WO2017181447A1 - 一种流动型芯片级底部填充胶及其制备方法 - Google Patents

一种流动型芯片级底部填充胶及其制备方法 Download PDF

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WO2017181447A1
WO2017181447A1 PCT/CN2016/081230 CN2016081230W WO2017181447A1 WO 2017181447 A1 WO2017181447 A1 WO 2017181447A1 CN 2016081230 W CN2016081230 W CN 2016081230W WO 2017181447 A1 WO2017181447 A1 WO 2017181447A1
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parts
epoxy resin
filler
reaction kettle
agent
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PCT/CN2016/081230
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English (en)
French (fr)
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闫善涛
王建斌
陈田安
解海华
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烟台德邦科技有限公司
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Publication of WO2017181447A1 publication Critical patent/WO2017181447A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention belongs to the technical field of filling adhesive preparation, and in particular relates to a flow type chip grade underfill rubber and a preparation method thereof.
  • the underfill is widely used in electronic packaging materials.
  • the underfill is usually made of epoxy resin, which has excellent properties such as high toughness, corrosion resistance, high viscosity and good insulation.
  • most of the underfills currently have shortcomings such as high brittleness, low reliability, large internal stress, poor heat resistance, and poor moisture resistance, which can only meet the requirements of secondary packaging.
  • the present invention is directed to the shortcomings of the prior art described above, and provides a flow type chip-level underfill adhesive and a preparation method thereof.
  • a flow type chip-level underfill adhesive the components of which are composed of the following parts by weight: epoxy resin 18 parts to 30 parts, toughening agent 1 part to 3 parts, wetting
  • the dispersing agent is 0.1 part by weight to 1 part
  • the coupling agent is 0.1 part to 1 part
  • the carbon black is 0.1 part to 0.5 part
  • the filler is 50 parts to 70 parts
  • the curing agent is 8 parts to 15 parts.
  • the epoxy resin is a mixture of two or more of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a polycyclic aromatic epoxy resin, and a novolac type epoxy resin.
  • the bisphenol A type epoxy resin is E51, E44 or EPON 825;
  • the bisphenol F type epoxy resin is EPIKOTE 862 or EPIKOTE 983U;
  • the polycyclic aromatic epoxy resin is EPICLON HP4700, EPICLONHP4500 or EPICLONHP4032;
  • the phenolic epoxy resin is DEN 431, DEN 438 or DEN 439 .
  • the beneficial effect of adopting the above further solution is that selecting different types of epoxy resin combinations can more effectively exert the advantages of various epoxy resins, so that thermal stability and thermal expansion coefficient reach an equilibrium point, thereby obtaining excellent comprehensive performance. .
  • the toughening agent is liquid end carboxylated nitrile rubber, methyl vinyl silicone rubber, dimethyl vinyl silicone rubber, methyl phenyl ethylene silicone rubber or methyl diphenyl vinyl silicone rubber.
  • the beneficial effect of the above further solution is that the addition of the toughening agent can adjust the toughness of the cured product, effectively increase the elastic modulus, lower the thermal expansion coefficient, and meet the impact resistance requirements.
  • the wetting and dispersing agent is a fatty alcohol polyoxyethylene ether, a fatty amine polyoxyethylene ether or an alkylphenol ethoxylate.
  • the beneficial effect of using the above further solution is that the addition of the wetting and dispersing agent effectively reduces the viscosity of the system and increases the flow wettability of the system.
  • the coupling agent is ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane or ⁇ -mercaptopropyltrimethoxysilane.
  • the carbon black is a high pigment carbon black.
  • the filler is a spherical silicon fine powder having a particle diameter of less than 15 ⁇ m and an average particle diameter of 1.5 ⁇ m to 7.5 ⁇ m.
  • the beneficial effect of adopting the above further solution is that the maximum particle size of the silicon micropowder is 15 ⁇ m and the average particle diameter is between 1.5 ⁇ m and 7.5 ⁇ m, so that the small gap chip can be quickly and well filled, and the spherical silicon micropowder is selected to make the fluidity of the resin and the filler. Achieve consistency.
  • the curing agent is a modified amine compound or an acid anhydride compound.
  • the modified amine compound is a modified aromatic amine, a modified polyamide or a modified double Cyanamide;
  • the acid anhydride compound is tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride or methylhexahydrophthalic anhydride.
  • a second object of the present invention is to provide a method for preparing a flow type chip-level underfill, which is as follows:
  • the temperature is controlled at 20 to 25 ° C, and 8 to 15 parts of the curing agent is weighed, and it is put into a reaction kettle and stirred under vacuum for 1 to 2 hours, and uniformly mixed to obtain a filling gel.
  • the stirring speed in the steps (1) to (3) was 1000 rpm; and the stirring speed in the step (4) was 300 rpm.
  • step (4) the stirring speed is lowered after the addition of the curing agent, and the heat generated by the stirring can be reduced.
  • the filler in the step (3) is uniformly mixed with other raw materials in the reaction vessel, and then ground in a three-roll mill, and then added to the reaction vessel, and allowed to stand at 40 to 80 °C.
  • the beneficial effect of using the above further solution is that the high temperature conditions facilitate the sufficient wetting and dispersion of the resin and the filler.
  • the vacuum degree of vacuuming in step (4) is less than -0.095 MPa, and nitrogen gas protection is required when the reactor is decompressed.
  • the invention has the beneficial effects that the chip-level underfill glue prepared by the invention does not use any kind of diluent and has the characteristics of fast flow speed, high reliability, low thermal expansion coefficient, high flexural modulus and low hygroscopicity.
  • the addition of the wetting and dispersing agent effectively reduces the viscosity and increases the flow speed. It is more effective to make the fillers evenly dispersed and ensure the reliability of the package components.
  • the invention is further illustrated by the examples and comparative examples.
  • the products obtained in the following examples and comparative examples were tested to test seven performance indexes of viscosity, flowability, water absorption, curing performance, thermal expansion coefficient, elastic modulus and shear strength.
  • Viscosity test using American TA company rheometer, speed 1.5s -1 , temperature 25 ° C, unit Pa ⁇ s.
  • Flow performance test a device consisting of a gap sheet and a cover slip, a slide glass having a gap of 50 ⁇ m (simulating package component gap), and measuring the time required for the product to flow 10 mm at 100 ° C, in units of s.
  • CTE coefficient of thermal expansion test
  • ASTM D696 standard using thermomechanical analysis (TMA) in ⁇ m/m °C.
  • the modulus of elasticity test was tested according to the American ASTM E1142 standard using a dynamic mechanical analyzer (DMA) in units of GPa.
  • DMA dynamic mechanical analyzer
  • Shear strength test curing conditions are cured at 150 ° C for 90 min, according to the Chinese GB / T7124-1986 test method, measuring AL / AL shear strength, unit MPa.
  • a method for preparing a flow type chip-level underfill is as follows:
  • the temperature is controlled at 20 to 25 ° C, and 80 g of methyltetracyanophthalic anhydride is weighed, and the mixture is placed in a reaction vessel and evacuated, and stirred at 300 rpm for 1 to 2 hours, and uniformly mixed to obtain a filling gel.
  • a method for preparing a flow type chip-level underfill is as follows:
  • the temperature is controlled at 20 to 25 ° C, 100 g of modified aromatic amine is weighed, put into a reaction kettle, vacuumed, stirred at 300 rpm for 1 to 2 h, and uniformly mixed to obtain a filling gel.
  • a method for preparing a flow type chip-level underfill is as follows:
  • a method for preparing a flow type chip-level underfill is as follows:
  • the temperature is controlled at 20 to 25 ° C, 150 g of hexahydrophthalic anhydride is weighed, put into a reaction kettle, vacuumed, stirred at 300 rpm for 1 to 2 h, and uniformly mixed to obtain a filling gel.
  • a method for preparing a chip-level underfill the steps are as follows:
  • the temperature is controlled at 20 to 25 ° C, 150 g of hexahydrophthalic anhydride is weighed, put into a reaction kettle, vacuumed, stirred at 300 rpm for 1 to 2 h, and uniformly mixed to obtain a filling gel.
  • a method for preparing a chip-level underfill the steps are as follows:
  • the chip-level underfill produced by the present invention has a curing time longer than that of the second-level underfill, and is faster in flow time than the secondary underfill, so that the glue is filled and cured.
  • This determines that the chip-level underfill produced by the present invention has higher reliability and meets the requirements of the first-level high-density chip-scale package.
  • the addition of the wetting and dispersing agent in the present invention has a significant effect of effectively lowering the viscosity and increasing the flow rate. Since the chip-level underfill does not use any thinner, it has higher reliability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Epoxy Resins (AREA)

Abstract

一种流动型芯片级底部填充胶，其组分按如下重量份组成：环氧树脂18份～30份、增韧剂1份～3份、润湿分散剂0.1份～1份、偶联剂0.1份～1份、炭黑0.1份～0.5份、填料50份～70份和固化剂8份～15份，该填充胶具有热膨胀系数低、弯曲模量高、吸湿性低等特点，所述润湿分散剂的加入有效地降低黏度，增加流动速度，使得填料分散均匀，保证了封装元器件的可靠性。

Description

一种流动型芯片级底部填充胶及其制备方法 技术领域
本发明属于填充胶制备技术领域，尤其涉及一种流动型芯片级底部填充胶及其制备方法。
背景技术
随着电子封装产业日新月异的发展，对电子封装材料也提出了更加苛刻的要求。由于硅材料制成的芯片热膨胀系数远低于基板，为了保护芯片、锡球和焊点并增强芯片的可靠性，底部填充胶被广泛应用于电子封装材料。底部填充胶通常选用环氧树脂体系为材料，它具有韧性高、耐腐蚀、粘性高及绝缘性好等优良性能。但是目前大部分底部填充胶都存在脆性大、可靠性低、内应力大、耐热性差、耐湿气性差等缺点，仅能满足二级封装要求。
发明内容
本发明针对上述现有技术存在的不足，提供一种流动型芯片级底部填充胶及其制备方法。
本发明解决上述技术问题的技术方案如下：一种流动型芯片级底部填充胶，其组分按如下重量份组成：环氧树脂18份～30份、增韧剂1份～3份、润湿分散剂0.1份～1份、偶联剂0.1份～1份、炭黑0.1份～0.5份、填料50份～70份和固化剂8份～15份。
进一步，所述的环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、多环芳香族环氧树脂、酚醛型环氧树脂中的两种以上混合。
更进一步，所述的双酚A型环氧树脂为E51、E44或EPON 825；所述 的双酚F型环氧树脂为EPIKOTE 862或EPIKOTE 983U；所述的多环芳香族环氧树脂为EPICLON HP4700、EPICLONHP4500或EPICLONHP4032；所述的酚醛型环氧树脂为DEN 431、DEN 438或DEN 439。
采用上述进一步方案的有益效果是，选择不同类型的环氧树脂配合，可以更有效的发挥各种环氧树脂的优点，使得热稳定性、热膨胀系数等达到一个平衡点，从而得到优异的综合性能。
进一步，所述的增韧剂为液体端羧基丁腈橡胶、甲基乙烯基硅橡胶、二甲基乙烯硅橡胶、甲基苯基乙烯硅橡胶或甲基二苯基乙烯硅橡胶。
采用上述进一步方案的有益效果是，增韧剂的加入可以调节固化物的韧性，有效的增加弹性模量，降低热膨胀系数，满足抗冲击的要求。
进一步，所述的润湿分散剂为脂肪醇聚氧乙烯醚、脂肪胺聚氧乙烯醚或烷基酚聚氧乙烯醚。
采用上述进一步方案的有益效果是，润湿分散剂的加入有效的降低体系黏度，增加体系流动润湿性。
进一步，所述的偶联剂为β－(3，4－环氧环己基)乙基三甲氧基硅烷、γ－缩水甘油氧基丙基三甲氧基硅烷或γ－巯基丙基三甲氧基硅烷的一种或两种以上混合。
进一步，所述的炭黑为高色素炭黑。
进一步，所述的填料为粒径小于15μm且平均粒径为1.5μm～7.5μm的球形硅微粉。
采用上述进一步方案的有益效果是，硅微粉最大粒径15μm且平均粒径在1.5μm～7.5μm之间，保证小间隙芯片能快速良好的填充，选取球形硅微粉，使得树脂和填料的流动性达到一致。
进一步，所述的固化剂为改性胺类化合物或酸酐类化合物。
更进一步，所述的改性胺类化合物为改性芳香胺、改性聚酰胺或改性双 氰胺；所述的酸酐类化合物为四氢苯酐、六氢苯酐、甲基四氢苯酐或甲基六氢苯酐。
本发明的第二个目的在于提供一种流动型芯片级底部填充胶的制备方法，步骤如下：
(1)称取环氧树脂18份～30份和炭黑0.1份～0.5份，投入反应釜中搅拌0.5～1h，混合均匀后，研磨后投入反应釜中；
(2)称取增韧剂1份～3份、润湿分散剂0.1份～1份和偶联剂0.1份～1份，将其投入反应釜中搅拌1～2h，混合均匀；
(3)称取填料50份～70份，将其投入反应釜中搅拌2～4小时，混合均匀，经研磨后再投入反应釜中，温度控制在40～80℃，静置3～8h；
(4)温度控制在20～25℃，称取固化剂8份～15份，将其投入反应釜中抽真空搅拌1～2h，混合均匀，即得填充胶。
进一步，步骤(1)-(3)中的搅拌转速为1000rpm；步骤(4)中的搅拌转速为300rpm。
采用上述进一步方案的有益效果是，步骤(4)中在加入固化剂后降低搅拌速度，能够降低搅拌产生的热量。
进一步，步骤(3)中的填料在反应釜中与其他原料混合均匀后，经过三辊研磨机研磨后再加入反应釜中，在40～80℃静置。
采用上述进一步方案的有益效果是，高温条件有利于树脂和填料充分润湿分散。
进一步，步骤(4)中抽真空的真空度小于-0.095MPa，反应釜泄压时需通入氮气保护。
本发明的有益效果是：本发明制得的芯片级底部填充胶，不采用任何种类的稀释剂并具有流动速度快、可靠性高、热膨胀系数低、弯曲模量高、吸湿性低等特点，润湿分散剂的加入有效的降低黏度，增加流动速度的作用显 著，更加有效的使得填料分散均匀，保证了封装元器件的可靠性。
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。
通过实施例和比较例进一步说明本发明。对下述实施例和比较例得到的产品进行测试，分别测试其黏度、流动性能、吸水率、固化性能、热膨胀系数、弹性模量、剪切强度七个性能指标。
黏度测试，使用美国TA公司流变仪，转速1.5s-1，温度25℃，单位Pa·s。
流动性能测试，由间隙片和盖玻片、载玻片组成间隙为50μm(模拟封装元器件间隙)的装置，在100℃时测试产品流动10mm所需时间，单位s。
吸水率测试，使用饱和蒸汽测试(PCT)，温度121℃，湿度100％R.H.，时间20h。
固化性能测试，使用示差扫描量热法(DSC)，恒温150℃产品完全固化所需的固化时间，单位min。
热膨胀系数测试(CTE)，依据美国ASTM D696标准，使用热机械分析法(TMA)测试，单位μm/m℃。
弹性模量测试，依据美国ASTM E1142标准，使用动态力学分析仪(DMA)测试，单位GPa。
剪切强度测试，固化条件为150℃下固化90min，依据中国GB/T7124-1986测试方法，测量AL/AL剪切强度，单位MPa。
实施例1
一种流动型芯片级底部填充胶的制备方法，步骤如下：
(1)称取双酚A型环氧树脂E51 80g、酚醛型环氧树脂DEN 431 100g和炭黑5g，投入反应釜中以1000rpm的速度搅拌0.5～1h，混合均匀后，研 磨后投入反应釜中；
(2)称取液体端羧基丁腈橡胶20g、脂肪醇聚氧乙烯醚10g和γ－巯基丙基三甲氧基硅烷5g，将其投入反应釜中以1000rpm的速度搅拌1～2h，混合均匀；
(3)称取平均粒径7.5μm的硅微粉700g，将其投入反应釜中以1000rpm的速度搅拌2～4小时，混合均匀，经研磨后再投入反应釜中，温度控制在40～80℃，静置3～8h；
(4)温度控制在20～25℃，称取甲基四氰苯酐80g，将其投入反应釜中抽真空、以300rpm的速度搅拌1～2h，混合均匀，即得填充胶。
实施例2
一种流动型芯片级底部填充胶的制备方法，步骤如下：
(1)称取双酚F型环氧树脂EPIKOTE 983U 120g、多环芳香族环氧树脂EPICLON HP4700 100g和炭黑5g，投入反应釜中以1000rpm的速度搅拌0.5～1h，混合均匀后，研磨后投入反应釜中；
(2)称取甲基苯基乙烯硅橡胶30g、脂肪胺聚氧乙烯醚10g和β－(3，4－环氧环己基)乙基三甲氧基硅烷5g，将其投入反应釜中搅拌1～2h，混合均匀；
(3)称取平均粒径1.5μm的硅微粉630g，将其投入反应釜中以1000rpm的速度搅拌2～4小时，混合均匀，经研磨后再投入反应釜中，温度控制在40～80℃，静置3～8h；
(4)温度控制在20～25℃，称取改性芳香胺100g，将其投入反应釜中抽真空、以300rpm的速度搅拌1～2h，混合均匀，即得填充胶。
实施例3
一种流动型芯片级底部填充胶的制备方法，步骤如下：
(1)称取双酚A型环氧树脂E44 160g、多环芳香族环氧树脂EPICLON  HP4500 100g和炭黑5g，投入反应釜中以1000rpm的速度搅拌0.5～1h，混合均匀后，研磨后投入反应釜中；
(2)称取二甲基苯基乙烯硅橡胶20g、脂肪胺聚氧乙烯醚5g和β－(3，4－环氧环己基)乙基三甲氧基硅烷10g，将其投入反应釜中以1000rpm的速度搅拌1～2h，混合均匀；
(3)称取平均粒径5μm的硅微粉560g，将其投入反应釜中以1000rpm的速度搅拌2～4小时，混合均匀，经研磨后再投入反应釜中，温度控制在40～80℃，静置3～8h；
(4)温度控制在20～25℃，称取改性双氰胺140g，将其投入反应釜中抽真空、以300rpm的速度搅拌1～2h，混合均匀，即得填充胶。
实施例4
一种流动型芯片级底部填充胶的制备方法，步骤如下：
(1)称取双酚F型环氧树脂EPIKOTE 862环氧树脂150g、酚醛型环氧树脂DEN 439 150g和炭黑5g，投入反应釜中以1000rpm的速度搅拌0.5～1h，混合均匀后，研磨后投入反应釜中；
(2)称取甲基苯基乙烯硅橡胶30g、烷基酚聚氧乙烯醚5g和γ－缩水甘油氧基丙基三甲氧基硅烷10g，将其投入反应釜中以1000rpm的速度搅拌1～2h，混合均匀；
(3)称取平均粒径3μm的硅微粉500g，将其投入反应釜中以1000rpm的速度搅拌2～4小时，混合均匀，经研磨后再投入反应釜中，温度控制在40～80℃，静置3～8h；
(4)温度控制在20～25℃，称取六氢苯酐150g，将其投入反应釜中抽真空、以300rpm的速度搅拌1～2h，混合均匀，即得填充胶。
对比例1
一种芯片级底部填充胶的制备方法，步骤如下：
(1)称取双酚F型环氧树脂EPIKOTE 983U 120g、多环芳香族环氧树脂EPICLON HP4700 100g和炭黑5g，投入反应釜中以1000rpm的速度搅拌0.5～1h，混合均匀后，研磨后投入反应釜中；
(2)称取甲基苯基乙烯硅橡胶30g和β－(3，4－环氧环己基)乙基三甲氧基硅烷5g，将其投入反应釜中以1000rpm的速度搅拌1～2h，混合均匀；
(3)称取平均粒径1.5μm硅微粉630g，将其投入反应釜中以1000rpm的速度搅拌2～4小时，混合均匀，经研磨后再投入反应釜中，温度控制在40～80℃，静置3～8h；
(4)温度控制在20～25℃，称取六氢苯酐150g，将其投入反应釜中抽真空、以300rpm的速度搅拌1～2h，混合均匀，即得填充胶。
对比例2
一种芯片级底部填充胶的制备方法，步骤如下：
(1)称取称取3,4-环氧环己基甲基-3,4-环氧环己基甲酸酯400g、双(7-氧杂双环[4.1.0]3-庚甲基)己二酸酯400g和六氟锑酸盐5g，投入反应釜中以1000rpm的速度搅拌0.5～1h，混合均匀后，研磨后投入反应釜中；
(2)控制温度在15℃～20℃，称取丙烯酸环氧树脂100g、丙烯酸丁酯50g、1,4-丁二醇30g、β－(3，4－环氧环己基)乙基三甲氧基硅烷10g、过氧化苯甲酰3g和炭黑2g投入反应釜中抽真空、以500rpm的速度搅拌2～4h，混合均匀，即得填充胶。
将上述实施例1-4制得的填充胶与对比例1-2制备的填充胶进行性能指标测试，数据结果如表1所示。
表1性能指标比较
Figure PCTCN2016081230-appb-000001
Figure PCTCN2016081230-appb-000002
从表1的数据可以看出，本发明制得的芯片级底部填充胶，在固化时间上长于二级底部填充胶，在流动时间上快于二级底部填充胶，使得胶水在填充及固化过程中形成更少的内部缺陷；在热膨胀系数、吸水率、弯曲模量、剪切强度等方面较二级封装底部填充胶都有明显优势。这就决定了本发明制得的芯片级底部填充胶具有更高的可靠性，符合一级高密度芯片级封装的要求。另外，本发明中润湿分散剂的加入，有效的降低黏度，增加流动速度的作用显著。由于该芯片级底部填充胶不使用任何稀释剂，具有更高的可靠性。
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 (9)

  1. 一种流动型芯片级底部填充胶，其特征在于，其组分按如下重量份组成：环氧树脂18份～30份、增韧剂1份～3份、润湿分散剂0.1份～1份、偶联剂0.1份～1份、炭黑0.1份～0.5份、填料50份～70份和固化剂8份～15份。
  2. 根据权利要求1所述的填充胶，其特征在于，所述的环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂、多环芳香族环氧树脂、酚醛型环氧树脂中的两种以上混合。
  3. 根据权利要求2所述的填充胶，其特征在于，所述的双酚A型环氧树脂为E51、E44或EPON 825；所述的双酚F型环氧树脂为EPIKOTE 862或EPIKOTE 983U；所述的多环芳香族环氧树脂为EPICLON HP4700、EPICLONHP4500或EPICLONHP4032；所述的酚醛型环氧树脂为DEN 431、DEN 438或DEN 439。
  4. 根据权利要求1所述的填充胶，其特征在于，所述的增韧剂为液体端羧基丁腈橡胶、甲基乙烯基硅橡胶、二甲基乙烯硅橡胶、甲基苯基乙烯硅橡胶或甲基二苯基乙烯硅橡胶；
    所述的润湿分散剂为脂肪醇聚氧乙烯醚、脂肪胺聚氧乙烯醚或烷基酚聚氧乙烯醚；
    所述的偶联剂为β－(3，4－环氧环己基)乙基三甲氧基硅烷、γ－缩水甘油氧基丙基三甲氧基硅烷或γ－巯基丙基三甲氧基硅烷的一种或两种以上混合；
    所述的炭黑为高色素炭黑；
    所述的填料为粒径小于15μm且平均粒径为1.5μm～7.5μm的球形硅微粉。
  5. 根据权利要求1所述的填充胶，其特征在于，所述的固化剂为改性胺类化合物或酸酐类化合物。
  6. 根据权利要求5所述的填充胶，其特征在于，所述的改性胺类化合物为改性芳香胺、改性聚酰胺或改性双氰胺；所述的酸酐类化合物为四氢苯酐、六氢苯酐、甲基四氢苯酐或甲基六氢苯酐。
  7. 一种权利要求1所述的流动型芯片级底部填充胶的制备方法，其特征在于，步骤如下：
    (1)称取环氧树脂18份～30份和炭黑0.1份～0.5份，投入反应釜中搅拌0.5～1h，混合均匀，研磨后投入反应釜中；
    (2)称取增韧剂1份～3份、润湿分散剂0.1份～1份和偶联剂0.1份～1份，将其投入反应釜中搅拌1～2h，混合均匀；
    (3)称取填料50份～70份，将其投入反应釜中搅拌2～4小时，混合均匀，经研磨后再投入反应釜中，温度控制在40～80℃，静置3～8h；
    (4)温度控制在20～25℃，称取固化剂8份～15份，将其投入反应釜中抽真空搅拌1～2h，混合均匀，即得填充胶。
  8. 根据权利要求7所述的制备方法，其特征在于，步骤(1)-(3)中的搅拌转速为1000rpm；步骤(4)中的搅拌转速为300rpm。
  9. 根据权利要求7所述的制备方法，其特征在于，步骤(4)中抽真空的真空度小于-0.095MPa，反应釜泄压时通入氮气保护。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111793457A (zh) * 2019-04-09 2020-10-20 安徽米兰士装饰材料有限公司 一种环保新型免砸砖钢化膜防水胶及其制备方法
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* Cited by examiner, † Cited by third party
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CN115820181B (zh) * 2022-12-07 2024-09-27 东莞市新懿电子材料技术有限公司 一种基于复合纳米填料的底部填充胶及其制备方法与应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4536524A (en) * 1981-04-21 1985-08-20 Capsulated Systems, Inc. Microencapsulated epoxy adhesive system
CN102559115A (zh) * 2011-12-22 2012-07-11 烟台德邦科技有限公司 一种芯片级底部填充胶及其制备方法
CN103937433A (zh) * 2014-04-01 2014-07-23 烟台德邦科技有限公司 一种高可靠性环保型底部填充材料及其制备方法
CN105295796A (zh) * 2015-11-27 2016-02-03 烟台德邦科技有限公司 一种高可靠性环氧底部填充胶及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102174241B (zh) * 2010-12-31 2015-04-22 东莞市阿比亚能源科技有限公司 一种用于光伏组件的银浆
CN102863936B (zh) * 2012-10-09 2014-07-02 株洲时代新材料科技股份有限公司 一种加热固化型双组分环氧灌封胶及其制备方法
EP2752437A1 (de) * 2013-01-08 2014-07-09 Sika Technology AG Härter für emissionsarme Epoxidharz-Produkte
CN103923590B (zh) * 2014-04-08 2016-06-08 广东生益科技股份有限公司 一种黑色树脂组合物及用该树脂组合物制备黑色胶膜的方法
CN104497496A (zh) * 2014-12-05 2015-04-08 东莞市海旭新材料技术有限公司 一种适于喷涂/手糊工艺的树脂体系及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4536524A (en) * 1981-04-21 1985-08-20 Capsulated Systems, Inc. Microencapsulated epoxy adhesive system
CN102559115A (zh) * 2011-12-22 2012-07-11 烟台德邦科技有限公司 一种芯片级底部填充胶及其制备方法
CN103937433A (zh) * 2014-04-01 2014-07-23 烟台德邦科技有限公司 一种高可靠性环保型底部填充材料及其制备方法
CN105295796A (zh) * 2015-11-27 2016-02-03 烟台德邦科技有限公司 一种高可靠性环氧底部填充胶及其制备方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111793457A (zh) * 2019-04-09 2020-10-20 安徽米兰士装饰材料有限公司 一种环保新型免砸砖钢化膜防水胶及其制备方法
CN113088035A (zh) * 2021-03-31 2021-07-09 厦门市宜帆达新材料有限公司 一种改性环氧树脂及包含该改性环氧树脂的环氧树脂绝缘材料
CN113637439A (zh) * 2021-08-03 2021-11-12 四川天邑康和通信股份有限公司 应用于光模块核心光器件封装的胶水配方及其调配方法
CN113773776A (zh) * 2021-09-24 2021-12-10 深圳市美之电实业有限公司 一种防水黏合剂的制备方法
CN115521745A (zh) * 2022-10-08 2022-12-27 深圳市安伯斯科技有限公司 一种抗剥离效果好的喇叭磁路胶制备方法

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