Preparation method and application of high-adhesive epoxy molding compound

Abstract

The invention relates to the field of electronic packaging material preparation, and in particular to a preparation method and application of a high-adhesive epoxy molding compound. The epoxy molding compound comprises the following raw materials: 6-12 parts of epoxy resin, 4-7 parts of phenolic resin, 70-85 parts of inorganic filler, 0.1-0.4 parts of accelerator, 0.2-0.5 parts of stress relief agent, 0.1-0.3 parts of adhesion agent and 0.2-1.5 parts of auxiliary agent, wherein the accelerator is any one of azole accelerators, the stress relief agent is lauromacrogol 400, and the adhesion agent is 3-mercaptopropyltrimethoxysilane. The invention adds the accelerator, the stress relief agent and the adhesion agent in the process of preparing the high-adhesive epoxy molding compound, wherein the accelerator can be compounded with the stress relief agent and the adhesion agent for synergistic enhancement, so that the adhesion of the epoxy molding compound to a nickel-plated frame can be significantly improved, and at the same time, the epoxy molding compound can be kept to have good fluidity and mold flow, and the delamination between the epoxy molding compound and the nickel-plated frame can be effectively reduced, and the invention has a wide application prospect.

Description

Technical Field

[0001] The invention relates to the field of electronic packaging material preparation, and in particular to a preparation method of a high-adhesive epoxy molding compound and application thereof. Background Art

[0002] Epoxy resin (EP) has outstanding mechanical properties, bonding properties, electrical insulation and thermal stability, and is widely used in aerospace, automobiles, electronic devices and other fields. Epoxy molding compounds have the advantages of simple production process, low production cost and high reliability, making them widely used in aerospace, photovoltaic, power electrical appliances and other fields. In recent years, with the development of electronic packaging product technology, nickel-plated frames have become a trend in electronic packaging products. However, metal nickel is prone to oxidation reaction when in contact with air, forming a dense oxide protective film, which seriously affects the performance of electronic products.

[0003] At present, epoxy molding compounds have strong adhesion to copper-plated or silver-plated frames, but when such epoxy molding compounds are used for nickel-plated frames, the adhesion is relatively small. In addition, the presence of moisture and stress will cause stratification between the epoxy molding compounds and the nickel-plated metal frames. For example, when moisture comes into contact with the metal frame, it will react with the metal to form hydrated oxides, and the hydrated oxides will further absorb moisture, resulting in a vicious cycle, and eventually leading to stratification between the epoxy molding compounds and the metal frames. As for stress, the thermal expansion coefficients of epoxy molding compounds and metal frames are generally not of the same level and vary greatly. When the materials are heated, different materials have different stresses due to different thermal expansion coefficients. When the stress of one of the materials is greater than the interfacial bonding force, stratification will occur, which causes stratification between the epoxy resin and the nickel-plated metal frame.

[0004] To this end, patent document CN109467880B discloses a method for improving the reliability of semiconductor devices encapsulated by epoxy resin compositions, by spraying a liquid organic substance on the surface of semiconductor devices encapsulated by epoxy molding compound, thereby improving the reliability of semiconductor devices. However, this method is relatively complicated to operate and fails to improve the adhesion of epoxy molding compound to nickel-plated frames. Patent document CN114456755A discloses an epoxy resin composition and its preparation method and application. The invention provides two promoting adhesives. Through the coordination effect between the two promoting adhesives and the metal frame, although the adhesion between the system and the nickel-plated frame is improved, the content of the promoting adhesive is relatively large during the process, which will lead to poor fluidity of the epoxy molding compound, which may affect its normal use.

[0005] Therefore, in view of the above-mentioned related technologies, it is urgent to develop a preparation method and application of a high-adhesive epoxy molding compound. Summary of the invention

[0006] In view of this, the purpose of the present invention is to provide a preparation method of a high-adhesive epoxy molding compound and its application, so as to solve the problem of easy delamination between the epoxy molding compound and the nickel-plated frame in the prior art.

[0007] Based on the above purpose, the present invention provides a preparation method of a high-adhesive epoxy molding compound and its application.

[0008] A high-adhesive epoxy molding compound comprises the following raw materials in parts by weight:

[0009] 6-12 parts of epoxy resin, 4-7 parts of phenolic resin, 70-85 parts of inorganic filler, 0.1-0.4 parts of accelerator, 0.2-0.5 parts of stress release agent, 0.1-0.3 parts of adhesive, 0.2-1.5 parts of auxiliary agent;

[0010] The accelerator is any one of the nitrogen azole accelerators;

[0011] The stress-releasing agent is lauromacrogol 400;

[0012] The adhesive is 3-mercaptopropyltrimethoxysilane.

[0013] Preferably, the epoxy resin is any one of a multifunctional epoxy resin, a phenolic epoxy resin, a biphenyl epoxy resin, an aliphatic epoxy resin, a polyaromatic epoxy resin, a dicyclopentadiene epoxy resin and an o-cresol epoxy resin.

[0014] Preferably, the phenolic resin is any one of a multifunctional phenolic resin, a biphenyl phenolic resin, a biphenyl-phenol phenolic resin, a linear phenolic resin and a phenol aralkyl phenolic resin.

[0015] Preferably, the inorganic filler is any one of silicon dioxide, aluminum oxide, boron nitride, boron carbide and silicon carbide.

[0016] Preferably, the azole accelerator is any one of 3-amino-1,2,4-triazole, 5-aminotetrazolyl and 1H-1,2,3-triazole.

[0017] Preferably, the auxiliary agent includes carbon black, a flame retardant, a release agent and an ion capture agent.

[0018] Preferably, the flame retardant is aluminum hydroxide; the release agent is a mixture of palm wax and polyethylene synthetic wax in a mass ratio of 0.1:0.2; and the ion capture agent is hydrotalcite.

[0019] A method for preparing a high-adhesive epoxy molding compound comprises the following steps:

[0020] Add epoxy resin, phenolic resin, inorganic filler, accelerator, stress release agent, adhesion agent and auxiliary agent into a high-speed mixer in sequence, mix evenly, melt and mix at 60-110°C, cool and crush into powder after removal, and then preform to obtain epoxy molding compound.

[0021] The invention discloses an application of an epoxy molding compound with high bonding strength, wherein the epoxy molding compound is applied to the field of chip packaging, semiconductor packaging, electronic devices and electromechanical product packaging protection.

[0022] Beneficial effects of the present invention:

[0023] The invention can significantly improve the adhesion of the epoxy molding compound to the nickel-plated frame and effectively reduce the delamination between the epoxy molding compound and the nickel-plated frame by adding an accelerator, a stress relief agent and a sealant during the preparation of the epoxy molding compound with high adhesion.

[0024] The accelerator provided by the present invention can produce a chelating effect with the nickel-plated frame to improve the adhesion between the epoxy molding compound and the nickel-plated frame. At the same time, the compounding of the sealant and the stress relief agent can improve the adhesion between the epoxy molding compound and the nickel-plated frame while maintaining the epoxy molding compound having good fluidity and mold flow, thereby effectively improving the comprehensive performance of the epoxy molding compound. DETAILED DESCRIPTION

[0025] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0026] o-Cresol epoxy resin was purchased from Nanya Electronic Materials (Kunshan) Co., Ltd., model number NPCN-701;

[0027] Phenolic resin 1 is a linear phenolic resin purchased from Shandong Shengquan New Materials Co., Ltd., model PF-8010;

[0028] Phenolic resin 2 is a linear phenolic resin purchased from Shandong Shengquan New Materials Co., Ltd., model PF-8011;

[0029] Inorganic filler 1 is spherical silica, purchased from Jiangsu Lianrui New Materials Co., Ltd., model number NQ1130;

[0030] Inorganic filler 2 is angular silica, purchased from Jiangsu Lianrui New Materials Co., Ltd., model DF1200B;

[0031] Accelerator 1 is 3-amino-1,2,4-triazole, purchased from Hubei Longxin Chemical Industry Co., Ltd., CAS No. 61-82-5;

[0032] Accelerator 2 is 5-aminotetrazolyl, purchased from Shandong Nengju Chemical Co., Ltd., CAS No. 4418-61-5;

[0033] Accelerator 3 is 1H-1,2,3-triazole, purchased from Hubei Jianchu Biopharmaceutical Co., Ltd., CAS No. 288-36-8;

[0034] 2-Methylimidazole, purchased from Nanjing Musen Chemical Co., Ltd., CAS No. 693-98-1;

[0035] 2,4-Dimethylimidazole, purchased from Hubei Longxin Chemical Industry Co., Ltd., CAS No. 930-62-1;

[0036] The stress-releasing agent was lauromacrogol 400, purchased from Hubei Longxin Chemical Industry Co., Ltd., with a CAS number of 9043-30-5;

[0037] 3-Mercaptopropyltrimethoxysilane was purchased from Zhuoli (Shanghai) Materials Co., Ltd., CAS No. 4420-74-0;

[0038] Carbon black was purchased from Mitsubishi Corporation of Japan, model number MA-600;

[0039] Aluminum hydroxide was purchased from SHOWA DENKO;

[0040] Palm wax was purchased from East Asia Chemical Co., Ltd.

[0041] Polyethylene synthetic wax was purchased from Clariant, model PED-522;

[0042] Hydrotalcite was purchased from Shanghai Huazhongrong Industry and Trade Co., Ltd.

[0043] Embodiment 1: A method for preparing a high-adhesive epoxy molding compound, comprising the following steps:

[0044] 6g of o-cresol epoxy resin, 2g of phenolic resin 1, 2g of phenolic resin 2, 35g of inorganic filler 1, 35g of inorganic filler 2, 0.1g of accelerator 1, 0.2g of lauroyl alcohol 400, 0.1g of 3-mercaptopropyltrimethoxysilane, 0.35g of carbon black, 0.25g of release agent, 0.4g of flame retardant and 0.3g of ion capture agent are added into a high-speed mixer in sequence, mixed evenly, melt-kneaded at 60°C, removed and cooled and crushed into powdery material, and then preformed to obtain epoxy molding compound.

[0045] Embodiment 2: A method for preparing a high-adhesive epoxy molding compound comprises the following steps:

[0046] 7g of o-cresol epoxy resin, 3g of phenolic resin 1, 2g of phenolic resin 2, 35g of inorganic filler 1, 40g of inorganic filler 2, 0.1g of 2-methylimidazole, 0.1g of accelerator 2, 0.3g of lauroyl alcohol 400, 0.2g of 3-mercaptopropyltrimethoxysilane, 0.35g of carbon black, 0.25g of release agent, 0.4g of flame retardant and 0.3g of ion capture agent are added into a high-speed mixer in sequence, mixed evenly, melt-kneaded at 70°C, removed, cooled and crushed into powdery material, and then preformed to obtain epoxy molding compound.

[0047] Embodiment 3: A method for preparing a high-adhesive epoxy molding compound comprises the following steps:

[0048] 8g of o-cresol epoxy resin, 2g of phenolic resin 1, 3g of phenolic resin 2, 40g of inorganic filler 1, 40g of inorganic filler 2, 0.2g of accelerator 3, 0.4g of lauroyl alcohol 400, 0.3g of 3-mercaptopropyltrimethoxysilane, 0.35g of carbon black, 0.25g of release agent, 0.4g of flame retardant and 0.3g of ion capture agent are added into a high-speed mixer in sequence, mixed evenly, melt-kneaded at 80°C, removed, cooled and crushed into powdery material, and then preformed to obtain epoxy molding compound.

[0049] Embodiment 4: A method for preparing a high-adhesive epoxy molding compound comprises the following steps:

[0050] 9 g of o-cresol epoxy resin, 2 g of phenolic resin 1, 3 g of phenolic resin 2, 40 g of inorganic filler 1, 45 g of inorganic filler 2, 0.3 g of accelerator 4, 0.5 g of lauroyl alcohol 400, 0.1 g of 3-mercaptopropyltrimethoxysilane, 0.35 g of carbon black, 0.25 g of release agent, 0.4 g of flame retardant and 0.3 g of ion capture agent are added into a high-speed mixer in sequence, mixed evenly, melt-kneaded at 90° C., removed, cooled and crushed into powdery material, and then preformed to obtain epoxy molding compound.

[0051] Embodiment 5: A method for preparing a high-adhesive epoxy molding compound comprises the following steps:

[0052] 10g of o-cresol epoxy resin, 3g of phenolic resin 1, 3g of phenolic resin 2, 40g of inorganic filler 1, 45g of inorganic filler 2, 0.4g of accelerator 1, 0.5g of lauroyl alcohol 400, 0.2g of 3-mercaptopropyltrimethoxysilane, 0.35g of carbon black, 0.25g of release agent, 0.4g of flame retardant and 0.3g of ion capture agent are added into a high-speed mixer in sequence, mixed evenly, melt-kneaded at 100°C, removed and cooled and crushed into powdery material, and then preformed to obtain epoxy molding compound.

[0053] Embodiment 6: A method for preparing a high-adhesive epoxy molding compound, comprising the following steps:

[0054] 11g of o-cresol epoxy resin, 3g of phenolic resin 1, 3g of phenolic resin 2, 40g of inorganic filler 1, 45g of inorganic filler 2, 0.1g of accelerator 2, 0.4g of lauroyl alcohol 400, 0.3g of 3-mercaptopropyltrimethoxysilane, 0.35g of carbon black, 0.25g of release agent, 0.4g of flame retardant and 0.3g of ion capture agent are added into a high-speed mixer in sequence, mixed evenly, melt-kneaded at 110°C, removed, cooled and crushed into powdery material, and then pre-formed to obtain epoxy molding compound.

[0055] Embodiment 7: A method for preparing a high-adhesive epoxy molding compound comprises the following steps:

[0056] 12g of o-cresol epoxy resin, 3g of phenolic resin 1, 4g of phenolic resin 2, 40g of inorganic filler 1, 45g of inorganic filler 2, 0.2g of accelerator 3, 0.5g of lauroyl alcohol 400, 0.3g of 3-mercaptopropyltrimethoxysilane, 0.35g of carbon black, 0.25g of release agent, 0.4g of flame retardant and 0.3g of ion capture agent are added into a high-speed mixer in sequence, mixed evenly, melt-kneaded at 110°C, removed, cooled and crushed into powdery material, and then preformed to obtain epoxy molding compound.

[0057] Comparative Example 1:

[0058] Compared with Example 1, the accelerator 1 was not added in the preparation process of the epoxy molding compound in this comparative example, and the remaining steps and parameters were the same, which will not be repeated in this comparative example, and finally the epoxy molding compound was obtained.

[0059] Comparative Example 2:

[0060] Compared with Example 1, in this comparative example, lauromacrogol 400 was not added during the preparation of the epoxy molding compound, and the remaining steps and parameters were the same, which will not be repeated in this comparative example, and finally the epoxy molding compound was obtained.

[0061] Comparative Example 3:

[0062] Compared with Example 1, this comparative example does not add 3-mercaptopropyltrimethoxysilane during the preparation of the epoxy molding compound. The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, the epoxy molding compound is obtained.

[0063] Comparative Example 4:

[0064] Compared with Example 1, in this comparative example, accelerator 1, lauroyl alcohol 400 and 3-mercaptopropyltrimethoxysilane were not added during the preparation of the epoxy molding compound, and the remaining steps and parameters were the same, which will not be repeated in this comparative example, and finally the epoxy molding compound was obtained.

[0065] Performance Testing

[0066] Spiral flow length: Refer to EMMI-1-66 standard, use a mold to measure the spiral flow, under the conditions of 175℃ molding temperature, 6.9MPa injection mold pressure, and 120s hardening time, the spiral flow length is measured, and the unit is cm;

[0067] Metal bonding test: This method measures the bonding strength between epoxy resin molding materials and metal nickel under different temperature conditions. The epoxy molding material compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 are poured into a mold. The molding temperature is 175° C., the injection pressure is 6.9 MPa, and the curing time is 120 seconds. The epoxy resin molding material is encapsulated on the metal nickel surface, and then the bonding strength at different temperatures is tested using a crystal pusher. Five groups of parallel samples are tested for each test, and the average value is taken for statistics.

[0068] Reliability test: First, the epoxy molding compound composition prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was used to encapsulate the required devices using a molding machine, and then the encapsulated nickel-plated frame was placed in an oven at 175° C. for 6 hours. After the nickel-plated frame was taken out, the stratification was analyzed using an ultrasonic scanning microscope. The results are shown in Table 1 below:

[0069] Table 1

[0070]

[0071] Data Analysis:

[0072] As can be seen from Table 1, since no accelerator 1 was added in Comparative Example 1, no lauromacrogol 400 was added in Comparative Example 2, no 3-mercaptopropyltrimethoxysilane was added in Comparative Example 3, and no accelerator 1 was added in Comparative Example 4, and no lauromacrogol 400 and 3-mercaptopropyltrimethoxysilane were added, the comprehensive performance of the epoxy molding compound finally prepared was poor. Among them, since no accelerator 1 was added to Comparative Example 1 and Comparative Example 4, although the flow length was lengthened, the adhesion to the nickel-plated frame was poor, and the addition of accelerator 1 reduced the fluidity of Comparative Example 2 and Comparative Example 3, and since no adhesion agent and stress relief agent were added, the delamination phenomenon was obvious. The epoxy molding compound prepared in Example 1 to Example 7 has a greater adhesion to metallic nickel, better inhibition of delamination, and a better spiral flow length. It can be seen that the epoxy molding compound prepared by the present invention can ensure good adhesion to the nickel-plated frame while also ensuring good fluidity and mold flow of the epoxy molding compound. This may be because the promoter 1 is electron-rich, so that it can produce a chelating effect with metallic nickel, thereby improving the adhesion between the epoxy molding compound and metallic nickel. In addition, the use of the compounded adhesive and the flexible long-chain polylaurin 400 can improve the adhesion between the epoxy molding compound and metallic nickel while maintaining good fluidity and mold flow of the epoxy molding compound, effectively reducing the delamination between the epoxy molding compound and metallic nickel.

[0073] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0074] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A high-adhesive epoxy molding compound, characterized in that: Including the following raw materials by weight: 6-12 parts of epoxy resin, 4-7 parts of phenolic resin, 70-85 parts of inorganic filler, 0.1-0.4 parts of accelerator, 0.2-0.5 parts of stress release agent, 0.1-0.3 parts of adhesive, 0.2-1.5 parts of auxiliary agent; The accelerator is any one of the nitrogen azole accelerators; The stress-releasing agent is lauromacrogol 400; The adhesive is 3-mercaptopropyltrimethoxysilane; The azole accelerator is any one of 3-amino-1,2,4-triazole, 5-aminotetrazolyl and 1H-1,2,3-triazole.

2. The high-adhesive epoxy molding compound according to claim 1, characterized in that: The epoxy resin is any one of multifunctional epoxy resin, phenolic epoxy resin, biphenyl epoxy resin, aliphatic epoxy resin, polyaromatic epoxy resin, dicyclopentadiene epoxy resin, dicyclopentadiene epoxy resin and o-cresol epoxy resin.

3. The high-adhesive epoxy molding compound according to claim 1, characterized in that: The phenolic resin is any one of multifunctional phenolic resin, biphenyl phenolic resin, biphenyl-phenol phenolic resin, linear phenolic resin and phenol aralkyl phenolic resin.

4. The high-adhesive epoxy molding compound according to claim 1, characterized in that: The inorganic filler is any one of silicon dioxide, aluminum oxide, boron nitride, boron carbide and silicon carbide.

5. The high-adhesive epoxy molding compound according to claim 1, characterized in that: The auxiliary agents include carbon black, flame retardant, release agent and ion capture agent.

6. The high-adhesive epoxy molding compound according to claim 5, characterized in that: The flame retardant is aluminum hydroxide; the release agent is obtained by mixing palm wax and polyethylene synthetic wax in a mass ratio of 0.1:0.2; and the ion capture agent is hydrotalcite.

7. A method for preparing a high-adhesive epoxy molding compound according to any one of claims 1 to 6, characterized in that: The following steps are involved: Add epoxy resin, phenolic resin, inorganic filler, accelerator, stress release agent, adhesion agent and auxiliary agent into a high-speed mixer in sequence, mix evenly, melt and mix at 60-110°C, cool and crush into powder after removal, and then preform to obtain epoxy molding compound.

8. The method for preparing a high-adhesive epoxy molding compound according to claim 7, characterized in that: The epoxy molding compound is used in the field of chip packaging, semiconductor packaging, electronic devices and electromechanical product packaging protection.

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