WO2022002278A1 - Conductive microsphere for anisotropic conductive adhesive film and preparation method therefor - Google Patents

Conductive microsphere for anisotropic conductive adhesive film and preparation method therefor Download PDF

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WO2022002278A1
WO2022002278A1 PCT/CN2021/109952 CN2021109952W WO2022002278A1 WO 2022002278 A1 WO2022002278 A1 WO 2022002278A1 CN 2021109952 W CN2021109952 W CN 2021109952W WO 2022002278 A1 WO2022002278 A1 WO 2022002278A1
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microspheres
microsphere
conductive
meth
anisotropic conductive
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PCT/CN2021/109952
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French (fr)
Chinese (zh)
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张竞
郑国栋
郑争
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台州天舒新材料科技有限公司
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Publication of WO2022002278A1 publication Critical patent/WO2022002278A1/en

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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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals

Definitions

  • the present invention is to provide a method for making high-conductivity microspheres and a method for preparing anisotropic conductive adhesive/film.
  • the conductive microspheres are made of hard-core-soft-shell microspheres composed of a highly cross-linked polydivinylbenzene hard core and a linear polymer soft shell, which are then coated with a conductive metal layer on the surface.
  • the degree of cross-linking of polydivinylbenzene hard core microspheres is more than 30%, and it does not deform under hot pressing conditions, while the linear polymer soft shell softens and deforms under hot pressing conditions, and the thickness of the soft shell layer is about the diameter of the core. 8%-20%.
  • the toughness of the hard core makes the microspheres less likely to be broken under hot pressing, which not only ensures the number of effective conductive microspheres, but also increases the pressure operating range for hot pressing.
  • the outer layer of the soft shell microspheres is deformed under hot pressing to form a large contact area with the electrode, which greatly increases the contact conductivity.
  • conductive microspheres formed by electroless plating of conductive metal materials, and anisotropic conductive materials mixed with binder resins are the mainstream direction of microelectronic circuit connection today.
  • Anisotropic conductive materials are widely used in the packaging of microelectronic devices, such as LCD TV screens, personal computers, cameras, and mobile phones.
  • the anisotropic conductive adhesive/film usually needs to apply a certain pressure and temperature during the application process to ensure low contact resistance and fast curing of the adhesive.
  • the temperature will soften the polymer microspheres in the conductive microspheres, and the degree of softening is related to the temperature.
  • the conductive microspheres are deformed while achieving a large contact area and low contact resistance.
  • the application of excessive pressure will cause some of the conductive microspheres to rupture, and the conductive microspheres will lose their conductivity. Especially in the case of uneven distribution of microsphere particles, the breakage rate of conductive microspheres will be higher.
  • the present invention provides a new method for producing "core-shell type" conductive microspheres.
  • the high cross-linked polymer core microspheres in the present invention are measured by hot pressing, and the microspheres are not damaged under the pressure of 150 C o and 80 kg/cm 2 .
  • Each conductive microsphere between the electrodes plays a conductive role, and the number of effective conductive microsphere particles is maintained at a high level.
  • the outer layer of the soft shell is softened under hot pressing conditions, and the area in contact with the electrode is significantly increased, which effectively improves the conductivity of a single conductive microsphere.
  • the conductive microspheres are deformed into ellipses under hot pressing, and the contact area with the electrodes increases, but they cannot form a completely flat contact like soft spheres, and the conductivity of each conductive microsphere cannot be maximized.
  • the increased pressure can increase the conductivity of the single conductive microspheres. However, it will cause the microspheres to rupture, which will damage the conductivity.
  • the only way to increase the overall conductivity is to increase the concentration of conductive microspheres, with the consequence of increasing the risk of short circuits in the horizontal (XY) direction.
  • the 2.5-micron microspheres copolymerized with 25% hydroxyethyl methacrylate and 75% divinylbenzene were used as the starting microspheres (the microspheres were TS025HM microspheres provided by Taizhou Tianshu New Material Technology Co., Ltd., the particle size distribution of the microspheres was The coefficient of variation was 3.0%).
  • 20 g of TS025HM microspheres and 9.5 g of triethylamine were added to a 500 ml round bottom flask containing 200 ml of tetrahydrofuran. Under electromagnetic stirring, 20 g of 2-bromopropionyl bromide was added dropwise to the above mixture, and the reaction continued for 12 hours.
  • Solution B was transferred into solution A with a syringe and magnetically stirred for 10 hours at room temperature. Then use a syringe to transfer solution C into solutions A-B and stir magnetically for 5 hours at room temperature. Filter, wash thoroughly with tetrahydrofuran and methanol. After vacuum drying at 100°C for two hours, 34.1 g of core-shell microspheres were obtained. The particle size of the microspheres was 3.0 microns, and the coefficient of variation of the particle size distribution was 3.5%.
  • the above-mentioned 3.0-micron core-shell microspheres were used as starting microspheres.
  • 30g core-shell microspheres and 3.7 g of tris(2-aminoethyl)amine were added to a 500 ml round bottom flask containing 250 ml of DMF. Under magnetic stirring, the solution was heated to 105°C and the reaction was continued for 5 hours. After cooling, filter and rinse thoroughly with deionized water.
  • the polyamine-modified microspheres were dried under vacuum at 100°C for two hours. The microspheres were analyzed by infrared spectroscopy, and the glycidyl ester groups on the surface of the microspheres were completely converted into amine groups.
  • microsphere surface carrier is activated in the catalyst.
  • the above-mentioned palladium salt-loaded microspheres were added to a 5000 ml round bottom flask containing 1000 ml of distilled water. Under magnetic stirring, the solution was heated to 60°C, 2000 ml of 10% dimethylamine borane (DMAB) was added, and the reaction was continued for 20 minutes. After cooling, filter and rinse thoroughly with deionized water. Palladium-activated microspheres were obtained.
  • DMAB dimethylamine borane
  • composition of the thin electroless copper plating solution is: 20g nickel sulfate, 25g sodium hypophosphite, 15g sodium acetate, 15ml additives, pH value is 4.5.
  • the gold coating is about 70 nm.
  • the gold plating solution is an ordinary plating solution.
  • the 2.9-micron microspheres polymerized with 65% divinylbenzene were used as the starting microspheres (the numbered TS0029-Y microspheres were provided by Taizhou Tianshu New Material Technology Co., Ltd., and the particle size distribution coefficient of variation of the microspheres was 2.6%).
  • the initiator microspheres were obtained.
  • the microspheres were analyzed by infrared spectroscopy, and the hydroxyl groups on the surface of the microspheres were completely converted into 2-bromopropionate groups.
  • microspheres copolymerized with 25% chloromethylstyrene and 75% divinylbenzene were used as the starting microspheres, and the particle size distribution coefficient of variation of the microspheres was 2.8% (the microspheres were provided by Taizhou Tianshu New Material Technology Co., Ltd. TS003CI microspheres).
  • the soft-shell and hard-core conductive microspheres of the present invention can maximize the contact area of the conductive microspheres and improve the conductivity under the condition of hot pressing.
  • the conductive microspheres are not broken under hot pressing conditions. Maintain the effective number of conductive microspheres and improve the conductivity.
  • the soft-shell and hard-core conductive microspheres provided by the present invention can meet the further miniaturization circuit connection requirements of integrated circuits and electronic devices.

Abstract

The present invention belongs to the field of conductive material preparation, and particularly relates to a conductive microsphere for an anisotropic conductive adhesive/film. A "core-shell" microsphere is made by using a monodisperse and highly cross-linked microsphere as a core base sphere, and then grafting a linear polymer onto the surface of the base sphere to form a soft-shell outer layer; and then, a "core-shell" conductive microsphere is made by means of the electroless plating of metals (nickel or silver) and the secondary electrochemical plating of gold on the surface of the microsphere. The invention effectively solves the problem that an existing ordinary conductive microsphere is broken under a large attaching pressure range, which causes a decrease in the number of effective conductive microspheres between electrodes and an increase in the contact resistance.

Description

一种用于异方性导电胶膜的导电微球及其制备方法A kind of conductive microsphere for anisotropic conductive adhesive film and preparation method thereof 技术领域technical field
本发明是要提供一种制作高导电性微球及其用于异方性导电胶/膜制备方法。导电微球由高交联的聚二乙烯苯硬核和线性聚合物软壳组成的硬核软壳微球，后经表面镀覆导电金属层而制成。聚二乙烯苯硬核微球的交联度在30%以上，在热压条件下不变形，线性聚合物软壳 则热压条件下软化而变形，软壳层的厚度约为硬核直径的8%-20%。硬核的坚韧性使微球在热压下不易破裂，既保证了有效导电微球数目，又增加了热压贴合的压力操作范围。软壳微球外层在热压下变形，形成与电极大的接触面积，极大地增加接触导电性。The present invention is to provide a method for making high-conductivity microspheres and a method for preparing anisotropic conductive adhesive/film. The conductive microspheres are made of hard-core-soft-shell microspheres composed of a highly cross-linked polydivinylbenzene hard core and a linear polymer soft shell, which are then coated with a conductive metal layer on the surface. The degree of cross-linking of polydivinylbenzene hard core microspheres is more than 30%, and it does not deform under hot pressing conditions, while the linear polymer soft shell softens and deforms under hot pressing conditions, and the thickness of the soft shell layer is about the diameter of the core. 8%-20%. The toughness of the hard core makes the microspheres less likely to be broken under hot pressing, which not only ensures the number of effective conductive microspheres, but also increases the pressure operating range for hot pressing. The outer layer of the soft shell microspheres is deformed under hot pressing to form a large contact area with the electrode, which greatly increases the contact conductivity.
背景技术Background technique
以树脂微球为基材，经化学镀覆导电金属材料而成的导电微球，并经过与粘合剂树脂混合而成的各向异性导电材料，是现今微电子线路连接的主流方向。异方性导电材料广泛应用于微电子器件的封装，如液晶电视屏、个人电脑、照相机、手机。Using resin microspheres as the base material, conductive microspheres formed by electroless plating of conductive metal materials, and anisotropic conductive materials mixed with binder resins are the mainstream direction of microelectronic circuit connection today. Anisotropic conductive materials are widely used in the packaging of microelectronic devices, such as LCD TV screens, personal computers, cameras, and mobile phones.
技术问题technical problem
异方性导电胶/膜在应用过程中通常要施加一定的压力和温度，以保证较低的接触电阻及粘结剂快速固化。温度会使导电微球中高分子微球软化，软化的程度与温度相关。当压力下进行粘合时，导电微球发生形变，同时达到较大的接触面积，而取得低的接触电阻。但是施加过大的压力会导致部分导电微球破裂，而使导电微球失去导电性。尤其在微球颗粒分布不均匀的情况下，导电微球的破损率会更高。在实际粘合过程中，要从高的贴合压力取得大的接触面积与低的贴合力来减少微球破损率中寻找平衡点，这增加了贴合操作难度。尤其是在粘合不同电子线路，电极数量和电极面积均可能不同，电极间导电微球的数目会有很大的不同。这会直接改变每颗导电微球所承受的压力，导致极难掌控最佳贴合压力。此外，即使取得最佳的贴合压力，导电微球也存在一定的破损率。这使得电极间有效导电微球数目下降，接触电阻增高。The anisotropic conductive adhesive/film usually needs to apply a certain pressure and temperature during the application process to ensure low contact resistance and fast curing of the adhesive. The temperature will soften the polymer microspheres in the conductive microspheres, and the degree of softening is related to the temperature. When bonding is performed under pressure, the conductive microspheres are deformed while achieving a large contact area and low contact resistance. However, the application of excessive pressure will cause some of the conductive microspheres to rupture, and the conductive microspheres will lose their conductivity. Especially in the case of uneven distribution of microsphere particles, the breakage rate of conductive microspheres will be higher. In the actual bonding process, it is necessary to find a balance point from the high bonding pressure to obtain a large contact area and a low bonding force to reduce the breakage rate of the microspheres, which increases the difficulty of the bonding operation. Especially when bonding different electronic circuits, the number of electrodes and electrode area may be different, and the number of conductive microspheres between electrodes will be very different. This directly changes the pressure on each conductive microsphere, making it extremely difficult to control the optimum pressure for the fit. In addition, even with the best bonding pressure, the conductive microspheres still have a certain breakage rate. This reduces the number of effective conductive microspheres between electrodes and increases the contact resistance.
技术解决方案technical solutions
本发明针对上述导电微球缺陷，给出了一种新的“核壳型”导电微球制作方法，“核壳型”导电微球比现有导电微球有更高的导电性，并且对不同贴合压力有很大的忍耐度。即在很大的贴合压力范围，导电微球的接触电阻均可保持一致性。相对高的贴合压力下， 导电微球不产生破裂，保持有效导电微球数目。Aiming at the above-mentioned defects of the conductive microspheres, the present invention provides a new method for producing "core-shell type" conductive microspheres. There is a lot of tolerance for different fitting pressures. That is, the contact resistance of the conductive microspheres can be kept consistent in a wide range of bonding pressure. Under relatively high bonding pressure, the conductive microspheres do not break, and the effective number of conductive microspheres is maintained.
有益效果beneficial effect
本发明中高交联的聚合物内核微球，经热压实测，在150 C o , 80公斤/cm 2压力下，微球无破损。电极间每一粒导电微球都起到导电作用，有效导电微球颗粒数维持在高的水平。 软壳外层在热压条件下软化，与电极接触的面积显著增加，有效地提升了单个导电微球的导电性。 The high cross-linked polymer core microspheres in the present invention are measured by hot pressing, and the microspheres are not damaged under the pressure of 150 C o and 80 kg/cm 2 . Each conductive microsphere between the electrodes plays a conductive role, and the number of effective conductive microsphere particles is maintained at a high level. The outer layer of the soft shell is softened under hot pressing conditions, and the area in contact with the electrode is significantly increased, which effectively improves the conductivity of a single conductive microsphere.
普遍导电微球在热压下变形为椭圆形，与电极接触的面积有所增大，但并不能如软球体，形成完全平面的接触，每个导电微球的导电性不能取得最大化。 压力提高可以使单一导电微球的导电性增加。 但会导致微球破裂，反而损伤导电性。实验结果证实，积水的导电微球在压力超过30kg/ cm 2时，微球的破损率明显增加。因此，对普通导电微球，贴合压力成为了不能两全的一种操作。此外，在有效导电颗粒太较低情况下，增加总体导电性的途径，仅能依靠增加导电微球的浓度，其后果是增加水平方向（X-Y）方向的短路风险。 Generally, the conductive microspheres are deformed into ellipses under hot pressing, and the contact area with the electrodes increases, but they cannot form a completely flat contact like soft spheres, and the conductivity of each conductive microsphere cannot be maximized. The increased pressure can increase the conductivity of the single conductive microspheres. However, it will cause the microspheres to rupture, which will damage the conductivity. The results confirmed that the water conducting microspheres pressure exceeds 2:00 30kg / cm, breakage of the microspheres is significantly increased. Therefore, for ordinary conductive microspheres, the bonding pressure has become an operation that cannot do both. Furthermore, where the effective conductive particles are too low, the only way to increase the overall conductivity is to increase the concentration of conductive microspheres, with the consequence of increasing the risk of short circuits in the horizontal (XY) direction.
附图说明Description of drawings
无附图说明。No accompanying drawings.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
实施例Example 11 。.
（1）微球引发剂。(1) Microsphere initiator.
以25% 甲基丙烯酸羟基乙酯与75%二乙烯苯共聚的2.5微米微球为起始微球（微球为台州天舒新材料科技有限公司提供的TS025HM微球，微球的粒径分布变异系数为3.0%）。将20g的TS025HM微球 和9.5g的三乙基胺加入到含200ml四氢呋喃的500ml圆底烧瓶中。在电磁搅拌下，将20g 2-溴丙酰溴滴加到上述混合液，反应持续12小时。过滤，用去四氢呋喃、甲醇彻底清洗。经真空100℃干燥两小时，得引发剂微球。微球经红外光谱分析，微球表面羟基团被完全转化为2-溴丙酸酯基团。The 2.5-micron microspheres copolymerized with 25% hydroxyethyl methacrylate and 75% divinylbenzene were used as the starting microspheres (the microspheres were TS025HM microspheres provided by Taizhou Tianshu New Material Technology Co., Ltd., the particle size distribution of the microspheres was The coefficient of variation was 3.0%). 20 g of TS025HM microspheres and 9.5 g of triethylamine were added to a 500 ml round bottom flask containing 200 ml of tetrahydrofuran. Under electromagnetic stirring, 20 g of 2-bromopropionyl bromide was added dropwise to the above mixture, and the reaction continued for 12 hours. Filter, wash thoroughly with tetrahydrofuran and methanol. After vacuum drying at 100°C for two hours, the initiator microspheres were obtained. The microspheres were analyzed by infrared spectroscopy, and the hydroxyl groups on the surface of the microspheres were completely converted into 2-bromopropionate groups.
（2）核壳型微球。(2) Core-shell microspheres.
将20.0 g微球引发剂和19.0 g甲基丙烯酸甲基酯加入到含550 ml的四氢呋喃的1000ml圆底烧瓶中 （溶液A），用氮气除氧。 将1.8 g CuBr 和 3.2 g MeCyclam 加入到含150 ml的四氢呋喃的500ml圆底烧瓶中（溶液B）, 用氮气除氧,。将4.0 g甲基丙烯酸环氧丙基酯加入到含250 ml的四氢呋喃的500ml圆底烧瓶中 （溶液C）, 用氮气除氧。用针筒将溶液B转移入溶液A，室温下，磁搅拌10 小时。再用针筒将溶液C转移入溶液A-B，室温下，磁搅拌5 小时。过滤，用去四氢呋喃、甲醇彻底清洗。经真空100℃干燥两小时，得34.1 g核壳型微球。微球的粒径为 3.0微米，粒径分布变异系数为3.5%。20.0 g of the microsphere initiator and 19.0 g of methyl methacrylate were added to a 1000 ml round bottom flask containing 550 ml of tetrahydrofuran (solution A) and deoxygenated with nitrogen. Add 1.8 g of CuBr and 3.2 g of MeCyclam to a 500-ml round-bottom flask (solution B) containing 150 ml of tetrahydrofuran, and deoxygenate with nitrogen. Add 4.0 g of glycidyl methacrylate to a 500 ml round bottom flask containing 250 ml of tetrahydrofuran (solution C) and deoxygenate with nitrogen. Solution B was transferred into solution A with a syringe and magnetically stirred for 10 hours at room temperature. Then use a syringe to transfer solution C into solutions A-B and stir magnetically for 5 hours at room temperature. Filter, wash thoroughly with tetrahydrofuran and methanol. After vacuum drying at 100°C for two hours, 34.1 g of core-shell microspheres were obtained. The particle size of the microspheres was 3.0 microns, and the coefficient of variation of the particle size distribution was 3.5%.
（3）多胺表面修饰。(3) Polyamine surface modification.
以上述3.0微米核壳型微球为起始微球。将30g的核壳型微球 和3.7g的三（2-氨基乙基）胺加入到含250ml的DMF的500ml圆底烧瓶中。在电磁搅拌下，将溶液加热至105℃，反应持续5小时。冷却后过滤，用去离子水彻底清洗。经真空100℃干燥两小时，得多胺修饰的微球。微球经红外光谱分析，微球表面环氧丙基酯基团被完全转化为胺基基团。The above-mentioned 3.0-micron core-shell microspheres were used as starting microspheres. 30g core-shell microspheres and 3.7 g of tris(2-aminoethyl)amine were added to a 500 ml round bottom flask containing 250 ml of DMF. Under magnetic stirring, the solution was heated to 105°C and the reaction was continued for 5 hours. After cooling, filter and rinse thoroughly with deionized water. The polyamine-modified microspheres were dried under vacuum at 100°C for two hours. The microspheres were analyzed by infrared spectroscopy, and the glycidyl ester groups on the surface of the microspheres were completely converted into amine groups.
(4) 微球表面载体在催化剂活化。(4) The microsphere surface carrier is activated in the catalyst.
将30g由上述多胺表面修饰反应得到的多胺修饰后的核壳型微球加入到含1000ml蒸馏水的5000ml圆底烧瓶中。在电磁搅拌下，将溶液加热至60℃，加入1000ml 0.05% (NH)2PdCl4溶液。 反应持续30分钟。冷却后过滤，用去离子水彻底清洗。30 g of the polyamine-modified core-shell microspheres obtained by the above-mentioned polyamine surface modification reaction were added to a 5000 ml round-bottomed flask containing 1000 ml of distilled water. Under magnetic stirring, the solution was heated to 60°C and 1000ml of 0.05% (NH)2PdCl4 solution was added. The reaction continued for 30 minutes. After cooling, filter and rinse thoroughly with deionized water.
将上述载钯盐的微球加入含1000ml蒸馏水的5000ml圆底烧瓶中。在电磁搅拌下，将溶液加热至60℃，加入2000ml 10%的二甲基胺硼烷（DMAB），反应持续20分钟。冷却后过滤，用去离子水彻底清洗。得钯活化微球。The above-mentioned palladium salt-loaded microspheres were added to a 5000 ml round bottom flask containing 1000 ml of distilled water. Under magnetic stirring, the solution was heated to 60°C, 2000 ml of 10% dimethylamine borane (DMAB) was added, and the reaction was continued for 20 minutes. After cooling, filter and rinse thoroughly with deionized water. Palladium-activated microspheres were obtained.
(5) 化学镀表面镀镍。(5) Electroless nickel plating on the surface.
将40g 由上述反应得到的钯活化微球微球加入到含1000ml薄镀化学镀镍液的5000ml圆底烧瓶中。在电磁搅拌下，将溶液加热至90℃。反应持续120分钟。冷却后过滤，用去离子水彻底清洗。得50g镀镍微球，镍镀层约80 纳米。  40 g of the palladium-activated microspheres obtained by the above reaction were added to a 5000 ml round bottom flask containing 1000 ml of electroless nickel plating solution for thin plating. The solution was heated to 90°C under magnetic stirring. The reaction continued for 120 minutes. After cooling, filter and rinse thoroughly with deionized water. 50 g of nickel-plated microspheres were obtained, and the nickel-plated layer was about 80 nanometers. 
薄镀化学镀铜液组成为: 20g硫酸镍、25 g次亚磷酸钠、15 g醋酸钠，15ml 添加剂，pH值为4.5。The composition of the thin electroless copper plating solution is: 20g nickel sulfate, 25g sodium hypophosphite, 15g sodium acetate, 15ml additives, pH value is 4.5.
(6) 滚镀金镀层。(6) Barrel gold plating.
将按上述薄镀方法所得的50 g镀镍核壳型微球加入到四升小型滚镀装置，转速为20/分钟，10安倍电流，电解4.5小时。得镀镍/金微球。金镀层约70 纳米。镀金液为普通电镀液。50 g of nickel-plated core-shell microspheres obtained by the above-mentioned thin plating method were added to a four-liter small barrel plating device, the rotating speed was 20/min, the current was 10 ampere, and the electrolysis was performed for 4.5 hours. Nickel/gold plated microspheres were obtained. The gold coating is about 70 nm. The gold plating solution is an ordinary plating solution.
本发明的实施方式。Embodiments of the present invention.
实施例Example 22 。.
其他步骤同实施例1，不同在于：The other steps are the same as in Example 1, except that:
（1）微球引发剂。(1) Microsphere initiator.
以65%的二乙烯苯聚合的2.9微米微球为起始微球（编号为TS0029-Y微球为台州天舒新材料科技有限公司提供，微球的粒径分布变异系数为2.6%）。 (A)将20g的TS0029-Y微球和2.0 g硼氢化钠加入到含200ml四氢呋喃的500ml圆底烧瓶中，冰浴。将20ml 含8.0 BF 3 g的四氢呋喃溶液滴加入到上述溶液，在电磁搅拌下，室温下，反应持续3小时。然后，加入20ml 冰水，调节pH 至 8，再加入20ml 35% 双氧水。过滤，用去四氢呋喃、甲醇彻底清洗。经真空100℃干燥两小时，得羟基化微球。(B) 将20g的上述羟基化微球 和9.5g的三乙基胺加入到含200ml四氢呋喃的500ml圆底烧瓶中在电磁搅拌下，将20g 2-溴丙酰溴滴加到上述混合液，反应持续12小时。过滤，用去四氢呋喃、甲醇彻底清洗。经真空100℃干燥两小时，得引发剂微球。微球经红外光谱分析，微球表面羟基团被完全转化为2-溴丙酸酯基团。 The 2.9-micron microspheres polymerized with 65% divinylbenzene were used as the starting microspheres (the numbered TS0029-Y microspheres were provided by Taizhou Tianshu New Material Technology Co., Ltd., and the particle size distribution coefficient of variation of the microspheres was 2.6%). (A) 20 g of TS0029-Y microspheres and 2.0 g of sodium borohydride were added to a 500 ml round-bottomed flask containing 200 ml of tetrahydrofuran, ice bath. 20 ml of a tetrahydrofuran solution containing 8.0 BF 3 g was added dropwise to the above solution, and the reaction was continued for 3 hours at room temperature under electromagnetic stirring. Then, add 20ml of ice water to adjust the pH to 8, and then add 20ml of 35% hydrogen peroxide. Filter, wash thoroughly with tetrahydrofuran and methanol. After drying under vacuum at 100°C for two hours, hydroxylated microspheres were obtained. (B) 20g of above-mentioned hydroxylated microspheres and 9.5g of triethylamine were added to a 500ml round-bottomed flask containing 200ml of tetrahydrofuran and under electromagnetic stirring, 20g of 2-bromopropionyl bromide was added dropwise to the above-mentioned mixed solution, The reaction continued for 12 hours. Filter, wash thoroughly with tetrahydrofuran and methanol. After vacuum drying at 100°C for two hours, the initiator microspheres were obtained. The microspheres were analyzed by infrared spectroscopy, and the hydroxyl groups on the surface of the microspheres were completely converted into 2-bromopropionate groups.
实施例Example 33 。.
其他步骤同实施例1，不同在于：The other steps are the same as in Example 1, except that:
（1）微球引发剂。(1) Microsphere initiator.
以25%氯甲基苯乙烯与75%二乙烯苯共聚的3.0微米微球为起始微球，微球的粒径分布变异系数为2.8%（微球为台州天舒新材料科技有限公司提供的TS003CI微球）。The 3.0-micron microspheres copolymerized with 25% chloromethylstyrene and 75% divinylbenzene were used as the starting microspheres, and the particle size distribution coefficient of variation of the microspheres was 2.8% (the microspheres were provided by Taizhou Tianshu New Material Technology Co., Ltd. TS003CI microspheres).
（2）核壳型微球(2) Core-shell microspheres
将20.0 g微球引发剂和19.0 g甲基苯乙烯加入到含550 ml的四氢呋喃的1000ml圆底烧瓶中 （溶液A），用氮气除氧。 将1.8 g CuBr 和 4.0 g bipy 加入到含150 ml的四氢呋喃的500ml圆底烧瓶中（溶液B）, 用氮气除氧,。将4.0 g氯甲基苯乙烯加入到含250 ml的四氢呋喃的500ml圆底烧瓶中 （溶液C）, 用氮气除氧。用针筒将溶液B转移入溶液A，室温下，磁搅拌10小时。再用针筒将溶液C转移入溶液A-B，室温下，磁搅拌5小时。过滤，用去四氢呋喃、甲醇彻底清洗。经真空100℃干燥两小时，得34.1 g核壳型微球。微球的粒径为 3.6微米，粒径分布变异系数为2.9%。Add 20.0 g of microsphere initiator and 19.0 g of methylstyrene to a 1000 ml round bottom flask (solution A) containing 550 ml of tetrahydrofuran and deoxygenate with nitrogen. Add 1.8 g of CuBr and 4.0 g of bipy to a 500-ml round-bottom flask (solution B) containing 150 ml of tetrahydrofuran, deoxygenated with nitrogen,. Add 4.0 g of chloromethylstyrene to a 500 ml round bottom flask containing 250 ml of tetrahydrofuran (solution C) and deoxygenate with nitrogen. Transfer solution B into solution A with a syringe and stir magnetically for 10 hours at room temperature. Then use a syringe to transfer solution C into solutions A-B and stir magnetically for 5 hours at room temperature. Filter, wash thoroughly with tetrahydrofuran and methanol. After vacuum drying at 100°C for two hours, 34.1 g of core-shell microspheres were obtained. The particle size of the microspheres was 3.6 microns, and the coefficient of variation of the particle size distribution was 2.9%.
工业实用性。Industrial applicability.
随着微电子工业的进步，集成电路微型化。电子器件的线路连接技术更加依赖于高性能的异方性导电胶/膜。与现有技术相比，本发明优势是：With the advancement of the microelectronics industry, integrated circuits are miniaturized. The wiring technology of electronic devices relies more on high-performance anisotropic conductive adhesives/films. Compared with the prior art, the advantages of the present invention are:
1、本发明的软壳硬核导电微球在热压条件下，可以最大限度地提高导电微球接触面积，提高导电性。1. The soft-shell and hard-core conductive microspheres of the present invention can maximize the contact area of the conductive microspheres and improve the conductivity under the condition of hot pressing.
2、与普通导电微球相比，在热压条件下导电微球不破碎。维持有效导电微球粿粒数，提高导电性。2. Compared with ordinary conductive microspheres, the conductive microspheres are not broken under hot pressing conditions. Maintain the effective number of conductive microspheres and improve the conductivity.
3、本发明提供的软壳硬核导电微球， 能够满足集成电路及电子器件进一步微型化电路连接要求。3. The soft-shell and hard-core conductive microspheres provided by the present invention can meet the further miniaturization circuit connection requirements of integrated circuits and electronic devices.
序列表自由内容Sequence Listing Free Content
无。none.

Claims (10)

  1. 一种用于异方性导电胶/膜的导电微球，其特征在于，所述的导电微球内层为高交联的聚合物硬核微球，外层为线性聚合物软壳，且外层的表层涂覆铜、银、镍或金作为导电金属层，其中所述的内层硬核微球的交联度在30%以上；内层硬核微球的颗粒粒径在1微米～10微米，外层软壳层的厚度为内层硬核微球直径的8%-20%。A conductive microsphere for anisotropic conductive adhesive/film, characterized in that the inner layer of the conductive microsphere is a highly cross-linked polymer hard core microsphere, and the outer layer is a linear polymer soft shell, and The surface layer of the outer layer is coated with copper, silver, nickel or gold as a conductive metal layer, wherein the cross-linking degree of the inner layer hard core microspheres is more than 30%; the particle size of the inner layer hard core microspheres is 1 micron ~10 microns, and the thickness of the outer soft shell layer is 8%-20% of the diameter of the inner hard core microspheres.
  2. 根据权利要求1所述的一种用于异方性导电胶/膜的导电微球，其特征在于，所述的内层为高交联的聚合物硬核微球，共聚物组成包括由二乙烯苯、苯乙烯、氯甲基苯乙烯、（甲基）丙烯酸羟基乙酯或马来酸酐单体聚合而成。The conductive microsphere for anisotropic conductive adhesive/film according to claim 1, wherein the inner layer is a highly cross-linked polymer hard core microsphere, and the copolymer consists of two It is polymerized from vinylbenzene, styrene, chloromethylstyrene, hydroxyethyl (meth)acrylate or maleic anhydride monomers.
  3. 根据权利要求1所述的一种用于异方性导电胶/膜的导电微球，其特征在于，所述的内层硬核微球的表面被修饰为原子转移聚合反应的引发剂。The conductive microsphere for anisotropic conductive adhesive/film according to claim 1, wherein the surface of the inner hard core microsphere is modified as an initiator of atom transfer polymerization.
  4. 根据权利要求1所述的一种用于异方性导电胶/膜的导电微球，其特征在于，所述的外层为经原子转移聚合反应产生的线性或低交联的聚合物软壳，聚合物组成包括苯乙烯、甲基苯乙烯、甲氧基苯乙烯、氯甲基苯乙烯、羟基苯乙烯、羧基苯乙烯、醛基苯乙烯、（甲基）丙烯酸、（甲基）丙烯酸甲基酯、（甲基）丙烯酸乙基酯、（甲基）丙烯酸丁基酯、（甲基）丙烯酸羟基乙酯、（甲基）丙烯酸环氧丙基酯或（甲基）丙烯酸（二甲基胺）乙基酯。The conductive microsphere for anisotropic conductive adhesive/film according to claim 1, wherein the outer layer is a linear or low cross-linked polymer soft shell produced by atom transfer polymerization , the polymer composition includes styrene, methylstyrene, methoxystyrene, chloromethylstyrene, hydroxystyrene, carboxystyrene, aldehyde styrene, (meth)acrylic acid, (meth)acrylic acid methyl ester, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate or (meth)acrylate (dimethyl) amine) ethyl ester.
  5. 根据权利要求1所述的一种用于异方性导电胶/膜的导电微球，其特征在于，所述的外层包含羟基、羧基、胺基、醛基、环氧基、苯酚基或酸酐官能基团。The conductive microsphere for anisotropic conductive adhesive/film according to claim 1, wherein the outer layer comprises a hydroxyl group, a carboxyl group, an amine group, an aldehyde group, an epoxy group, a phenol group or a Anhydride functional groups.
  6. 根据权利要求1所述的一种用于异方性导电胶/膜的导电微球，其特征在于，所述的外层为聚苯乙烯或聚苯乙烯衍生物，聚（甲基）丙烯酸酯或聚（甲基）丙烯酸酯衍生物或它们的嵌段共聚物。The conductive microsphere for anisotropic conductive adhesive/film according to claim 1, wherein the outer layer is polystyrene or polystyrene derivatives, poly(meth)acrylate Or poly(meth)acrylate derivatives or their block copolymers.
  7. 根据权利要求1所述的一种用于异方性导电胶/膜的导电微球，其特征在于，所述的内层硬核微球选用交联度为30%以上的聚合物微球，交联度在30%-95%范围。A kind of conductive microspheres for anisotropic conductive adhesive/film according to claim 1, characterized in that, the inner layer hard core microspheres are selected from polymer microspheres with a cross-linking degree of more than 30%, The degree of crosslinking is in the range of 30%-95%.
  8. 根据权利要求1所述的一种用于异方性导电胶/膜的导电微球，其特征在于，所述的内层硬核微球的颗粒粒径在2微米～6微米。The conductive microsphere for anisotropic conductive adhesive/film according to claim 1, wherein the particle size of the inner layer hard core microsphere is 2-6 micrometers.
  9. 根据权利要求1所述的一种用于异方性导电胶/膜的导电微球，其特征在于，所述的导电微球的粒径分布变异系数小于10%。The conductive microsphere for anisotropic conductive adhesive/film according to claim 1, wherein the particle size distribution variation coefficient of the conductive microsphere is less than 10%.
  10. 根据权利要求1-9任一所述的一种用于异方性导电胶/膜的导电微球的制备方法，其特征在于，主要包括下述步骤：A kind of preparation method of conductive microspheres for anisotropic conductive adhesive/film according to any one of claims 1-9, is characterized in that, mainly comprises the following steps:
    （1）制备引发剂微球，(1) Preparation of initiator microspheres,
    （2）制备核壳型微球，(2) Preparation of core-shell microspheres,
    （3）制备多胺表面修饰微球，(3) Preparation of polyamine surface-modified microspheres,
    具有能与多胺分子反应的官能团的聚合物微球与多胺反应，以达成胺基修饰微球表面，多胺分子来自乙二胺、丙二胺、二乙基三胺、三乙基四胺、四乙基五胺、三（2-氨基乙基）胺及低分子量聚乙烯亚胺（PEI），Polymer microspheres with functional groups that can react with polyamine molecules react with polyamines to achieve amine group-modified microsphere surfaces. Polyamine molecules are derived from ethylenediamine, propylenediamine, diethyltriamine, triethyltetramine amine, tetraethylpentamine, tris(2-aminoethyl)amine and low molecular weight polyethyleneimine (PEI),
    （4）制备活化微球，(4) Preparation of activated microspheres,
    多胺修饰的微球与铂、钯、锡盐作用，并经还原剂将盐还原为铂、钯、锡或混合金属覆载的活化基球，The polyamine-modified microspheres interact with platinum, palladium, and tin salts, and the salts are reduced to platinum, palladium, tin or mixed metal-loaded activated base spheres by a reducing agent.
    （5）制备导电微球(5) Preparation of conductive microspheres
    （5.1）化学镀表面镀金属薄层，所述的镀铜、银、镍的导电微球的初始镀层厚度为50纳米～150纳米；(5.1) The electroless plating surface is plated with a thin metal layer, and the initial thickness of the conductive microspheres plated with copper, silver and nickel is 50 nanometers to 150 nanometers;
    （5.2）化学镀金属厚层或电滚镀金属厚层，所述的镀铜、银、镍或金的导电微球的镀层厚度为80纳米～150纳米。(5.2) Electroless metal plating thick layer or electric barrel plating metal thick layer, the thickness of the copper, silver, nickel or gold plated conductive microspheres is 80 nanometers to 150 nanometers.
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