CN106146729A - 一种自修复柔性印刷电路板及其制备方法 - Google Patents
一种自修复柔性印刷电路板及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种自修复柔性印刷电路板及其制备方法，所述电路板的基材由基于动态硼酸酯键的自修复水凝胶弹性体构成，所述基材所含原料及各原料的重量份数为：含亲水基团的烯类单体或聚合物30‑70份，含羟基的烯类单体或聚合物5‑35份，含硼化合物2‑8份，水15‑35份，自由基引发剂0.5‑1份。本发明通过羟基与硼酸根形成的动态硼酸酯键赋予水凝胶弹性体自我修复功能，硼酸酯键作为动态共价键，兼具共价键的强度、物理交联的可逆性与可塑性，从而赋予材料自修复性能，延长材料的使用周期；同时，其原料廉价易得，制备工艺简单，且具有较好的综合机械性能。
Description
技术领域
本发明涉及功能高分子材料技术领域，尤其是涉及一种自修复柔性印刷电路板及其制备方法。
背景技术
传统的柔性电路板(FPC)是以聚酰亚胺或聚酯薄膜为基材制成，具有许多硬性印刷电路板不具备的优点，例如它可以自由弯曲、卷绕、折叠。利用FPC可大大缩小电子产品的体积，适用电子产品向高密度、小型化、高可靠方向发展的需要。因此，FPC在航天、军事、移动通讯、手提电脑、计算机外设、PDA、数字相机等领域或产品上得到了广泛的应用。柔性印刷线路板有单面、双面和多层板之分。所采用的基材以聚酰亚胺覆铜板为主，与兼有机械保护和良好电气绝缘性能的覆盖膜通过压制而成最终产品。双面、多层印制线路板的表层和内层导体通过金属化实现内外层电路的电气连接。
但是，现有的柔性电路板制造成本高，周期长，耐折性不足且破裂受损即意味着报废；在印制电路和使用过程中会出现微观裂纹或损伤，导致材料电路不良，降低材料的有效使用寿命。
发明内容
针对现有技术存在的上述问题，本申请人提供了一种自修复柔性印刷电路板及其制备方法。本发明电路板使用具有自修复性能的弹性体作为基材，该弹性体基材所需原料均已商业化，价廉易得，可大大降低电路板的成本；同时本发明赋予电路板自修复性能，可解决传统印刷电路板在使用过程中受损后性能下降和报废的问题，延长材料的服务周期和使用寿命。
本发明的技术方案如下：
一种自修复柔性印刷电路板，所述电路板的基材由基于动态硼酸酯键的自修复水凝胶弹性体构成。
所述基材所含原料及各原料的重量份数为：
所述含亲水基团的烯类单体或聚合物为丙烯酸类、丙烯酰胺类、聚乙二醇丙烯酸酯类中的一种或多种。
所述含亲水基团的烯类单体或聚合物为丙烯酸、甲基丙烯酸、丙烯酰胺、N,N-二甲基丙烯酰胺、N-羟甲基丙烯酰胺、聚乙二醇单甲醚丙烯酸酯、聚乙二醇二丙烯酸酯中的一种或多种。
所述含羟基的烯类单体或聚合物为丙烯酸-2-羟基乙酯、丙烯酸-β-羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯醇中的一种或多种。
所述自由基引发剂为2,2-二乙氧基苯乙酮、安息香双甲醚、2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮中的一种。
所述含硼化合物为硼酸、硼砂、氧化硼中的一种或多种。
一种所述自修复柔性印刷电路板的制备方法，所述方法包括以下步骤：
(1)将含亲水基团的烯类单体或聚合物30-70份、含羟基的烯类单体或聚合物5-35份、含硼化合物2-8份、水15-35份和自由基引发剂0.5-1份按比例投入容器内，使用混匀仪震荡搅拌5-10min，再向溶液中通氮气3-5min；
(2)将步骤(1)所得混合溶液置于自制模具中，使用254nm紫外灯进行辐照15-20min，即得到基于硼酸酯键的自修复水凝胶弹性体；
(3)将步骤(2)所得基于硼酸酯键的自修复水凝胶弹性体作为基材，通过印制电路技术，即可得到所述的自修复柔性印刷电路板。
所述步骤(2)中自制模具由两块玻璃板夹住硅胶圈制得，玻璃板尺寸为30mm×75mm×1mm，硅胶圈厚度为2mm。
本发明有益的技术效果在于：
(1)本发明采用商业化的单体作为基材原料，价廉易得，成本低；
(2)本发明采用“一锅法”制备自修复水凝胶弹性体基材，制备方法简单易行；
(3)本发明引入含亲水基团的烯类单体或聚合物和含羟基的烯类单体或聚合物，从而使基材具有弹性体的特性，具有优良的耐折性；
(4)本发明引入含羟基的烯类单体或聚合物，与硼酸根形成动态硼酸酯键，兼具共价键的稳定性和物理交联的可逆性，赋予基材优异的机械性能和本征自修复性能，修复过程无需外界催化剂或光热等刺激。
附图说明
图1为本发明自修复柔性印刷电路板自修复及机械性能示意图。
图2为实施例1所得自修复水凝胶弹性体修复前后的应力-应变曲线。
图3为实施例1所得自修复水凝胶弹性体的修复照片。
具体实施方式
下面结合附图和实施例，对本发明进行具体描述。
实施例1
一种自修复柔性印刷电路板的制备方法，所述方法包括以下步骤：
(1)将9g N,N-二甲基丙烯酰胺、1g 2-羟乙基丙烯酸酯、0.25g硼砂、4g水和0.05g2,2-二乙氧基苯乙酮按比例投入容器内，使用混匀仪震荡搅拌5min，再向溶液中通氮气3min；
(2)将步骤(1)所得混合溶液置于自制模具中，使用254nm紫外灯进行辐照18min，即得到基于硼酸酯键的自修复水凝胶弹性体；
(3)将步骤(2)所得基于硼酸酯键的自修复水凝胶弹性体作为基材，通过印制电路技术，即可得到所述的自修复柔性印刷电路板。
所述自制模具由两块玻璃板夹住硅胶圈制得，玻璃板尺寸为30mm×75mm×1mm，硅胶圈厚度为2mm。
实施例2
一种自修复柔性印刷电路板的制备方法，所述方法包括以下步骤：
(1)将7g N,N-二甲基丙烯酰胺、3g甲基丙烯酸羟乙酯、0.75g硼砂、4g水和0.05g2,2-二乙氧基苯乙酮按比例投入容器内，使用混匀仪震荡搅拌10min，再向溶液中通氮气5min；
(2)将步骤(1)所得混合溶液置于自制模具中，使用254nm紫外灯进行辐照15min，即得到基于硼酸酯键的自修复水凝胶弹性体；
(3)将步骤(2)所得基于硼酸酯键的自修复水凝胶弹性体作为基材，通过印制电路技术，即可得到所述的自修复柔性印刷电路板。
所述自制模具由两块玻璃板夹住硅胶圈制得，玻璃板尺寸为30mm×75mm×1mm，硅胶圈厚度为2mm。
实施例3
一种自修复柔性印刷电路板的制备方法，所述方法包括以下步骤：
(1)将5g丙烯酰胺、5g甲基丙烯酸羟丙酯、1.25g硼砂、6g水和0.05g 2,2-二乙氧基苯乙酮按比例投入容器内，使用混匀仪震荡搅拌8min，再向溶液中通氮气4min；
(2)将步骤(1)所得混合溶液置于自制模具中，使用254nm紫外灯进行辐照20min，即得到基于硼酸酯键的自修复水凝胶弹性体；
(3)将步骤(2)所得基于硼酸酯键的自修复水凝胶弹性体作为基材，通过印制电路技术，即可得到所述的自修复柔性印刷电路板。
所述自制模具由两块玻璃板夹住硅胶圈制得，玻璃板尺寸为30mm×75mm×1mm，硅胶圈厚度为2mm。
实施例4
一种自修复柔性印刷电路板的制备方法，所述方法包括以下步骤：
(1)将5g丙烯酰胺、5g甲基丙烯酸羟丙酯、1.25g硼酸、6g水和0.05g 2,2-二乙氧基苯乙酮按比例投入容器内，使用混匀仪震荡搅拌8min，调节pH值为9，再向溶液中通氮气4min；
(2)将步骤(1)所得混合溶液置于自制模具中，使用254nm紫外灯进行辐照20min，即得到基于硼酸酯键的自修复水凝胶弹性体；
(3)将步骤(2)所得基于硼酸酯键的自修复水凝胶弹性体作为基材，通过印制电路技术，即可得到所述的自修复柔性印刷电路板。
所述自制模具由两块玻璃板夹住硅胶圈制得，玻璃板尺寸为30mm×75mm×1mm，硅胶圈厚度为2mm。
实施例5
一种自修复柔性印刷电路板的制备方法，所述方法包括以下步骤：
(1)将5g聚乙二醇单甲醚丙烯酸酯、5g甲基丙烯酸羟丙酯、1.25g硼酸、6g水和0.05g 2,2-二乙氧基苯乙酮按比例投入容器内，使用混匀仪震荡搅拌8min，调节pH值为9，再向溶液中通氮气4min；
(2)将步骤(1)所得混合溶液置于自制模具中，使用254nm紫外灯进行辐照20min，即得到基于硼酸酯键的自修复水凝胶弹性体；
(3)将步骤(2)所得基于硼酸酯键的自修复水凝胶弹性体作为基材，通过印制电路技术，即可得到所述的自修复柔性印刷电路板。
所述自制模具由两块玻璃板夹住硅胶圈制得，玻璃板尺寸为30mm×75mm×1mm，硅胶圈厚度为2mm。
测试例：
将实施例1制备的自修复水凝胶弹性体从中间切开，并将断面迅速接触结合到一起，然后将水凝胶弹性体放置于密闭容器中，室温下自修复48h，将修复前、后的水凝胶弹性体在室温下进行拉伸测试。
图2为实施例1所得水凝胶弹性体修复前后的应力-应变曲线，由图2可以看出该自修复水凝胶弹性体具有优异的机械性能，断裂强度为0.57MPa，断裂伸长率为480％，在修复48h后修复效率接近100％。
图3所示为水凝胶弹性体修复照片，从照片中可以发现，修复后的水凝胶在切口处的痕迹几乎消失，且可以拉伸至原长的数倍。
Claims (9)
1.一种自修复柔性印刷电路板，其特征在于所述电路板的基材由基于动态硼酸酯键的自修复水凝胶弹性体构成。
2.根据权利要求1所述的自修复柔性印刷电路板，其特征在于所述基材所含原料及各原料的重量份数为：
3.根据权利要求2所述的自修复柔性印刷电路板，其特征在于所述含亲水基团的烯类单体或聚合物为丙烯酸类、丙烯酰胺类、聚乙二醇丙烯酸酯类中的一种或多种。
4.根据权利要求2或3所述的自修复柔性印刷电路板，其特征在于所述含亲水基团的烯类单体或聚合物为丙烯酸、甲基丙烯酸、丙烯酰胺、N,N-二甲基丙烯酰胺、N-羟甲基丙烯酰胺、聚乙二醇单甲醚丙烯酸酯、聚乙二醇二丙烯酸酯中的一种或多种。
5.根据权利要求2所述的自修复柔性印刷电路板，其特征在于所述含羟基的烯类单体或聚合物为丙烯酸-2-羟基乙酯、丙烯酸-β-羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、丙烯醇中的一种或多种。
6.根据权利要求2所述的自修复柔性印刷电路板，其特征在于所述自由基引发剂2,2-二乙氧基苯乙酮、安息香双甲醚、2-羟基-4-(2-羟乙氧基)-2-甲基苯丙酮中的一种。
7.根据权利要求2所述的自修复柔性印刷电路板，其特征在于所述含硼化合物为硼酸、硼砂、氧化硼中的一种或多种。
8.一种权利要求2所述的自修复柔性印刷电路板的制备方法，其特征在于所述方法包括以下步骤：
(1)将含亲水基团的烯类单体或聚合物30-70份、含羟基的烯类单体或聚合物5-35份、含硼化合物2-8份、水15-35份和自由基引发剂0.5-1份按比例投入容器内，使用混匀仪震荡搅拌5-10min，再向溶液中通氮气3-5min；
(2)将步骤(1)所得混合溶液置于自制模具中，使用254nm紫外灯进行辐照15-20min，即得到基于硼酸酯键的自修复水凝胶弹性体；
(3)将步骤(2)所得基于硼酸酯键的自修复水凝胶弹性体作为基材，通过印制电路技术，即可得到所述的自修复柔性印刷电路板。
9.根据权利要求8所述的制备方法，其特征在于所述步骤(2)中自制模具由两块玻璃板夹住硅胶圈制得，玻璃板尺寸为30mm×75mm×1mm，硅胶圈厚度为2mm。
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