足，提供一种用于mini LED背板的覆铜板的制备方法及覆铜板，制得的覆铜板板材的Tg≥220℃，Z轴CTE≤15ppm/℃，耐热性方面：T288>120min，耐热性更好，尺寸稳定性更好，且抗紫外线，耐辐射，反射率高。
为解决上述技术问题，本发明的实施方式公开了一种用于mini LED背板的覆铜板的制备方法，包括如下步骤：
(1)制备胶液：按重量份数计，将20-40份特种环氧树脂、20-40份改性BT树脂、20-40份SMA树脂、5-20份六氢苯酐、5-30份含磷阻燃剂、0.1-20份交联固化剂及固化促进剂、5-20份增韧剂、0.1-1份偶联剂、40-100份溶剂、50-150份填充材料混合，乳化搅拌均匀；
(2)将电子级玻璃纤维布浸渍在步骤(1)制得的树脂后，经过100-200℃的上胶机，制得半固化片，控制含胶量为45％-55％；
(3)取若干张步骤(2)制得的半固化片叠加在一起，双面各覆有一张铜箔，得板材；将板材与不锈钢板上下对应叠合，送入真空压机，经过热压，制得用于mini LED背板的覆铜板。
在上述技术方案的基础上，本发明还可做如下改进：
进一步，步骤(1)中，所述SMA树脂，可以提前溶解于溶剂中配制成溶液，促进其快速溶解。
进一步，步骤(1)中，所述特种环氧树脂为抗紫外线抗辐射环氧树脂、聚丙烯酸酯改性酚醛环氧树脂、氰酸酯改性环氧树脂的一种或两种混合。
其中，所述特种环氧树脂可以使用日本大赛璐2021P脂环族环氧树脂，环氧当量130-130g/Eq，色度(p-l-Co)50max，耐高温，耐黄变，耐天候，透明性良好，卤素含量低，电气绝缘性优异；所述SMA树脂为苯乙烯与马来酸酐的共聚物，共聚比例为6:1，所述SMA树脂的分子量在6000-6500之间，结构式为：
Figure BDA0003684917010000021
其中，x:y为6:1，1≤y≤500，n为正整数。
进一步，步骤(1)中，所述改性BT树脂为双烯封端棒状酰亚胺改性BT树脂或长链双马来酰亚胺改性的氰酸酯树脂的一种或两种。
进一步，步骤(1)中，所述含磷阻燃剂为磷腈化合物或间苯二酚双[二(2,6-二甲基苯基)]磷酸酯中的一种或两种。
进一步，所述磷腈化合物含磷量为13％wt，是以P、N交替双键排列为主链结构的一类无机化合物，以环状或线性结构存在，是在磷原子上接入苯氧基，苯氧基的引入使磷腈化合物成为无机化合物和有机化合物相结合的产物，是一种良好的无卤的环保型绿色阻燃剂。所述磷腈化合物具有如下结构式：
Figure BDA0003684917010000031
所述间苯二酚双[二(2,6-二甲基苯基)]磷酸酯为一种缩聚型磷酸酯阻燃剂，其含磷量为10.5％wt。
进一步，步骤(1)中，所述交联固化剂及固化促进剂为2-乙基-4甲基咪唑或胺类催化剂的一种或两种，所述增韧剂为氢化的丁苯橡胶或苯酚联苯型环氧树脂的一种或两种，所述偶联剂为KH-570，所述溶剂为甲苯、丙酮、丁酮、二甲苯中的一种或两种以上。其中，胺类催化剂优选异佛尔酮二胺。
进一步，步骤(1)中，所述填充材料为金红石型钛白粉、氧化铝、云母粉、球硅的一种或两种以上混合，粒径为0.5-20μm。
其中，所述钛白粉中TiO2含量达95％，平均粒径为3-5μm，最大粒径不超过20μm；白度>95％。填充材料最后添加。
进一步，在步骤(2)中，所述电子级玻璃纤维布经过硅烷偶联剂处理，所述电子级玻璃纤维布为E玻纤布或NE玻纤布的任意一种。半固化片胶化时间控制在180-220秒(160℃)。
进一步，步骤(3)中，所述热压条件为温度100-250℃、压力70-150kgf/cm2、热压时间150-300min。
可根据不同厚度要求调整半固化片的数量，将板材与不锈钢板上下对应叠合后，先铺高耐热毛毡，再送入真空压机，热压120-240min。
本发明的实施方式还公开了一种用于mini LED背板的覆铜板，采用上述制备方法制备得到。
与现有技术相比，本发明的有益效果如下：
(1)本发明中的环氧树脂耐辐射，耐高温，配合高反射型的白色填料，制得的背板反射性好，耐候性强，Tg高；
(2)本发明中的改性BT树脂具有极低的热膨胀系数(CTE)，适应mini LED背板使用时对对准度和加工精度的要求；
(3)本发明中的SMA树脂，能大大提高覆铜板的Tg值和热变形温度；
(4)本发明中的六氢苯酐是小分子酸酐，提高了交联密度，可以提高其耐热性，以及减少自由体积从而提高韧性和降低吸水性，制造出的PCB在高温无铅焊过程中产生的应力有所减少，Tg也更高；
(5)本发明中的阻燃剂由于独特的自熄功能，具有较高的热分解温度和阻燃效果，可以达到UL-94VO级阻燃性能，阻燃性能大大优于传统阻燃体系；且发烟及有毒气体少，是一种环境友好型阻燃材料，能满足欧盟RollS指令及WEEE指令的要求；
(6)本发明的胶液中加入的填充剂，如金红石型钛白粉，反射率高，耐黄变，耐紫外线，粒径小，分散性好，制得的PCB板具有较低的成型收缩率、热膨胀系数和很好的尺寸稳定性；
(7)本发明制得的覆铜板板材CTE(热膨胀系数)低至15ppm/℃，Tg高达220℃，T288>120min，反射率(A态)>90％，适应mini LED对耐热和尺寸稳定性等的要求，大大提高了封装效率和PCB板可靠性。
具体实施方式
以下由特定的具体实施例说明本发明的实施方式，本领域技术人员可由本说明书所揭示的内容轻易地了解本发明的其他优点及功效。虽然本发明的描述将结合较佳实施例一起介绍，但这并不代表此发明的特征仅限于该实施方式。恰恰相反，结合实施方式作发明介绍的目的是为了覆盖基于本发明的权利要求而有可能延伸出的其它选择或改造。为了提供对本发明的深度了解，以下描述中将包含许多具体的细节。本发明也可以不使用这些细节实施。此外，为了避免混乱或模糊本发明的重点，有些具体细节将在描述中被省略。需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
实施例1
一种用于mini LED背板的覆铜板的制备方法，包括如下步骤：
(1)制备树脂胶液：按重量份数计，将20份特种环氧树脂(2021P脂环族环氧树脂)、40份双烯封端棒状酰亚胺改性BT树脂、30份SMA树脂(共聚比例6：1)、7份六氢苯酐、30份含磷阻燃剂磷腈化合物、0.07份2-乙基-4甲基咪唑、10份增韧剂(氢化的丁腈橡胶)、0.5份偶联剂KH-570、100份丁酮、90份填充材料钛白粉、20份填充材料球硅混合、乳化搅拌均匀；
(2)将电子级2116玻璃纤维布浸渍在步骤(1)制得的树脂后，经过140℃的上胶机，制得半固化片，控制含胶量为45％-55％，胶化时间为200±20秒；
(3)取若干张步骤(2)制得的半固化片叠加在一起，双面各覆有一张铜箔，得板材；将板材与不锈钢板上下对应叠合，送入真空压机，在220℃、120kgf/cm2条件下热压180min，制得用于mini LED背板的覆铜板。
实施例2
一种用于mini LED背板的覆铜板的制备方法，包括如下步骤：
(1)制备树脂胶液：按重量份数计，将30份特种环氧树脂(聚丙烯酸酯改性酚醛环氧树脂)、20份双烯封端棒状酰亚胺改性BT树脂、40份SMA树脂(共聚比例6：1)、10份六氢苯酐、20份间苯二酚双[二(2,6-二甲基苯基)(磷酸酯磷含量为10.5％wt)、0.05份2-乙基-4甲基咪唑、0.5份异佛尔酮二胺、10份增韧剂(氢化的丁腈橡胶)、0.5份偶联剂KH-570、80份丁酮、20份甲苯、70份填充材料钛白粉、40份填充材料云母粉混合，乳化搅拌均匀；
(2)将电子级7628玻璃纤维布浸渍在步骤(1)制得的树脂胶液中，经过140℃的上胶机，胶化时间控制在200±20秒，制得半固化片，控制含胶量43％-46％；
(3)取6张步骤(2)制得的半固化片叠加在一起，双面各覆有一张35μm铜箔，得板材；将板材与不锈钢板上下对应叠合，铺高耐热毛毡，送入真空压机，在215℃、150kgf/cm2条件下热压200min，制得用于mini LED背板的覆铜板。
对比例
一种覆铜板的制备方法，包括如下步骤：
(1)制备树脂胶液：按重量份数计，将40份PPE树脂(双羟基封端聚苯醚低聚物)、140份双环戊二烯环氧树脂、10份DDS(4,4'-二氨基二苯砜)树脂、0.3份交联固化剂2-甲基-4-乙基咪唑、0.5份分散剂BYK-W 903、100份溶剂丙酮、20份阻燃剂四溴双酚A、40份填充材料高纯超细球形纳米非晶态硅微粉混合，乳化搅拌均匀；
(2)将电子级玻璃纤维布浸渍在步骤(1)制得的树脂胶液中，经过170℃的上胶机，胶化时间控制在95秒，制得半固化片；
(3)取6张步骤(2)制得的半固化片叠加在一起，双面各覆有一张18μm铜箔，得板材；将板材与不锈钢板上下对应叠合，铺高耐热毛毡，送入真空压机，在240℃、120kgf/cm2条件下热压180min，制得覆铜板。
实施例1-2和对比例所得样品的各项性能测试实验数据如表1所示。
表1实施例1-2和对比例所得样品的各项性能测试实验数据对照表
Figure BDA0003684917010000061
由表1可以看出，实施例1-2制得的覆铜板板材Z-CTE(热膨胀系数)低至15ppm/℃，Tg高达220℃，T288>120min，反射率(A态)>90％，相比于对比例，实施例1-2制备的覆铜板，Z-CTE、Tg、T288、反射率的测试效果均优异很多，证明本发明制备的覆铜板具有较低的CTE、较高的Tg和较高的耐热性及较高的反射率。可以满足mini LED背板的使用条件。
本发明的树脂胶液中，使用改性BT树脂和特种环氧树脂作为主体树脂，引入六氢苯酐作为等小分子在环氧树脂骨架中引入联苯基团，可以提高其耐热性，以及减少自由体积从而提高韧性和降低吸水性，制造出的PCB在高温无铅焊过程中产生的应力有所减少。添加了苯乙烯-马来酸酐共聚物(SMA树脂)增加了玻璃化转变和热变形温度。改性BT树脂既保留了BT树脂原本具有的优良的耐热性，很低的耐金属离子迁移性，并具有很好的尺寸稳定性，即CTE很低，还大幅改善了其介电性能和机械加工性能。特种环氧树脂抗紫外线抗辐射，与添加的钛白粉共同提高了覆铜板的反射率。本发明制得的覆铜板板材CTE(热膨胀系数)低至15ppm/℃，Tg高达220℃，T288>120min,反射率(A态)>90％，适应mini LED对耐热和尺寸稳定性等的要求，大大提高了封装效率和PCB板可靠性。
虽然通过参照本发明的某些优选实施方式，已经对本发明进行了描述，但本领域的普通技术人员应该明白，以上内容是结合具体的实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。本领域技术人员可以在形式上和细节上对其作各种改变，包括做出若干简单推演或替换，而不偏离本发明的精神和范围。

Claims (10)

1.一种用于mini LED背板的覆铜板的制备方法，其特征在于，包括如下步骤：
(1)制备胶液：按重量份数计，将20-40份特种环氧树脂、20-40份改性BT树脂、20-40份SMA树脂、5-20份六氢苯酐、5-30份含磷阻燃剂、0.1-20份交联固化剂及固化促进剂、5-20份增韧剂、0.1-1份偶联剂、40-100份溶剂、50-150份填充材料混合，乳化搅拌均匀；
(2)将电子级玻璃纤维布浸渍在步骤(1)制得的树脂后，经过100-200℃的上胶机，制得半固化片；
(3)取若干张步骤(2)制得的半固化片叠加在一起，双面各覆有一张铜箔，得板材；将板材与不锈钢板上下对应叠合，送入真空压机，经过热压，制得用于mini LED背板的覆铜板。
2.根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述特种环氧树脂为抗紫外线抗辐射环氧树脂、聚丙烯酸酯改性酚醛环氧树脂、氰酸酯改性环氧树脂的一种或两种混合。
3.根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述改性BT树脂为双烯封端棒状酰亚胺改性BT树脂或长链双马来酰亚胺改性的氰酸酯树脂的一种或两种。
4.根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述含磷阻燃剂为磷腈化合物或间苯二酚双[二(2,6-二甲基苯基)]磷酸酯中的一种或两种。
5.根据权利要求4所述的制备方法，其特征在于，所述磷腈化合物含磷量为13％wt，所述磷腈化合物具有如下结构式：
Figure FDA0003684913000000011
所述间苯二酚双[二(2,6-二甲基苯基)]磷酸酯的含磷量为10.5％wt。
6.根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述交联固化剂及固化促进剂为2-乙基-4甲基咪唑或胺类催化剂的一种或两种，所述增韧剂为氢化的丁苯橡胶或苯酚联苯型环氧树脂的一种或两种，所述偶联剂为KH-570，所述溶剂为甲苯、丙酮、丁酮、二甲苯中的一种或两种以上。
7.根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述填充材料为金红石型钛白粉、氧化铝、云母粉、球硅的一种或两种以上混合，粒径为0.5-20μm。
8.根据权利要求1所述的制备方法，其特征在于，在步骤(2)中，所述电子级玻璃纤维布经过硅烷偶联剂处理，所述电子级玻璃纤维布为E玻纤布或NE玻纤布的任意一种。
9.根据权利要求1所述的制备方法，其特征在于，步骤(3)中，所述热压条件为温度100-250℃、压力70-150kgf/cm2、热压时间150-300min。
10.一种用于mini LED背板的覆铜板，其特征在于，所述覆铜板采用权利要求1-9中任一项所述的制备方法制备得到。
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CN117004172B (zh) * 2023-08-14 2024-01-23 江苏耀鸿电子有限公司 一种覆铜板用高韧酚醛树脂胶液的制备方法

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