A low-warping, moisture-heat-resistant epoxy molding compound and its preparation method and application

Abstract

The present invention provides a low-warping, heat-resistant epoxy molding compound and its preparation method and application. The epoxy molding compound includes the following components by weight: 10 to 15 parts of epoxy monomer, 5 to 10 parts of phenolic epoxy resin, 10 to 20 parts of curing agent, 1 to 5 parts of active diluent, 0.1 to 0.5 parts of accelerator, 100 to 200 parts of silicon dioxide, 0.1 to 0.5 parts of colorant, 0.1 to 1 parts of coupling agent, 5 to 15 parts of high-performance nano-filling particles, and 0.1 to 1 parts of anti-hydrolysis agent; wherein the epoxy monomer includes at least one of naphthol epoxy resin and alicyclic epoxy resin. The present invention reduces the water absorption rate of the epoxy molding compound by silicon dioxide and high-performance nano-filling particles, prevents moisture in the environment from entering the interior of the epoxy molding compound, and combines with the anti-hydrolysis agent to consume a small amount of water vapor entering the interior of the epoxy molding compound, thereby improving the heat-resistant property of the epoxy molding compound as a whole, and also reduces the warpage of the epoxy molding compound after curing.

Description

Technical Field

[0001] The invention belongs to the technical field of integrated circuit packaging, and particularly relates to a low-warping, moisture-heat-resistant epoxy molding compound and a preparation method and application thereof. Background Art

[0002] Epoxy molding compound is an important part of the integrated circuit packaging industry, and is mainly used to protect integrated circuit components from damage by the external environment. With the continuous advancement of integrated circuit packaging technology, the requirements for epoxy molding compound are getting higher and higher. At present, during the curing process of epoxy molding compound, it is easy to absorb moisture in the environment, causing voids; the difference in thermal expansion coefficients of the three materials of substrate, chip and epoxy molding compound can also cause warping; and the poor dispersion of filling materials in epoxy resin can also cause defects such as flow marks and voids, thereby reducing the protective effect of epoxy molding compound on integrated circuit components.

[0003] Therefore, how to provide a low-warping, moisture-heat-resistant epoxy molding compound, reduce the warpage of the epoxy molding compound by adding high-performance nano-filler particles and anti-hydrolysis agents to the base material, and improve the moisture-heat resistance of the epoxy molding compound is a technical problem that technical personnel in this field urgently need to solve. Summary of the invention

[0004] The object of the present invention is to provide a low-warping, moisture-heat-resistant epoxy molding compound and a preparation method and application thereof, so as to solve at least one of the above-mentioned technical problems.

[0005] To achieve the above-mentioned purpose, the first aspect of the present invention provides a low-warping, moisture- and heat-resistant epoxy molding compound, which comprises the following components in parts by weight: 10 to 15 parts of epoxy monomer, 5 to 10 parts of phenolic epoxy resin, 10 to 20 parts of curing agent, 1 to 5 parts of reactive diluent, 0.1 to 0.5 parts of accelerator, 100 to 200 parts of silica, 0.1 to 0.5 parts of colorant, 0.1 to 1 parts of coupling agent, 5 to 15 parts of high-performance nano-filling particles, and 0.1 to 1 parts of anti-hydrolysis agent; wherein the epoxy monomer comprises at least one of naphthol epoxy resin and alicyclic epoxy resin.

[0006] In the first aspect, the high-performance nano-filler particles are made by in-situ polymerization of nano-silica particles by bisphenol F-type epoxy monomer.

[0007] In the first aspect, the anti-hydrolysis agent contains a carbodiimide structure.

[0008] In the first aspect, the curing agent is an acid anhydride curing agent, and the acid anhydride curing agent includes hexahydrophthalic anhydride.

[0009] In the first aspect, the accelerator is an amine accelerator, and the amine accelerator includes N,N-dimethylbenzylamine.

[0010] In the first aspect, the coupling agent is a silane coupling agent, and the silane coupling agent includes γ-glycidyloxypropyltrimethoxysilane.

[0011] In the first aspect, the colorant includes carbon black.

[0012] In the first aspect, the brand of the reactive diluent comprises Syna-Epoxy S-21.

[0013] The second aspect of the present invention provides a method for preparing the low-warping, moisture-resistant and heat-resistant epoxy molding compound as described in the first aspect, the preparation method comprising: adding each component according to its weight proportion into a stirring cup, stirring and mixing, and obtaining a slurry, wherein the weight proportions of each component specifically include: 10 to 15 parts of epoxy monomer, 5 to 10 parts of phenolic epoxy resin, 10 to 20 parts of curing agent, 1 to 5 parts of active diluent, 0.1 to 0.5 parts of accelerator, 100 to 200 parts of silica, 0.1 to 0.5 parts of colorant, 0.1 to 1 parts of coupling agent, 5 to 15 parts of high-performance nano-filling particles, and 0.1 to 1 parts of anti-hydrolysis agent; wherein the epoxy monomer comprises at least one of a naphthol epoxy resin and an alicyclic epoxy resin; transferring the slurry to a three-roll grinder for grinding to obtain a colloid; and vacuum degassing the colloid to obtain an epoxy molding compound.

[0014] The third aspect of the present invention provides an application of the low-warping, moisture-heat-resistant epoxy molding compound described in the first aspect in integrated circuit packaging.

[0015] Beneficial effects:

[0016] The invention provides a low-warping moisture-heat-resistant epoxy molding compound, which comprises the following components by weight: 10-15 parts of epoxy monomer, 5-10 parts of phenolic epoxy resin, 10-20 parts of curing agent, 1-5 parts of active diluent, 0.1-0.5 parts of accelerator, 100-200 parts of silicon dioxide, 0.1-0.5 parts of colorant, 0.1-1 parts of coupling agent, 5-15 parts of high-performance nano-filling particles, and 0.1-1 parts of anti-hydrolysis agent. The epoxy monomer and the phenolic epoxy resin are used as matrix materials, the performance of the epoxy monomer is enhanced by the phenolic epoxy resin, and the curing shrinkage of the epoxy molding compound is reduced; the water absorption rate of the epoxy molding compound is reduced by silicon dioxide and high-performance nano-filling particles, moisture in the environment is prevented from entering the interior of the epoxy molding compound, and a small amount of water vapor entering the interior of the epoxy molding compound is consumed in combination with the anti-hydrolysis agent, thereby improving the moisture-heat resistance of the epoxy molding compound as a whole, and also reducing the warping of the epoxy molding compound after curing. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the embodiments of this specification or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0018] Figure 1 A schematic diagram of the moisture and heat resistance principle of the epoxy molding compound provided by the present invention. DETAILED DESCRIPTION

[0019] The present invention will be described in detail below in conjunction with specific implementations and examples, and the advantages and various effects of the present invention will be more clearly presented. It should be understood by those skilled in the art that these specific implementations and examples are used to illustrate the present invention, rather than to limit the present invention.

[0020] Throughout the specification, unless otherwise specifically stated, the terms used herein should be understood as meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. In the event of a conflict, the present specification takes precedence.

[0021] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or obtained by existing methods.

[0022] The present invention provides a low-warping, moisture-heat-resistant epoxy molding compound, which comprises the following components in parts by weight: 10 to 15 parts of epoxy monomer, 5 to 10 parts of phenolic epoxy resin, 10 to 20 parts of curing agent, 1 to 5 parts of reactive diluent, 0.1 to 0.5 parts of accelerator, 100 to 200 parts of silicon dioxide, 0.1 to 0.5 parts of colorant, 0.1 to 1 parts of coupling agent, 5 to 15 parts of high-performance nano-filling particles, and 0.1 to 1 parts of anti-hydrolysis agent; wherein the epoxy monomer comprises at least one of naphthol epoxy resin and alicyclic epoxy resin.

[0023] Specifically, the present invention provides a low-warping, heat-resistant epoxy molding compound, which comprises the following components by weight: 10 to 15 parts of epoxy monomer, 5 to 10 parts of phenolic epoxy resin, 10 to 20 parts of curing agent, 1 to 5 parts of active diluent, 0.1 to 0.5 parts of accelerator, 100 to 200 parts of silicon dioxide, 0.1 to 0.5 parts of colorant, 0.1 to 1 parts of coupling agent, 5 to 15 parts of high-performance nano-filling particles, and 0.1 to 1 parts of anti-hydrolysis agent; The epoxy monomer and phenolic epoxy resin are used as the matrix materials. The phenolic epoxy resin is used to enhance the performance of the epoxy monomer and reduce the curing shrinkage of the epoxy molding compound. Silica and high-performance nano-filler particles are used to reduce the water absorption of the epoxy molding compound, prevent moisture in the environment from entering the interior of the epoxy molding compound, and combine with anti-hydrolysis agents to consume a small amount of water vapor entering the interior of the epoxy molding compound, thereby improving the moisture and heat resistance of the epoxy molding compound as a whole, and also reducing the warping of the epoxy molding compound after curing.

[0024] The available grades of naphthol epoxy resin include YLSE-900s; the available grades of alicyclic epoxy resin include S-06E; and the available grades of phenolic epoxy resin include N-730A.

[0025] In some possible embodiments, the high-performance nano-filler particles are made by in-situ polymerization of nano-silica particles by bisphenol F-type epoxy monomer.

[0026] This is because the high-performance nano-filler particles prepared by in-situ polymerization of nano-silica particles with bisphenol F epoxy monomers have excellent dispersibility in epoxy resins, which can solve the agglomeration of nano-particles, effectively fill the gaps, make the structure of the cured epoxy molding compound more compact, prevent water vapor from entering, and reduce the water absorption rate of the epoxy molding compound. The optional grades of high-performance nano-filler particles include NANOPOX 500 and EVONIK.

[0027] In some possible embodiments, the anti-hydrolysis agent contains a carbodiimide structure.

[0028] Those skilled in the art will understand that the anti-hydrolysis agent contains a carbodiimide structure (-N=C=N-), which preferentially reacts with water to form a urea group (-NH-CO-NH-), which can further cure the epoxy resin and improve its performance; it can also react with the carboxyl group of the anhydride curing agent after hydrolysis to further consume the moisture inside the epoxy molding compound. The optional grades of anti-hydrolysis agents include HyMax220.

[0029] In some possible embodiments, the curing agent is an acid anhydride curing agent, and the acid anhydride curing agent includes hexahydrophthalic anhydride.

[0030] This is because the use of anhydride curing agents to cure epoxy molding compounds has the advantages of fast curing reaction speed and low curing reaction temperature, and can be widely used in the field of integrated circuit packaging. In the present application, the carboxyl group generated by the anhydride curing agent during the reaction reacts with the carbodiimide structure in the anti-hydrolysis agent to generate a urea group, thereby improving the strength of the epoxy molding compound.

[0031] In some possible embodiments, the accelerator is an amine accelerator, and the amine accelerator includes N,N-dimethylbenzylamine.

[0032] Those skilled in the art will appreciate that selecting an amine accelerator can shorten the curing time and increase the reaction rate.

[0033] In some possible embodiments, the coupling agent is a silane coupling agent, and the silane coupling agent includes γ-glycidyloxypropyltrimethoxysilane.

[0034] This is because the silane coupling agent can react with the inorganic filler and the epoxy resin respectively, building a "molecular bridge" between the inorganic filler and the epoxy resin, which not only improves the compatibility of the two substances, but also improves the bonding strength of the epoxy molding compound.

[0035] In some possible embodiments, the colorant includes carbon black.

[0036] In some possible embodiments, the brand of the reactive diluent includes Syna-Epoxy S-21.

[0037] Those skilled in the art will appreciate that Syna-Epoxy S-21 is a bifunctional active diluent that can participate in the curing reaction to form a cured cross-linking network and improve the mechanical strength of the epoxy molding compound.

[0038] Based on a general inventive concept, the second aspect of the present invention provides a method for preparing the low-warping, moisture-heat-resistant epoxy molding compound as described in the first aspect, the preparation method comprising:

[0039] Add the components in proportion by weight into a stirring cup, stir and mix to obtain a slurry, wherein the proportion by weight of the components specifically includes: 10-15 parts of epoxy monomer, 5-10 parts of phenolic epoxy resin, 10-20 parts of curing agent, 1-5 parts of reactive diluent, 0.1-0.5 parts of accelerator, 100-200 parts of silicon dioxide, 0.1-0.5 parts of colorant, 0.1-1 parts of coupling agent, 5-15 parts of high-performance nano-filling particles, and 0.1-1 parts of anti-hydrolysis agent; wherein the epoxy monomer includes at least one of naphthol epoxy resin and alicyclic epoxy resin;

[0040] The slurry is transferred to a three-roll mill for grinding to obtain a jelly-like substance;

[0041] The colloid is subjected to vacuum degassing to obtain an epoxy molding compound.

[0042] Based on a general inventive concept, the third aspect of the present invention provides an application of the low-warping, moisture-heat-resistant epoxy molding compound described in the first aspect in integrated circuit packaging.

[0043] The present application will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are intended only to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods for which specific conditions are not specified in the following examples are usually measured according to national standards. If there is no corresponding national standard, then the conditions recommended by the manufacturer are followed.

[0044] The components of the epoxy molding compound in Examples 1-6 and Comparative Examples 1-3 are shown in Table 1 below in terms of weight percentage:

[0045] Table 1 Raw material components by weight

[0046]

[0047] The epoxy molding materials provided in Examples 1-6 and Comparative Examples 1-3 were subjected to a rotational viscosity test, a warpage test, and a moisture and heat resistance test. The specific test process is as follows:

[0048] 1. Rotational viscosity test: After the sample is placed at 25°C for 24 hours, use a Brookfield viscometer, place the glue in the 6R sleeve of the viscometer, select the SC4-14 rotor, adjust the viscometer speed to 20rpm, and read the viscosity value after 4 minutes;

[0049] 2. Warpage test method: Apply the glue evenly on the glass slide, bake it at 150℃ for 1 hour, and take it out after natural cooling; remove the residual resin around the glass slide, fix one side of the glass slide, and measure the distance of the glass slide warping with a ruler. This distance is recorded as the warpage;

[0050] 3. Moisture and heat resistance test: The glue is cured at 160℃ / 1h, and the initial Tg and initial modulus of the sample are measured by DMAQ800 instrument; the sample is placed in a steady-state moisture and heat aging life test box, and the humidity is set to 85% and the temperature is set to 130℃, and the Tg and modulus of the sample after aging for 96h and 192h are tested respectively; among them, DMAQ800 (TAInstruments) dynamic thermal mechanical analyzer adopts dual cantilever mode, the heating rate is 5℃ / min, the sample is the sample after curing at 160℃ / 1h, the size is 30mm×10mm×3mm, and the modulus and Tg are measured.

[0051] The test results are shown in Table 2 below:

[0052] Table 2 Test results

[0053]

[0054]

[0055] From the above table, we can see that:

[0056] (1) The experimental data of Comparative Examples 1-3 show that the epoxy molding compound prepared by using a single epoxy resin as the matrix material has a large warpage;

[0057] (2) Compared with Comparative Example 1, the epoxy molding compound prepared in Comparative Example 3 by adding high-performance nano-filling particles and anti-hydrolysis agent has lower warpage, and the Tg and modulus decrease slowly after aging for 96h and 192h under the conditions of humidity of 85% and temperature of 130°C, indicating that the addition of high-performance nano-filling particles and anti-hydrolysis agent can improve the moisture and heat resistance of epoxy molding compound;

[0058] (3) Compared with Comparative Example 3, the warpage of the epoxy molding compound prepared by adding phenolic epoxy resin in Example 1 was significantly reduced;

[0059] (4) It can be seen from the experimental data of Examples 1-6 that in the present application, increasing the solid content can reduce the warping of the epoxy molding compound; due to the addition of phenolic epoxy resin, the epoxy molding compound prepared using alicyclic epoxy resin has better moisture and heat resistance than the epoxy molding compound prepared using naphthol epoxy resin.

[0060] In summary, the present invention enhances the performance of alicyclic epoxy resin or naphthol epoxy resin by phenolic epoxy resin, and simultaneously adds high-performance nano-filler particles and anti-hydrolysis agent to overcome the defect of poor moisture and heat resistance caused by anhydride curing agent, thereby improving the moisture and heat resistance of epoxy molding compound and reducing the warping of epoxy molding compound.

[0061] When anhydride curing agents are used as curing agents to form anhydride epoxy cross-linked networks, the ester bonds in the system will decompose into carboxyl and hydroxyl compounds under high temperature and high humidity conditions, thereby reducing the thermal stability of the epoxy molding compound. The present application improves the moisture and heat resistance of the epoxy molding compound by adding high-performance nano-filler particles and anti-hydrolysis agents. The moisture and heat resistance principle is as follows: Figure 1 As shown: high-performance nano-filler particles solve the agglomeration of nano-particles, effectively fill the gaps, increase the packing density, and block moisture from entering the interior of the epoxy molding compound; under high humidity and high temperature conditions, the anhydride epoxy cross-linking network formed by the anhydride curing agent is decomposed, and the addition of an anti-hydrolysis agent can repair the broken anhydride epoxy cross-linking network, and can also absorb moisture to convert carbodiimide into urea, further curing the epoxy resin, and preventing the occurrence of voids during the curing process, thereby improving the moisture and heat resistance of the epoxy molding compound.

[0062] Finally, it should be noted that the terms "comprises," "includes," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements that are inherent to such process, method, article, or apparatus.

[0063] Although the preferred embodiments of the present invention have been described, those skilled in the art may make other changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0064] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A low-warpage, heat-resistant epoxy molding compound, characterized in that: The epoxy molding compound comprises the following components in parts by weight: 10 to 15 parts of epoxy monomer, 5 to 10 parts of phenolic epoxy resin, 10 to 20 parts of curing agent, 1 to 5 parts of reactive diluent, 0.1 to 0.5 parts of accelerator, 100 to 200 parts of silicon dioxide, 0.1 to 0.5 parts of colorant, 0.1 to 1 parts of coupling agent, 5 to 15 parts of high-performance nano-filling particles, and 0.1 to 1 parts of anti-hydrolysis agent; wherein the epoxy monomer comprises at least one of naphthol epoxy resin and alicyclic epoxy resin; The high-performance nano-filler particles are made by in-situ polymerization of nano-silicon dioxide particles by bisphenol F-type epoxy monomer; The anti-hydrolysis agent contains a carbodiimide structure.

2. The low-warpage, heat-resistant epoxy molding compound according to claim 1, characterized in that: The curing agent is an acid anhydride curing agent, and the acid anhydride curing agent includes hexahydrophthalic anhydride.

3. The low-warpage, moisture-heat-resistant epoxy molding compound according to claim 2, characterized in that: The accelerator is an amine accelerator, and the amine accelerator includes N,N-dimethylbenzylamine.

4. The low-warpage, moisture-heat-resistant epoxy molding compound according to claim 1, characterized in that: The coupling agent is a silane coupling agent, and the silane coupling agent includes γ-glycidyloxypropyltrimethoxysilane.

5. The low warpage heat and moisture resistant epoxy molding compound according to claim 1, characterized in that: The colorant includes carbon black.

6. The low-warpage, heat-resistant epoxy molding compound according to claim 1, characterized in that: The brands of the reactive diluent include Syna-Epoxy S-21.

7. A method for preparing a low-warpage, heat-resistant epoxy molding compound according to any one of claims 1 to 6, characterized in that: The preparation method comprises: Add the components in proportion by weight into a stirring cup, stir and mix to obtain a slurry, wherein the proportion by weight of the components specifically includes: 10-15 parts of epoxy monomer, 5-10 parts of phenolic epoxy resin, 10-20 parts of curing agent, 1-5 parts of reactive diluent, 0.1-0.5 parts of accelerator, 100-200 parts of silicon dioxide, 0.1-0.5 parts of colorant, 0.1-1 parts of coupling agent, 5-15 parts of high-performance nano-filling particles, and 0.1-1 parts of anti-hydrolysis agent; wherein the epoxy monomer includes at least one of naphthol epoxy resin and alicyclic epoxy resin; The slurry is transferred to a three-roll mill for grinding to obtain a jelly-like substance; The colloid is subjected to vacuum degassing to obtain an epoxy molding compound.

8. Use of the low-warpage, moisture-heat-resistant epoxy molding compound according to any one of claims 1 to 6 in integrated circuit packaging.

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