WO2021248724A1 - Underfill resin having stable adhesiveness under high temperature and preparation method therefor - Google Patents

Underfill resin having stable adhesiveness under high temperature and preparation method therefor Download PDF

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WO2021248724A1
WO2021248724A1 PCT/CN2020/114545 CN2020114545W WO2021248724A1 WO 2021248724 A1 WO2021248724 A1 WO 2021248724A1 CN 2020114545 W CN2020114545 W CN 2020114545W WO 2021248724 A1 WO2021248724 A1 WO 2021248724A1
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high temperature
stable adhesion
epoxy resin
mass
underfill adhesive
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PCT/CN2020/114545
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French (fr)
Chinese (zh)
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伍得
廖述杭
王�义
苏峻兴
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武汉市三选科技有限公司
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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • 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
    • 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

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  • the invention belongs to the technical field of underfill glues, and specifically relates to an underfill glue with stable adhesion at high temperature and a preparation method thereof.
  • the underfill is specially designed for wafers. Since the thermal expansion coefficient of silicon wafers is much lower than that of the substrate material, relative displacement will occur during the thermal cycle test, resulting in mechanical fatigue and poor soldering.
  • the underfill glue usually uses the principle of capillary action to penetrate into the bottom of the wafer and then solidify to avoid the displacement of the wafer relative to the substrate. After the chip is packaged, it will experience various high temperature, low temperature, temperature rise and fall, etc. During the high temperature process, the existing underfill glue easily loses its adhesion and fails.
  • the purpose of the present invention is to provide an underfill adhesive with stable adhesion at high temperature and a preparation method thereof.
  • the underfill adhesive with stable adhesion at high temperature contains the following ingredients:
  • the underfill rubber of the present invention further includes a colorant, and the colorant is 0-5 parts by mass, and this mass part does not include the endpoint 0.
  • the epoxy resin adopts bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl type epoxy resin, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate. One or more of.
  • the curing agent adopts one or more of modified amines, mercaptans, acid anhydrides, and phenolic resin curing agents.
  • the latent curing accelerator of the solid powder adopts 2-phenyl-4-methyl-5-hydroxymethylimidazole.
  • liquid latent curing accelerator adopts a modified amine curing accelerator.
  • organic modified bentonite adopts quaternary ammonium salt modified bentonite.
  • the preparation method of the underfill adhesive with stable adhesion at high temperature provided by the present invention includes:
  • the resulting mixture is ground on three rollers and rolled into a jelly;
  • the present invention has the following beneficial effects:
  • the present invention adopts both the latent curing accelerator and the organic modified bentonite, the adhesive force of the obtained filler will not become invalid with the increase of temperature, and it still maintains stable adhesive force at high temperature (150-200 DEG C).
  • the shear bond strength of the underfill adhesive of the present invention on the Cu interface increases with increasing temperature, and the shear bond strength curve at other interfaces is basically flat, although at some interfaces, the shear bond strength The strength curve has a downward trend, but the shear bond strength value is still higher after the decline.
  • Figure 1 is the variation curve of the shear bond strength at the Cu interface of the embodiment and the comparative example with temperature
  • Figure 2 is the change curve of the shear bond strength at the Si interface of the embodiment and the comparative example with temperature
  • Figure 3 is the variation curve of the shear bond strength at the SiNx interface of the embodiment and the comparative example with temperature
  • Figure 4 is the change curve of the shear bond strength at the PI interface of the embodiment and the comparative example with temperature
  • Fig. 5 is the change curve of the shear bond strength at the Solder mask interface of the embodiment and the comparative example with temperature.
  • the underfill adhesive with stable adhesion at high temperature provided by the present invention includes 20-60 parts by mass of epoxy resin, 5-30 parts by mass of curing agent, 0.1-5 parts by mass of solid or liquid latent curing accelerator, 40-80 parts by mass of inorganic filler, 0.3-10 parts by mass of organically modified bentonite; if necessary, 0-5 parts by mass of coloring agent, such as carbon black, may also be included.
  • the weight part of the epoxy resin is preferably 30-50
  • the weight part of the curing agent is preferably 10-25
  • the weight part of the latent curing accelerator is preferably 0.1-0.5
  • the weight part of the organically modified bentonite is preferably 0.5- 1.5.
  • Epoxy resin as the main resin generally can choose bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl type epoxy resin, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylmethyl
  • One or more of conventional epoxy resins such as acid esters, preferably bisphenol F epoxy resin and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate are used at the same time.
  • the curing agent can be selected from one or more of modified amines, mercaptans, acid anhydrides, and phenolic resin curing agents according to needs, preferably modified amine curing agents.
  • the chemical structural formula of the modified amine curing agent is Wherein, R 1 to R 3 are independently selected from hydrocarbon groups having 1 to 6 carbon atoms, that is, R 1 , R 2 , and R 3 are selected from hydrocarbon groups having 1 to 6 carbon atoms, R 1 , R 2 , R 3 Identical, partially identical, or completely different.
  • a solid or liquid latent curing accelerator is selected.
  • the latent curing accelerator refers to a compound that is in an inactive state at room temperature and is activated by heating and functions as a curing accelerator. Choose a latent curing accelerator. Under normal temperature conditions, the viscosity of the underfill glue will not increase within 12 hours, which can significantly extend the use time of the underfill glue.
  • the solid latent curing accelerator in the present invention is preferably 2-phenyl-4-methyl-5-hydroxymethylimidazole in solid powder form, and its chemical structure is For example, 2P4MHZ.
  • the liquid latent curing accelerator is preferably a modified amine curing accelerator, such as fujicure7000 and fujicure7001 among the fujicure series curing agents of Fuji Kasei Corporation.
  • the inorganic filler is selected from well-known inorganic fillers, such as spherical fused silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, magnesium oxide, magnesium silicate, and the like.
  • Organically modified bentonite uses organic modified flaky silicate, and quaternary ammonium salt modified bentonite can be used, such as GARAMITE-1958 bentonite.
  • Organically modified bentonite uses natural bentonite as a raw material, and uses the layered structure of montmorillonite in bentonite and its ability to swell and disperse into colloidal clay particles in water or organic solvents. Through ion exchange technology, its layered structure The negatively charged surface is modified by inserting organic covering agent.
  • Quaternary ammonium salt type cationic modifier is a commonly used bentonite organic modifier.
  • the modified organic bentonite has good high temperature stability and chemical stability.
  • the structure of the solid or liquid latent curing accelerator is easy to combine with the organic modified bentonite. Under high temperature conditions, the cured product can be tightly cross-linked to maintain the stability of the structure, so that the interface adhesion does not decrease.
  • the latent accelerator and the organic modified bentonite are selected to enable the underfill rubber to be cured, and the adhesion of the interface can still be maintained at a high temperature.
  • the formulations of the examples and comparative examples are shown in Table 1.
  • the interface shear bond strength of Examples 1 to 2 and Comparative Examples 1 to 2 are tested.
  • For the test standard see ASTM D1002-2010. Dispens the underfill glue on the test interface.
  • the test interface has Cu, Si, SiNx, PI, and Solder mask (ie, solder mask), and the test results are shown in Table 2.
  • the shear bond strength of the filler on the Cu interface increases with the increase of temperature, and the shear bond strength at other interfaces
  • the curve is basically flat. Although the shear bond strength curve has a downward trend at some interfaces, the shear bond strength value after the decline is still higher than the shear bond strength value of Comparative Examples 1-2. Therefore, it can be seen that the underfill of the present invention has the strongest adhesion stability at high temperatures.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

An underfill resin having stable adhesiveness under high temperature and preparation method therefor, comprising 20~60 parts by mass of epoxy resin, 5~30 parts by mass of curing agent, 0.1~5 parts by mass of solid or liquid latent curing accelerator, 40~80 parts by mass of inorganic filler, 0.3~10 parts by mass of organic modified bentonite, and 0~5 parts by mass of colorant where needed. Since the latent curing accelerator and the organic modified bentonite are simultaneously adopted, adhesiveness of the underfill resin obtained does not weaken with rising temperature, and adhesiveness is kept stable under high temperature.

Description

[根据细则37.2由ISA制定的发明名称]　高温下粘着力稳定的底部填充胶及其制备方法[Name of invention formulated by ISA according to Rule 37.2] 　Underfill adhesive with stable adhesion at high temperature and its preparation method 技术领域Technical field
本发明属于底部填充胶技术领域，具体涉及一种高温下粘着力稳定的底部填充胶及其制备方法。The invention belongs to the technical field of underfill glues, and specifically relates to an underfill glue with stable adhesion at high temperature and a preparation method thereof.
背景技术Background technique
底部填充胶是专为晶片而设计，由于硅质晶片的热膨胀系数比基板材质低很多，因此,在热循环测试中会产生相对位移，导致机械疲牢从而引起不良焊接。底部填充胶通常是利用毛细作用原理来滲透到晶片底部，然后固化，从而避免晶片相对基板的位移。晶片在封装后会经历各种高温、低温、升降温等，高温过程中现有的底部填充胶易失去粘着力，从而发生失效。The underfill is specially designed for wafers. Since the thermal expansion coefficient of silicon wafers is much lower than that of the substrate material, relative displacement will occur during the thermal cycle test, resulting in mechanical fatigue and poor soldering. The underfill glue usually uses the principle of capillary action to penetrate into the bottom of the wafer and then solidify to avoid the displacement of the wafer relative to the substrate. After the chip is packaged, it will experience various high temperature, low temperature, temperature rise and fall, etc. During the high temperature process, the existing underfill glue easily loses its adhesion and fails.
发明内容Summary of the invention
本发明的目的是提供一种高温下粘着力稳定的底部填充胶及其制备方法。The purpose of the present invention is to provide an underfill adhesive with stable adhesion at high temperature and a preparation method thereof.
本发明提供的高温下粘着力稳定的底部填充胶，其含有如下成分：The underfill adhesive with stable adhesion at high temperature provided by the present invention contains the following ingredients:
Figure PCTCN2020114545-appb-000001
Figure PCTCN2020114545-appb-000001
本发明底部填充胶还包括着色剂，所述着色剂为0～5质量份，该质量份不包括端点0。The underfill rubber of the present invention further includes a colorant, and the colorant is 0-5 parts by mass, and this mass part does not include the endpoint 0.
进一步的，环氧树脂采用双酚A环氧树脂、双酚F环氧树脂、联苯型环氧树脂、3,4-环氧环己基甲基3,4-环氧环己基甲酸酯中的一种或多种。Further, the epoxy resin adopts bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl type epoxy resin, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate. One or more of.
进一步的，固化剂采用改性胺类、硫醇类、酸酐类、酚醛树脂类固化剂中的一种或几种。Further, the curing agent adopts one or more of modified amines, mercaptans, acid anhydrides, and phenolic resin curing agents.
进一步的，固态粉末的潜在性固化促进剂采用2-苯基-4-甲基-5-羟甲基咪唑。Furthermore, the latent curing accelerator of the solid powder adopts 2-phenyl-4-methyl-5-hydroxymethylimidazole.
进一步的，液态的潜在性固化促进剂采用改性胺类固化促进剂。Further, the liquid latent curing accelerator adopts a modified amine curing accelerator.
进一步的，有机改性膨润土采用季铵盐改性膨润土。Further, the organic modified bentonite adopts quaternary ammonium salt modified bentonite.
本发明提供的上述高温下粘着力稳定的底部填充胶的制备方法，包括：The preparation method of the underfill adhesive with stable adhesion at high temperature provided by the present invention includes:
将环氧树脂、固化剂、潜在性固化促进剂、无机填料、有机改性膨润土按权利要求1的质量份混合；Mix the epoxy resin, curing agent, latent curing accelerator, inorganic filler, and organically modified bentonite according to the mass parts of claim 1;
所得混合物在三滚筒上研磨，辊成胶状物；The resulting mixture is ground on three rollers and rolled into a jelly;
对膏状物进行真空脱泡。Vacuum degas the paste.
和现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明同时采用潜在性固化促进剂和有机改性膨润土，所得填充胶的粘着力不会随温度升高而失效，其在高温(150～200℃)下仍然保持稳定的粘着力。The present invention adopts both the latent curing accelerator and the organic modified bentonite, the adhesive force of the obtained filler will not become invalid with the increase of temperature, and it still maintains stable adhesive force at high temperature (150-200 DEG C).
参见图1～5，本发明底部填充胶在Cu界面上的剪切粘结强度随温度升高而提高，在其他界面剪切粘结强度曲线基本平缓，虽然在有的界面，剪切粘结强度曲线有下降趋势，但下降后其剪切粘结强度值仍然较高。Referring to Figures 1 to 5, the shear bond strength of the underfill adhesive of the present invention on the Cu interface increases with increasing temperature, and the shear bond strength curve at other interfaces is basically flat, although at some interfaces, the shear bond strength The strength curve has a downward trend, but the shear bond strength value is still higher after the decline.
附图说明Description of the drawings
图1为实施例和对比例在Cu界面的剪切粘结强度随温度的变化曲线；Figure 1 is the variation curve of the shear bond strength at the Cu interface of the embodiment and the comparative example with temperature;
图2为实施例和对比例在Si界面的剪切粘结强度随温度的变化曲线；Figure 2 is the change curve of the shear bond strength at the Si interface of the embodiment and the comparative example with temperature;
图3为实施例和对比例在SiNx界面的剪切粘结强度随温度的变化曲线；Figure 3 is the variation curve of the shear bond strength at the SiNx interface of the embodiment and the comparative example with temperature;
图4为实施例和对比例在PI界面的剪切粘结强度随温度的变化曲线；Figure 4 is the change curve of the shear bond strength at the PI interface of the embodiment and the comparative example with temperature;
图5为实施例和对比例在Solder mask界面的剪切粘结强度随温度的变化曲线。Fig. 5 is the change curve of the shear bond strength at the Solder mask interface of the embodiment and the comparative example with temperature.
具体实施方式detailed description
本发明提供的高温下粘着力稳定的底部填充胶，包括20～60质量份的环氧树脂，5～30质量份的固化剂，0.1～5质量份的固态或液态的潜在性固化促进剂，40～80质量份的无机填料，0.3～10质量份的有机改性膨润土；根据需要还可以包括0～5质量份的着色剂，例如炭黑。其中，环氧树脂的重量份优选为30～50，固化剂的重量份优选为10～25，潜在性固化促进剂的重量份优选为0.1～0.5，有机改性膨润土的重量份优选为0.5～1.5。The underfill adhesive with stable adhesion at high temperature provided by the present invention includes 20-60 parts by mass of epoxy resin, 5-30 parts by mass of curing agent, 0.1-5 parts by mass of solid or liquid latent curing accelerator, 40-80 parts by mass of inorganic filler, 0.3-10 parts by mass of organically modified bentonite; if necessary, 0-5 parts by mass of coloring agent, such as carbon black, may also be included. Among them, the weight part of the epoxy resin is preferably 30-50, the weight part of the curing agent is preferably 10-25, the weight part of the latent curing accelerator is preferably 0.1-0.5, and the weight part of the organically modified bentonite is preferably 0.5- 1.5.
环氧树脂作为主体树脂，一般可选用双酚A环氧树脂、双酚F环氧树脂、联苯型环氧树脂、3,4-环氧环己基甲基3,4-环氧环己基甲酸酯等常规环氧树脂中的一种或多种，优选同时采用双酚F环氧树脂和3,4-环氧环己基甲基3,4-环氧环己基甲酸酯。Epoxy resin as the main resin, generally can choose bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl type epoxy resin, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylmethyl One or more of conventional epoxy resins such as acid esters, preferably bisphenol F epoxy resin and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate are used at the same time.
固化剂可根据需要选用改性胺类、硫醇类、酸酐类、酚醛树脂类固化剂中的一种或几种，优选改性胺类固化剂。改性胺类固化剂的化学结构式为
Figure PCTCN2020114545-appb-000002
其中，R 1～R 3彼此独立地表示选自碳原子数1～6的烃基，即R 1、R 2、R 3选自碳原子数1～6的烃基，R 1、R 2、R 3完全相同、部分相同或完全不同。 The curing agent can be selected from one or more of modified amines, mercaptans, acid anhydrides, and phenolic resin curing agents according to needs, preferably modified amine curing agents. The chemical structural formula of the modified amine curing agent is
Figure PCTCN2020114545-appb-000002
Wherein, R 1 to R 3 are independently selected from hydrocarbon groups having 1 to 6 carbon atoms, that is, R 1 , R 2 , and R 3 are selected from hydrocarbon groups having 1 to 6 carbon atoms, R 1 , R 2 , R 3 Identical, partially identical, or completely different.
底部填充胶通常使用液态咪唑类促进剂，例如2E4MZ促进剂，导致底部填充胶常温下固化速度较快，粘度增大较快，使用时效很短。本发明则选用固态或液态的潜在性固化促进剂，潜在性固化促进剂指室温下为不活泼状态，而加热使其活化并作为固化促进剂发挥功能的化合物。选择潜在性固化促进剂，在常温条件下，底部填充胶在12h内粘度不会增大，可显著延长底部填充胶的使用时效。Underfills usually use liquid imidazole accelerators, such as 2E4MZ accelerators, which result in faster curing of underfills at room temperature, rapid increase in viscosity, and short use time. In the present invention, a solid or liquid latent curing accelerator is selected. The latent curing accelerator refers to a compound that is in an inactive state at room temperature and is activated by heating and functions as a curing accelerator. Choose a latent curing accelerator. Under normal temperature conditions, the viscosity of the underfill glue will not increase within 12 hours, which can significantly extend the use time of the underfill glue.
本发明中固态潜在性固化促进剂优选固态粉末状的2-苯基-4-甲基-5-羟甲基咪唑，其化学结构式为
Figure PCTCN2020114545-appb-000003
例如2P4MHZ。液态潜在性固化促进剂优选改性胺类固化促进剂，例如日本富士化成公司的fujicure系列固化剂之中的fujicure7000、fujicure7001。 The solid latent curing accelerator in the present invention is preferably 2-phenyl-4-methyl-5-hydroxymethylimidazole in solid powder form, and its chemical structure is
Figure PCTCN2020114545-appb-000003
For example, 2P4MHZ. The liquid latent curing accelerator is preferably a modified amine curing accelerator, such as fujicure7000 and fujicure7001 among the fujicure series curing agents of Fuji Kasei Corporation.
无机填料选用公知的无机填料，例如球状熔融二氧化硅、结晶二氧化硅、氧化铝、氮化硼、氮化铝、氮化硅、氧化镁、硅酸镁等。The inorganic filler is selected from well-known inorganic fillers, such as spherical fused silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, magnesium oxide, magnesium silicate, and the like.
有机改性膨润土采用有机物改性片状硅酸盐，可选用季铵盐改性膨润土，例如GARAMITE-1958膨润土。有机改性膨润土其以天然膨润土为原料，利用膨润土中蒙脱石的层片状结构及其能在水或有机溶剂中溶胀分散成胶体级粘粒特性，通过离子交换技术在其层片状结构中带负电荷的表面被改性，插入有机覆盖剂制成。季铵盐型的阳离子改性剂是一种常用的膨润土有机改性剂。改性后的有机膨润土具有良好的高温稳定性及化学稳定性。而固态或液态潜在性固化促进剂的结构易与有机改性膨润土相结合，在高温条件下，固化物能紧密交联，能保持结构的稳定，从而界面粘着力不降低。本发明通过选择潜在性促进剂和有机改性膨润土，来使底部填充胶固化后，在高温下仍能保持界面粘着力不降低。Organically modified bentonite uses organic modified flaky silicate, and quaternary ammonium salt modified bentonite can be used, such as GARAMITE-1958 bentonite. Organically modified bentonite uses natural bentonite as a raw material, and uses the layered structure of montmorillonite in bentonite and its ability to swell and disperse into colloidal clay particles in water or organic solvents. Through ion exchange technology, its layered structure The negatively charged surface is modified by inserting organic covering agent. Quaternary ammonium salt type cationic modifier is a commonly used bentonite organic modifier. The modified organic bentonite has good high temperature stability and chemical stability. The structure of the solid or liquid latent curing accelerator is easy to combine with the organic modified bentonite. Under high temperature conditions, the cured product can be tightly cross-linked to maintain the stability of the structure, so that the interface adhesion does not decrease. In the present invention, the latent accelerator and the organic modified bentonite are selected to enable the underfill rubber to be cured, and the adhesion of the interface can still be maintained at a high temperature.
为了使本发明的目的、技术方案及有益效果更加清楚明白，以下将结合实施例和对比例，来进一步详细说明本发明的技术效果。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions, and beneficial effects of the present invention clearer, the technical effects of the present invention will be further described in detail below in conjunction with embodiments and comparative examples. It should be understood that the specific embodiments described here are only used to explain the present invention, but not used to limit the present invention.
实施例和对比例配方见表1，对实施例1～2及对比例1～2进行界面剪切粘结强度检测，检测标准参见ASTM D1002-2010，将底部填充胶点胶于测试界面上一5mm*5mm的区域，经150℃固化1h后，用万能拉力机测试分别25℃、150℃、200℃下的剪切粘结强度。本实施例测试界面有Cu、Si、SiNx、PI、Solder mask(即阻焊层)，检测结果见表2。The formulations of the examples and comparative examples are shown in Table 1. The interface shear bond strength of Examples 1 to 2 and Comparative Examples 1 to 2 are tested. For the test standard, see ASTM D1002-2010. Dispens the underfill glue on the test interface. In the area of 5mm*5mm, after curing at 150°C for 1 hour, use a universal tensile machine to test the shear bond strength at 25°C, 150°C, and 200°C. In this embodiment, the test interface has Cu, Si, SiNx, PI, and Solder mask (ie, solder mask), and the test results are shown in Table 2.
表1 实施例和对比例的配方Table 1 Formulas of Examples and Comparative Examples
Figure PCTCN2020114545-appb-000004
Figure PCTCN2020114545-appb-000004
Figure PCTCN2020114545-appb-000005
Figure PCTCN2020114545-appb-000005
表2 实施例和对比例的剪切粘结强度Table 2 Shear bond strength of Examples and Comparative Examples
Figure PCTCN2020114545-appb-000006
Figure PCTCN2020114545-appb-000006
Figure PCTCN2020114545-appb-000007
Figure PCTCN2020114545-appb-000007
基于表2的剪切粘结强度作出图1～5所示的剪切粘结强度随温度的变化曲线，从图1～5可以明显看出，当采用普通固化促进剂并添加有机改性膨润土时(即对比例1)，随着温度升高，填充胶在Cu、Si、Solder mask界面上的剪切粘结强度基本平缓，但有下降趋势；但在SiNx和PI界面上，则随温度升高下降。当采用潜在性固化促进剂但不添加有机改性膨润土时(即对比例2)，不管在哪种界面，随着温度升高，填充胶的剪切粘结强度均是急剧下降。当同时采用潜在性固化促进剂和有机改性膨润土时(即实施例1～2)，填充胶在Cu界面上的剪切粘结强度随温度升高而提高，在其他界面剪切粘结强度曲线基本平缓，虽然在有的界面，剪切粘结强度曲线有下降趋势，但下降后其剪切粘结强度值仍然高于对比例1～2的剪切粘结强度值。因此可以看出，本发明底部填充胶高温下粘着力稳定性最强。Based on the shear bond strength in Table 2, the curves of shear bond strength with temperature shown in Figures 1 to 5 are drawn. It is obvious from Figures 1 to 5 that when common curing accelerators are used and organic modified bentonite is added (Ie Comparative Example 1), as the temperature increases, the shear bond strength of the filler on the Cu, Si, and Solder mask interfaces is basically flat, but there is a downward trend; but at the SiNx and PI interfaces, it changes with temperature. Rise and fall. When a latent curing accelerator is used but no organically modified bentonite is added (ie, comparative example 2), no matter what kind of interface, as the temperature increases, the shear bond strength of the filler drops sharply. When latent curing accelerator and organic modified bentonite are used at the same time (i.e. Examples 1-2), the shear bond strength of the filler on the Cu interface increases with the increase of temperature, and the shear bond strength at other interfaces The curve is basically flat. Although the shear bond strength curve has a downward trend at some interfaces, the shear bond strength value after the decline is still higher than the shear bond strength value of Comparative Examples 1-2. Therefore, it can be seen that the underfill of the present invention has the strongest adhesion stability at high temperatures.
上述实施例仅为用来说明本发明技术方案及技术效果，对于本领域内的技术人员，在上述说明基础上还可以做出其他不同形式的变化或变动，而这些属于本发明实质精神而衍生出的其他变化或变动仍属于本发明保护范围。The above-mentioned embodiments are only used to illustrate the technical solutions and technical effects of the present invention. For those skilled in the art, on the basis of the above descriptions, other changes or changes in different forms can be made, and these are derived from the essential spirit of the present invention. Other changes or changes made still belong to the protection scope of the present invention.

Claims (8)

  1. 一种高温下粘着力稳定的底部填充胶，其特征是，其含有如下成分：An underfill adhesive with stable adhesion at high temperatures, which is characterized in that it contains the following ingredients:
    Figure PCTCN2020114545-appb-100001
    Figure PCTCN2020114545-appb-100001
  2. 如权利要求1所述的高温下粘着力稳定的底部填充胶，其特征是：The underfill adhesive with stable adhesion at high temperature according to claim 1, characterized in that:
    还包括着色剂，所述着色剂为0～5质量份，该质量份不包括端点0。A coloring agent is also included, and the coloring agent is 0-5 parts by mass, and this mass part does not include the endpoint 0.
  3. 如权利要求1所述的高温下粘着力稳定的底部填充胶，其特征是：The underfill adhesive with stable adhesion at high temperature according to claim 1, characterized in that:
    所述环氧树脂采用双酚A环氧树脂、双酚F环氧树脂、联苯型环氧树脂、3,4-环氧环己基甲基3,4-环氧环己基甲酸酯中的一种或多种。The epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl type epoxy resin, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate One or more.
  4. 如权利要求1所述的高温下粘着力稳定的底部填充胶，其特征是：The underfill adhesive with stable adhesion at high temperature according to claim 1, characterized in that:
    所述固化剂采用改性胺类、硫醇类、酸酐类、酚醛树脂类固化剂中的一种或几种。The curing agent adopts one or more of modified amines, mercaptans, acid anhydrides, and phenolic resin curing agents.
  5. 如权利要求1所述的高温下粘着力稳定的底部填充胶，其特征是：The underfill adhesive with stable adhesion at high temperature according to claim 1, characterized in that:
    固态粉末的潜在性固化促进剂采用2-苯基-4-甲基-5-羟甲基咪唑。The latent curing accelerator of the solid powder uses 2-phenyl-4-methyl-5-hydroxymethylimidazole.
  6. 如权利要求1所述的高温下粘着力稳定的底部填充胶，其特征是：The underfill adhesive with stable adhesion at high temperature according to claim 1, characterized in that:
    液态的潜在性固化促进剂采用改性胺类固化促进剂。The liquid latent curing accelerator adopts a modified amine curing accelerator.
  7. 如权利要求1所述的高温下粘着力稳定的底部填充胶，其特征是：The underfill adhesive with stable adhesion at high temperature according to claim 1, characterized in that:
    所述有机改性膨润土采用季铵盐改性膨润土。The organic modified bentonite adopts quaternary ammonium salt modified bentonite.
  8. 一种高温下粘着力稳定的底部填充胶的制备方法，其特征是：A preparation method of underfill adhesive with stable adhesion at high temperature, which is characterized by:
    将环氧树脂、固化剂、潜在性固化促进剂、无机填料、有机改性膨润土按权利要求1的质量份混合；Mix the epoxy resin, curing agent, latent curing accelerator, inorganic filler, and organically modified bentonite according to the mass parts of claim 1;
    所得混合物在三滚筒上研磨，辊成胶状物；The resulting mixture is ground on three rollers and rolled into a jelly;
    对膏状物进行真空脱泡。Vacuum degas the paste.
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