WO2018006235A1 - 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 PDF

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WO2018006235A1
WO2018006235A1 PCT/CN2016/088353 CN2016088353W WO2018006235A1 WO 2018006235 A1 WO2018006235 A1 WO 2018006235A1 CN 2016088353 W CN2016088353 W CN 2016088353W WO 2018006235 A1 WO2018006235 A1 WO 2018006235A1
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self
circuit board
printed circuit
parts
flexible printed
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PCT/CN2016/088353
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English (en)
French (fr)
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张洪吉
陈益鸣
陈明清
东为富
施冬键
李小杰
陆可钰
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江南大学
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Priority to PCT/CN2016/088353 priority Critical patent/WO2018006235A1/zh
Publication of WO2018006235A1 publication Critical patent/WO2018006235A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to the field of functional polymer materials, and more particularly to a self-healing flexible printed circuit board and a method of fabricating the same.
  • a conventional flexible circuit board is made of a polyimide or polyester film as a substrate, and has many advantages that a rigid printed circuit board does not have, for example, it can be freely bent, wound, and folded.
  • the use of FPC can greatly reduce the volume of electronic products, and is suitable for the development of electronic products in the direction of high density, miniaturization and high reliability. Therefore, FPC has been widely used in aerospace, military, mobile communications, laptop computers, computer peripherals, PDAs, digital cameras and other fields or products.
  • Flexible printed wiring boards are available in single-sided, double-sided, and multi-layer boards.
  • the substrate used is mainly made of polyimide copper clad laminate, and the final product is pressed by a cover film having both mechanical protection and good electrical insulation properties.
  • the surface and inner conductors of the double-sided, multi-layer printed wiring board are electrically connected to each other through metallization.
  • the existing flexible circuit board has high manufacturing cost, long cycle, insufficient folding endurance and damage to the rupture, which means scrapping; micro cracks or damage may occur during the printed circuit and the use process, resulting in poor material circuit. , reducing the effective life of the material.
  • the Applicant has provided a self-healing flexible printed circuit board and a method of fabricating the same.
  • the circuit board of the invention uses the self-repairing elastomer as the substrate, and the raw materials required for the elastomer substrate are commercialized, and are cheap and easy to obtain, and the cost of the circuit board can be greatly reduced;
  • the repair performance can solve the problem of performance degradation and scrapping of the traditional printed circuit board after being damaged during use, and prolong the service life and service life of the material.
  • a self-healing flexible printed circuit board, the substrate of the circuit board is self-healing based on dynamic borate bonds
  • the hydrogel elastomer is composed.
  • the raw materials contained in the substrate and the parts by weight of each raw material are:
  • the hydrophilic group-containing ethylenic monomer or polymer is one or more selected from the group consisting of acrylic acid, acrylamide, and polyethylene glycol acrylate.
  • the hydrophilic group-containing ethylenic monomer or polymer is acrylic acid, methacrylic acid, acrylamide, hydrazine, hydrazine-dimethyl acrylamide, hydrazine-methylol acrylamide, polyethylene glycol One or more of monomethyl ether acrylate and polyethylene glycol diacrylate.
  • the hydroxyl group-containing ethylenic monomer or polymer is 2-hydroxyethyl acrylate, ⁇ -hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and propylene alcohol. One or more.
  • the free radical initiator is 2,2-diethoxyacetophenone, benzoin dimethyl ether, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone One.
  • the boron-containing compound is one or more of boric acid, borax, and boron oxide.
  • a method of fabricating the self-healing flexible printed circuit board comprising the steps of:
  • the self-repairing flexible printed circuit board obtained by the circuit technology is obtained by using the borate-based self-repairing hydrogel elastomer obtained in the step (2) as a substrate.
  • the self-made mold in the step (2) is prepared by sandwiching two glass plates with a silicone ring, the size of the glass plate is 30 mm x 75 mm x l mm, and the thickness of the silicone ring is 2 mm.
  • the invention adopts a commercial monomer as a raw material of a substrate, which is cheap and easy to obtain, and has low cost;
  • the invention adopts a "one-pot method" to prepare a self-repairing hydrogel elastomer substrate, and the preparation method is simple and easy
  • the present invention introduces a hydrophilic group-containing ethylenic monomer or polymer and a hydroxyl group-containing ethylenic monomer or polymer, thereby imparting an elastomeric property to the substrate and having excellent folding resistance.
  • the present invention introduces a hydroxyl group-containing ethylenic monomer or polymer, and forms a dynamic borate ester bond with borate, which has both covalent bond stability and physical crosslink reversibility, and imparts excellent properties to the substrate.
  • the mechanical properties and intrinsic self-healing properties, the repair process does not require external catalyst or light and heat. .
  • FIG. 1 is a schematic view showing self-repair and mechanical properties of a self-repairing flexible printed circuit board according to the present invention.
  • FIG. 2 is a stress-strain curve before and after repair of the self-repairing hydrogel elastomer obtained in Example 1.
  • FIG. 3 is a photograph of the repair of the self-healing hydrogel elastomer obtained in Example 1.
  • a method of preparing a self-healing flexible printed circuit board comprising the steps of:
  • Borax 4 g of water and 0.05 g of 2,2-diethoxyacetophenone were put into the vessel in proportion, stirred and stirred for 5 min using a homomixer, and then nitrogen was passed through the solution for 3 min;
  • the self-repairing flexible printed circuit board can be obtained by a printed circuit technique using the borate-based self-repairing hydrogel elastomer obtained in the step (2) as a substrate.
  • the self-made mold is made by sandwiching two glass plates with a silicone ring, and the size of the glass plate is 30 mm x 75 mm x lm. m, the thickness of the silicone ring is 2mm.
  • a method of preparing a self-healing flexible printed circuit board comprising the steps of:
  • Borax 4 g of water and 0.05 g of 2,2-diethoxyacetophenone were put into the vessel in proportion, stirred and stirred for 10 min using a homomixer, and then nitrogen was passed through the solution for 5 min;
  • the self-repairing flexible printed circuit board can be obtained by a printed circuit technique using the borate-based self-repairing hydrogel elastomer obtained in the step (2) as a substrate.
  • the self-made mold is made by sandwiching two glass plates with a silicone ring, the size of the glass plate is 30 mm ⁇ 75 mm ⁇ lm m, and the thickness of the silicone ring is 2 mm.
  • a method of preparing a self-healing flexible printed circuit board comprising the steps of:
  • the self-repairing flexible printed circuit board obtained by the circuit technology is obtained by using the borate-based self-repairing hydrogel elastomer obtained in the step (2) as a substrate.
  • the self-made mold is made by sandwiching two glass plates with a silicone ring, the size of the glass plate is 30 mm ⁇ 75 mm ⁇ lm m, and the thickness of the silicone ring is 2 mm.
  • a method of preparing a self-healing flexible printed circuit board comprising the steps of: (1) 5 g of acrylamide, 5 g of hydroxypropyl methacrylate, 1.25 g of boric acid, 6 g of water, and 0.05 g of 2,2-diethoxyacetophenone were put into a container in proportion, and shaken using a homomixer. Stir for 8 min, adjust the pH to 9, and then pass nitrogen to the solution for 4 min;
  • the self-repairing flexible printed circuit board can be obtained by a printed circuit technique using the borate-based self-repairing hydrogel elastomer obtained in the step (2) as a substrate.
  • the self-made mold is made by sandwiching two glass plates with a silicone ring, the size of the glass plate is 30 mm ⁇ 75 mm ⁇ lm m, and the thickness of the silicone ring is 2 mm.
  • a method of fabricating a self-healing flexible printed circuit board comprising the steps of:
  • the self-repairing flexible printed circuit board can be obtained by a printed circuit technique using the borate-based self-repairing hydrogel elastomer obtained in the step (2) as a substrate.
  • the self-made mold is made by sandwiching two glass plates with a silicone ring, the size of the glass plate is 30 mm x 75 mm xlm m, and the thickness of the silicone ring is 2 mm.
  • Example 1 The self-repairing hydrogel elastomer prepared in Example 1 was cut from the middle, and the sections were quickly contacted and joined together, and then the hydrogel elastomer was placed in a closed container and self-repaired at room temperature for 48 hours. The hydrogel elastomers before and after the repair were subjected to a tensile test at room temperature.
  • Example 2 is a stress-strain curve before and after repair of the hydrogel elastomer obtained in Example 1. It can be seen from FIG. 2 that the self-repairing hydrogel elastomer has excellent mechanical properties, and the breaking strength is 0.57 MPa, and the fracture is 0.57 MPa. Elongation 480%, the repair efficiency is close to 100% after 48h repair.
  • Figure 3 shows a hydrogel elastomer repair photo. It can be seen from the photograph that the trace of the repaired hydrogel at the cut almost disappears and can be stretched several times longer than the original length.

Abstract

提供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。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

一种自修复柔性印刷电路板及其制备方法
技术领域
[0001] 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
[0002] 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。 禾 1」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。
[0003] 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。
技术问题
[0004] 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； 同吋本发明 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。
问题的解决方案
技术解决方案
[0005] 本发明的技术方案如下：
[0006] 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。
[0007] 所述基材所含原料及各原料的重量份数为：
[0008] 含亲水基团的烯类单体或聚合物 30-70份
[0009] 含羟基的烯类单体或聚合物 5-35份
[0010] 含硼化合物 2-8份
[0011] 水 15-35份
[0012] 自由基引发剂 0.5-1份。
[0013] 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。
[0014] 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、 Ν,Ν- 二甲基丙烯酰胺、 Ν-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。
[0015] 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。
[0016] 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。
[0017] 所述含硼化合物为硼酸、 硼砂、 氧化硼中的一种或多种。
[0018] 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：
[0019] ( 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;
[0020] (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；
[0021] (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。
[0022] 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 x75mmxlmm, 硅胶圈厚度为 2mm。
发明的有益效果 有益效果
[0023] 本发明有益的技术效果在于：
[0024] (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；
[0025] (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
[0026] (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；
[0027] (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。 。
对附图的简要说明
附图说明
[0028] 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。
[0029] 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。
[0030] 图 3为实施例 1所得自修复水凝胶弹性体的修复照片。
本发明的实施方式
[0031] 下面结合附图和实施例， 对本发明进行具体描述。
[0032] 实施例 1
[0033] 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：
[0034] (1) 将 9g N,N-二甲基丙烯酰胺、 lg 2-羟乙基丙烯酸酯、 0.25g
硼砂、 4g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 5min， 再向溶液中通氮气 3min;
[0035] (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；
[0036] (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。
[0037] 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 30mmx75mmxlm m， 硅胶圈厚度为 2mm。
[0038]
[0039] 实施例 2
[0040] 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：
[0041] ( 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 0.05g 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 10min， 再向溶液中通氮气 5min;
[0042] (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；
[0043] (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。
[0044] 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 30mmx75mmxlm m， 硅胶圈厚度为 2mm。
[0045]
[0046] 实施例 3
[0047] 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：
[0048] ( 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 4 min;
[0049] (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；
[0050] (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。
[0051] 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 30mmx75mmxlm m， 硅胶圈厚度为 2mm。
[0052]
[0053] 实施例 4
[0054] 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： [0055] ( 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;
[0056] (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；
[0057] (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。
[0058] 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 30mmx75mmxlm m， 硅胶圈厚度为 2mm。
[0059]
[0060] 实施例 5
[0061] 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：
[0062] ( 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;
[0063] (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；
[0064] (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。
[0065] 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 30mmx75mmxlm m， 硅胶圈厚度为 2mm。
[0066]
[0067] 测试例：
[0068] 将实施例 1制备的自修复水凝胶弹性体从中间切幵， 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。
[0069] 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

权利要求书
[权利要求 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。
[权利要求 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：
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。
[权利要求 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。
[权利要求 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。
[权利要求 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。
[权利要求 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。
[权利要求 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。
[权利要求 8] —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。
[权利要求 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 30mmx75mmxlmm ， 硅胶圈厚度为 2mm。
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