Epoxy resin composition and packaging material

Abstract

The invention discloses an epoxy resin composition and a packaging material. The epoxy resin composition comprises epoxy resin, a curing agent and a stress releasing agent, the structure of the stress releasing agent is as shown in a formula (1): # imgabs0 #, wherein R1 and R2 are independently selected from hydrogen atoms, C1-C3 substituted or unsubstituted alkoxy groups, and C1-C3 substituted or unsubstituted alkyl groups; r3 is selected from at least one of # imgabs 1 #; and n1, n2, n3, n4 and n5 can be independently and respectively an integer from 5 to 20. The epoxy resin provided by the embodiment of the invention is relatively low in warping degree after being cured, and phase separation does not exist.

Description

Technical Field

[0001] The present application relates to the technical field of packaging materials, and in particular to an epoxy resin composition and a packaging material. Background Art

[0002] At present, the integrated circuit industry continues to develop towards higher performance and smaller size, and the chip performance improvement brought by the traditional Moore's Law is gradually approaching the physical limit. As a breakthrough solution, advanced packaging technology has become an important technical route to improve chip integration and performance. In advanced packaging technologies such as Fan-out, 2.5D CoWoS, 3D packaging and chiplet, liquid molding compound (Liquid Molding Compound, LMC) is the core material for wafer reconstruction and multi-chip integration. However, during the wafer reconstruction process, the material needs to undergo complex process flows such as high-temperature reflow, back grinding, and cutting, which puts strict requirements on the warpage control of LMC. The warpage problem not only directly affects the product yield and reliability, but is also a key factor in determining whether high-precision chip interconnection can be achieved. The optimization and improvement of warpage control technology remains a major challenge facing the industry.

[0003] In the related art, a stress release agent (such as nitrile rubber) is generally added to the epoxy resin to reduce the warpage of the cured material. However, the cured material still has a high warpage and a phase separation problem. Summary of the invention

[0004] In view of this, the present application provides an epoxy resin composition and a packaging material, aiming to improve the problems of high warpage of existing packaging materials and phase separation of the cured materials.

[0005] In a first aspect, an embodiment of the present application provides an epoxy resin composition, comprising an epoxy resin, a curing agent, and a stress release agent; the structure of the stress release agent is shown in formula (1):

[0006]

[0007] Wherein, R1 and R2 are each independently selected from a hydrogen atom, a C1 to C3 substituted or unsubstituted alkoxy group, a C1 to C3 substituted or unsubstituted alkyl group; R3 is selected from At least one of; n1, n2, n3, n4 and n5 can independently be an integer of 5-20.

[0008] Optionally, R1 and R2 are each independently selected from a hydrogen atom or a methoxy group; and / or

[0009] The synthetic raw materials of the stress release agent include polyetheramine and allylphenol compounds.

[0010] Optionally, the stress release agent comprises at least one of the structures of formulas (2) to (4):

[0011]

[0012] Optionally, the mass ratio of the stress release agent to the epoxy resin composition is 0.1% to 3% by mass; and / or

[0013] The n1 is an integer of 10-20; and / or

[0014] The n2 is an integer of 5-15; and / or

[0015] The n3, n4 and n5 can be independently integers of 5-8.

[0016] Optionally, the mass ratio of the stress release agent to the epoxy resin composition is 0.1% to 2%.

[0017] Optionally, the epoxy resin composition further comprises an inorganic filler, the inorganic filler accounting for 60% to 93% of the epoxy resin composition by mass; and / or

[0018] The epoxy resin accounts for 2% to 10% of the epoxy resin composition; and / or

[0019] The curing agent accounts for 3% to 10% of the epoxy resin composition; and / or

[0020] The epoxy resin composition further comprises a silane coupling agent, wherein the silane coupling agent accounts for 0.2% to 1% of the epoxy resin composition; and / or

[0021] The epoxy resin composition further comprises a curing accelerator, wherein the curing accelerator accounts for 0.1% to 3% of the epoxy resin composition; and / or

[0022] The epoxy resin composition further includes a colorant, and the colorant accounts for 0.1% to 1% of the epoxy resin composition.

[0023] Optionally, the epoxy resin comprises an epoxy resin that is liquid at room temperature; and / or

[0024] The curing agent comprises at least one of aliphatic amines, aromatic amines, phenolic compounds, acid anhydrides and imidazole compounds; and / or

[0025] The inorganic filler comprises at least one of silicon dioxide, aluminum oxide, aluminum nitride, silicon carbide, boron nitride, zircon, calcium silicate, calcium carbonate and barium titanate; and / or

[0026] The average particle size of the inorganic filler is 2 μm to 100 μm; and / or

[0027] The silane coupling agent includes γ-(2,3-epoxypropyloxy)propyltrimethoxysilane, trimethyloxyphenylsilane, 3-aminopropyltriethoxysilane, 3-(isobutylacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, (3-aminopropyl)triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, At least one of silane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, and γ-anilinomethylethyldimethoxysilane; and / or

[0028] The curing accelerator is an imidazole compound or a tertiary amine salt.

[0029] Optionally, the epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin, naphthalene epoxy resin, aminophenol epoxy resin, polyalkylene glycol epoxy resin, and alicyclic epoxy resin.

[0030] Optionally, the bisphenol F epoxy resin has an epoxy equivalent of 155-165 g / eq; and / or

[0031] The bisphenol A epoxy resin has an epoxy equivalent of 172-176 g / eq; and / or

[0032] The epoxy equivalent of the naphthalene ring epoxy resin is 136-150 g / eq; and / or

[0033] The cycloaliphatic epoxy resin has an epoxy equivalent of 129-131 g / eq; and / or

[0034] By mass, the epoxy resin includes bisphenol F type epoxy resin, bisphenol A type epoxy resin, naphthalene ring epoxy resin and alicyclic epoxy resin, and the bisphenol F type epoxy resin: the bisphenol A type epoxy resin: the naphthalene ring epoxy resin: the alicyclic epoxy resin is (1.35 to 1.41): (1.5 to 1.6): (1.18 to 1.25): (0.79 to 0.85).

[0035] A second aspect of the present application provides a packaging material, wherein the packaging material is formed by curing the epoxy resin composition.

[0036] Beneficial effects:

[0037] In the present application, a stress release agent of formula (1) is added to the epoxy resin composition. The stress release agent has a long flexible chain segment, which can effectively release the internal stress, thereby helping to reduce the warpage of the epoxy resin composition. At the same time, the stress release agent has allyl end-capping, phenolic hydroxyl group, and imino group, which can improve the compatibility with the epoxy group and ensure the uniformity of the resin system structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without paying any creative work.

[0039] Figure 1 Figure a is the surface morphology of the liquid epoxy composition after curing in Example 2 of the present application; Figure b is the surface morphology of the liquid epoxy composition after curing in Comparative Example 2. DETAILED DESCRIPTION

[0040] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0042] In this application, unless otherwise stated, directional words such as "upper" and "lower" generally refer to the upper and lower parts of the device in actual use or working state, specifically the drawing direction in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of this application, the term "including" means "including but not limited to". The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish an order.

[0043] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0044] In the present application, "at least one" means one or more, and "plurality" means two or more. "One or more", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0045] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0046] At present, the integrated circuit industry continues to develop towards higher performance and smaller size, and the chip performance improvement brought by the traditional Moore's Law is gradually approaching the physical limit. As a breakthrough solution, advanced packaging technology has become an important technical route to improve chip integration and performance. In advanced packaging technologies such as Fan-out, 2.5D CoWoS, 3D packaging and chiplet, liquid molding compound (Liquid Molding Compound, LMC) is the core material for wafer reconstruction and multi-chip integration. However, during the wafer reconstruction process, the material needs to undergo complex process flows such as high-temperature reflow, back grinding, and cutting, which puts strict requirements on the warpage control of LMC. The warpage problem not only directly affects the product yield and reliability, but is also a key factor in determining whether high-precision chip interconnection can be achieved. The optimization and improvement of warpage control technology remains a major challenge facing the industry.

[0047] In the related art, a stress release agent (such as nitrile rubber) is generally added to the epoxy resin to reduce the warpage of the cured material. However, the warpage still exists, and the cured material has a phase separation problem.

[0048] In view of this, the embodiments of the present application provide a liquid epoxy resin composition and a preparation method and application thereof, aiming to improve the technical problems of high warpage and phase separation of the existing liquid epoxy resin composition after curing.

[0049] The first aspect of the embodiment of the present application provides an epoxy resin composition, comprising an epoxy resin, a curing agent and a stress release agent; the structure of the stress release agent is shown in formula (1):

[0050]

[0051] Wherein, R1 and R2 are each independently selected from a hydrogen atom, a C1 to C3 substituted or unsubstituted alkoxy group, a C1 to C3 substituted or unsubstituted alkyl group; R3 is selected from At least one of; n1, n2, n3, n4 and n5 can independently be integers of 5-20, that is, n1, n2, n3, n4 and n5 can independently be integers of 5 to 20.

[0052] It should be noted that, among them, the substituted or unsubstituted alkoxy group of C1 to C3 can be a substituted or unsubstituted methoxy group, a substituted or unsubstituted ethoxy group, or a substituted or unsubstituted propoxy group, which is not limited here. Correspondingly, the substituted or unsubstituted alkyl group of C1 to C3 can be a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, or a substituted or unsubstituted propyl group, which is not limited here. It should be noted that if the values ​​of n1, n2, n3, n4 and n5 are too small, for example, less than 5, the flexible chain in the molecular structure of the stress release agent is too short, and its toughening and warpage reduction effects are not obvious. If the values ​​of n1, n2, n3, n4 and n5 are too large, for example, greater than 20, the flexible chain in the molecular structure of the stress release agent is too long, which easily leads to a low modulus of the product after the epoxy resin composition is cured, and the mechanical properties are not ideal.

[0053] In the present application, a stress release agent of formula (1) is added to the epoxy resin composition. The stress release agent has a flexible chain segment of suitable length, which can effectively release internal stress, thereby reducing the warpage of the epoxy resin composition after curing, and having good mechanical properties. At the same time, the stress release agent has allyl end-capping, phenolic hydroxyl group, and imino group, which can improve the compatibility with the epoxy group, ensure the uniformity of the resin system structure, and further improve its mechanical properties.

[0054] In some embodiments of the present application, the stress release agent includes at least one of the structures of formulas (2) to (4):

[0055]

[0056]

[0057] In some embodiments of the present application, the stress release agent has a structure as shown in formula (2). Further, n2 is an integer of 5-15, that is, n2 is an integer of 5 to 15. Exemplarily, n2 is 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15.

[0058] Illustratively, the stress release agent of the structure shown in formula (2) can be prepared by the following synthesis route: a polyetheramine with an average molecular weight of 400 (20.00 g, 0.05 mol), 4-allyl-2-methoxyphenol (16.42 g, 0.1 mol) and formaldehyde (3.00 g, 0.1 mol) are mixed, stirred at 80° C. for 4 h until the reaction liquid becomes clear, and the resulting liquid is vacuum dried at 80° C. for 6 h to obtain a compound of the structure shown in formula (2).

[0059] In some embodiments of the present application, the stress release agent has a structure as shown in formula (3). Further, n1 is an integer of 10-20, that is, n1 is an integer of 10 to 20. Exemplarily, n1 is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0060] For example, the stress release agent of the structure shown in formula (3) can be prepared by the following synthesis route: polyethylene glycol diamine (20.00 g, 0.01 mol) with an average molecular weight of 600, 2-allyl-phenol (13.42 g, 0.1 mol), and formaldehyde (3.00 g, 0.1 mol) are added to a reactor according to a stoichiometric ratio, and the temperature is raised to 60° C. for stirring reaction. After the reaction liquid is clarified (about 4 hours), it is vacuum dried at 80° C. for 6 hours to obtain a compound of the structure shown in formula (3).

[0061] In some embodiments of the present application, the stress release agent has a structure as shown in formula (4). Further, n3, n4 and n5 can be independently integers of 5-8.

[0062] Illustratively, the stress release agent of the structure shown in formula (4) can be prepared by the following synthetic route: a polyetheramine with an average molecular weight of 440 (20.00 g, 0.045 mol), 4-allyl-phenol (13.42 g, 0.1 mol) and formaldehyde (3.00 g, 0.1 mol) are mixed, vigorously stirred at 60°C for 4 h until the reaction liquid becomes clear, and the resulting liquid is vacuum dried at 80°C for 6 h to obtain a compound of formula (4).

[0063] It should be noted that the structural stress release agents shown in formula (2), formula (3) and formula (4) in the present application can also be obtained on the market, and are not limited here. The stress release agent shown in formula (2) can be understood to include at least one of the multiple compounds corresponding to n2 being an integer from 5 to 15. Similarly, the stress release agent shown in formula (3) can be understood to include at least one of the multiple compounds corresponding to n1 being an integer from 10 to 20. The stress release agent shown in formula (4) can be understood to include at least one of the multiple compounds corresponding to n3, n4 and n5 being independently integers of 5-8.

[0064] In some embodiments of the present application, the mass ratio of the stress release agent to the epoxy resin composition is 0.5% to 3% by mass. Exemplarily, the mass ratio of the stress release agent to the epoxy resin composition is 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% and values ​​between any two of the above points.

[0065] In some embodiments of the present application, the mass ratio of the epoxy resin to the epoxy resin composition is 2% to 10% by mass. For example, the mass ratio of the epoxy resin to the epoxy resin composition is 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% and values ​​between any two of the above points.

[0066] In some embodiments of the present application, the epoxy resin includes an epoxy resin that is liquid at room temperature. Exemplarily, the epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin, dihydroxy naphthalene epoxy resin, aminophenol epoxy resin, and polyalkylene glycol epoxy resin. Preferably, the epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, and alicyclic epoxy resin.

[0067] In some embodiments of the present application, the curing agent includes at least one of aliphatic amines, aromatic amines, phenolic compounds, acid anhydrides, and imidazole compounds.

[0068] Exemplarily, the fatty amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyetheramine, and isophoronediamine.

[0069] Exemplarily, the aromatic amines include m-phenylenediamine, diaminodiphenylmethane, and diaminodiphenyl sulfone.

[0070] Exemplarily, the acid anhydride includes at least one of phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, and succinic anhydride. Exemplarily, the curing agent is one of m-phenylenediamine and diethyltetramethylimidazole, or a combination thereof.

[0071] Exemplarily, the imidazole compounds include dimethyl imidazole and diethyltetramethyl imidazole.

[0072] Preferably, the curing agent is one of m-phenylenediamine and diethyltetramethylimidazole or a combination thereof.

[0073] In some embodiments of the present application, the mass ratio of the curing agent content to the epoxy resin composition is 3% to 10%, calculated by mass. Exemplarily, the mass ratio of the epoxy resin to the epoxy resin composition is 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, and values ​​between any two of the above points.

[0074] In some embodiments of the present application, the epoxy resin composition further includes an inorganic filler, and the mass ratio of the inorganic filler to the epoxy resin composition is 60% to 93% by mass. Exemplarily, the mass ratio of the epoxy resin to the epoxy resin composition is 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 91%, 92%, 93% and values ​​between any two of the above points.

[0075] It should be noted that if the content of inorganic filler in the epoxy resin composition is too low, for example, less than 60%, the viscosity of the liquid epoxy resin composition is too low and its compatibility with the existing process is not ideal; if the content of inorganic filler in the epoxy resin composition is too high, for example, higher than 93%, the fluidity of the liquid epoxy resin composition deteriorates, which can easily lead to defects such as incomplete filling during the packaging process.

[0076] In some embodiments of the present application, the inorganic filler includes at least one of silicon dioxide, aluminum oxide, aluminum nitride, silicon carbide, boron nitride, zircon, calcium silicate, calcium carbonate and barium titanate. Exemplarily, the inorganic filler is spherical.

[0077] Further, the average particle size of the inorganic filler is 2μm to 100μm, that is, the average particle size of the inorganic filler is 2μm to 100μm. Exemplarily, the average particle size of the inorganic filler is 2μm, 5μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm, 50μm, 55μm, 60μm, 65μm, 70μm, 75μm, 80μm, 85μm, 90μm, 95μm, 100μm and values ​​between any two of the above points. Further, the average particle size of the inorganic filler is 25μm to 75μm.

[0078] In some embodiments of the present application, the average particle size of the inorganic filler is 2 μm to 50 μm. Furthermore, the average particle size of the inorganic filler is 10 μm to 20 μm.

[0079] In some embodiments of the present application, the epoxy resin composition further comprises a silane coupling agent, and the mass ratio of the silane coupling agent to the epoxy resin composition is 0.2% to 1% by mass. For example, the mass ratio of the silane coupling agent to the epoxy resin composition is 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% and values ​​between any two of the above points.

[0080] In some embodiments of the present application, the silane coupling agent includes γ-(2,3-epoxypropoxy)propyltrimethoxysilane, trimethyloxyphenylsilane, 3-aminopropyltriethoxysilane, 3-(isobutyleneoxy)propyltrimethoxysilane, vinyltrimethoxysilane, (3-aminopropyl)triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-aniline At least one of γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, and γ-anilinomethylethyldimethoxysilane.

[0081] In some embodiments of the present application, the epoxy resin composition further includes a curing accelerator, and the mass ratio of the curing accelerator to the epoxy resin composition is 0.1% to 3% by mass. Exemplarily, the mass ratio of the curing accelerator to the epoxy resin composition is 0.1%, 0.2%, 0.4%, 0.5%, 0.7%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3% and values ​​between any two of the above points. Preferably, the mass ratio of the curing accelerator to the epoxy resin composition is 0.2% to 2%.

[0082] Exemplarily, the curing accelerator is an imidazole compound or a tertiary amine salt. For example, the curing accelerator includes at least one of 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole.

[0083] In some embodiments of the present application, the epoxy resin composition further includes a colorant, and the mass ratio of the colorant to the epoxy resin composition is 0.1% to 1% by mass. Exemplarily, the mass ratio of the curing accelerator to the epoxy resin composition is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% and values ​​between any two of the above points. Further, the mass ratio of the colorant to the epoxy resin composition is 0.1% to 0.6%. It should be noted that the specific type of colorant does not belong to the main improvement of the present application and is not limited here.

[0084] In some embodiments of the present application, the epoxy resin composition includes epoxy resin, curing agent, inorganic filler, curing accelerator, silane coupling agent, stress release agent and colorant, and the epoxy resin: the curing agent: the inorganic filler: the curing accelerator: the silane coupling agent: the stress release agent: the colorant is (2~10): (3~10): (60~93): (0.3~3): (0.5~1): (0.1~1).

[0085] In some embodiments of the present application, the epoxy resin composition consists of epoxy resin, curing agent, inorganic filler, curing accelerator, silane coupling agent, stress release agent and colorant by mass.

[0086] In some embodiments of the present application, the epoxy resin composition includes, by mass, 0.5-25 parts (i.e., 0.5 to 25 parts) of epoxy resin, 1-20 parts of curing agent, 60-92 parts of inorganic filler, 0.05-2 parts of curing accelerator, 0.05-5 parts of silane coupling agent, 0.005-2 parts of stress release agent and 0.1 to 0.6 parts of colorant.

[0087] The embodiment of the present application also provides a method for preparing an epoxy resin composition, comprising the following steps: adding epoxy resin, curing agent, inorganic filler, curing accelerator, silane coupling agent, stress release agent and colorant into a reaction kettle according to a proportion, dispersing and mixing at 40-60° C. to obtain the liquid epoxy resin composition.

[0088] The epoxy resin composition in this application is further described below in conjunction with specific experimental tests.

[0089] According to the raw material composition and mass ratio in Table 1 and Table 2, each embodiment (Example 1 in Table 1 is abbreviated as "S1", Example 2 is abbreviated as "S2", and other embodiments are abbreviated by the same method) and a comparative example (Comparative Example 1 in Table 1 is abbreviated as "D1", and other comparative examples are abbreviated by the same method) were prepared, and the same curing process was used to cure them to obtain mechanical property test samples.

[0090] Table 1

[0091]

[0092]

[0093] Note: “ / ” in Table 1 means not added.

[0094] Table 2 Experimental raw materials

[0095] A1 Bisphenol F type epoxy resin, epoxy equivalent 155-165g / eq. A2 Bisphenol A type epoxy resin, epoxy equivalent 172-176g / eq. A3 Naphthalene epoxy resin, epoxy equivalent weight 136-150g / eq. A4 Alicyclic epoxy resin, epoxy equivalent weight 130g / eq. B Diethylenetriamine C <![CDATA[Fused spherical SiO2]]> D 2-Phenyl-4-methylimidazole E1 γ-anilinomethylmethyldimethoxysilane E2 γ-(2,3-Epoxypropyl)propyltrimethoxysilane F1 The compound represented by the structure of formula (2) F2 The compound represented by the structure of formula (3) F3 The compound represented by the structure of formula (4) F4 Nitrile rubber G Carbon Black

[0096] Experimental testing

[0097] Viscosity measurement: measured using an E-type viscometer at 25 revolutions per minute, with the unit of viscosity being Pa.s.

[0098] Warpage measurement: On a wafer with a thickness of 750μm and a diameter of 300mm, the sealing resin composition was compressed and molded at 5MPa and 125℃ for 5 minutes using a TOWA compression molding machine to obtain a packaging material with a thickness of 500μm. The prepared compression molded sample was cured at 150℃ for 2 hours to obtain a sample for warpage test. The warpage of the sample was determined by the TMD (topological deformation measurement) method: the plastic-sealed wafer was placed on the TMD device for high-precision three-dimensional topological scanning to obtain surface morphology data; the warpage deformation was calculated by analyzing the height deviation and deformation amount of the sample surface.

[0099] Mechanical properties measurement: Place a specimen that meets standard dimensions on two supporting points, apply a vertical load at a constant speed in the center of the specimen, record the force and deflection data during loading, and calculate the flexural strength and flexural modulus of the material using the formula.

[0100] The viscosity, warpage and mechanical properties of each experimental example were tested, and the test results are shown in Table 3.

[0101] Table 3

[0102]

[0103]

[0104] The difference between Examples 1 to 12 and Comparative Example 3 is whether a stress release agent is added. The test results show that the warpage deformation of Examples 1 to 12 is much lower than that of Comparative Example 3, and the bending strength is also improved to a certain extent. It can be seen that the stress release agent with the structure of formula (1) added in the examples of the present application is conducive to reducing the warpage deformation of the epoxy resin and improving its bending strength. It is worth mentioning that in the related art, nitrile rubber is generally added to the epoxy resin composition to reduce its warpage deformation. The stress release agent with the structure of formula (1) added in the present application has a lower warpage deformation than nitrile rubber, which has a surprising effect.

[0105] In addition, it is worth mentioning that the stress release agent having the structure of formula (1) added in the embodiments of the present application also solves the problem of phase separation when adding nitrile rubber to the epoxy resin composition in the related art. Figure 1 Figure b shows the surface morphology of the liquid epoxy composition in Comparative Example 2 after curing. Obvious phase separation can be observed, indicating that the stress release agent has been significantly precipitated. When other conditions remain unchanged, the nitrile rubber is removed from Comparative Example 3, and the phase separation phenomenon disappears. It can be seen that although adding nitrile rubber to the epoxy resin composition can also significantly reduce its warpage deformation, it still has the problem of phase separation after curing. Figure 1 Figure a in the middle shows the surface morphology of the liquid epoxy composition after curing in Example 2. The observation results show that the surface of the cured product is uniform and dense, and there is no phase separation phenomenon caused by the precipitation of the stress release agent.

[0106] It can be seen from the test results of Example 1, Example 7 to Example 10 that as the content of the stress release agent in the epoxy resin composition increases, the warpage deformation gradually decreases, but the mechanical properties gradually decrease and the viscosity gradually increases. When the content of the stress release agent is less than 2 parts, the bending strength is greater than 70MPa, and the viscosity at room temperature is less than 800Pa.s, which can be applied to the molding process of the existing liquid molding compound and has high mechanical properties and low warpage performance.

[0107] From the comparison of Examples 1 to 6, it can be seen that the stress release agent shown in formula (3) added to the epoxy resin composition has a lower warpage deformation than the stress release agents shown in formula (2) and formula (4). The possible reason is that the chain segment in the middle of the stress release agent shown in formula (3) is more flexible, which is more conducive to reducing the warpage of the epoxy resin composition having it.

[0108] The difference between Example 1 and Example 2 is that different silane coupling agents are used. The test results show that the silane coupling agent used in Example 2 can make the bending strength and full modulus of the material higher and the viscosity greater, indicating that its toughness is relatively high and the warpage is reduced accordingly.

[0109] The technical solutions provided by the embodiments of the present application are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea. At the same time, for technical personnel in this field, according to the idea of ​​the present application, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. An epoxy resin composition, characterized in that It includes epoxy resin, curing agent and stress release agent; the structure of the stress release agent is shown in formula (1): Wherein, R1 and R2 are each independently selected from a hydrogen atom, a C1 to C3 substituted or unsubstituted alkoxy group, a C1 to C3 substituted or unsubstituted alkyl group; R3 is selected from At least one of; n1, n2, n3, n4 and n5 can independently be an integer of 5-20.

2. The epoxy resin composition according to claim 1, wherein R1 and R2 are each independently selected from a hydrogen atom or a methoxy group; and / or The synthetic raw materials of the stress release agent include polyetheramine and allylphenol compounds.

3. The epoxy resin composition according to claim 1 or 2, characterized in that The stress release agent comprises at least one of the structures of formula (2) to (4):

4. The epoxy resin composition according to claim 3, characterized in that The mass ratio of the stress release agent to the epoxy resin composition is 0.1% to 3% by mass; and / or The n1 is an integer of 10-20; and / or The n2 is an integer of 5-15; and / or The n3, n4 and n5 can be independently integers of 5-8.

5. The epoxy resin composition according to claim 4, characterized in that The mass ratio of the stress release agent to the epoxy resin composition is 0.1% to 2%.

6. The epoxy resin composition according to claim 1, characterized in that The epoxy resin composition further comprises an inorganic filler, the inorganic filler accounting for 60% to 93% of the epoxy resin composition by mass; and / or The epoxy resin accounts for 2% to 10% of the epoxy resin composition; and / or The curing agent accounts for 3% to 10% of the epoxy resin composition; and / or The epoxy resin composition further comprises a silane coupling agent, wherein the silane coupling agent accounts for 0.2% to 1% of the epoxy resin composition; and / or The epoxy resin composition further comprises a curing accelerator, wherein the curing accelerator accounts for 0.1% to 3% of the epoxy resin composition; and / or The epoxy resin composition further includes a colorant, and the colorant accounts for 0.1% to 1% of the epoxy resin composition.

7. The epoxy resin composition according to claim 6, wherein The epoxy resin comprises an epoxy resin that is liquid at room temperature; and / or The curing agent comprises at least one of aliphatic amines, aromatic amines, phenolic compounds, acid anhydrides and imidazole compounds; and / or The inorganic filler comprises at least one of silicon dioxide, aluminum oxide, aluminum nitride, silicon carbide, boron nitride, zircon, calcium silicate, calcium carbonate and barium titanate; and / or The average particle size of the inorganic filler is 2 μm to 100 μm; and / or The silane coupling agent includes γ-(2,3-epoxypropyloxy)propyltrimethoxysilane, trimethyloxyphenylsilane, 3-aminopropyltriethoxysilane, 3-(isobutylacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, (3-aminopropyl)triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, At least one of silane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, and γ-anilinomethylethyldimethoxysilane; and / or The curing accelerator is an imidazole compound or a tertiary amine salt.

8. The epoxy resin composition according to claim 7, characterized in that The epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin, naphthalene epoxy resin, aminophenol epoxy resin, polyalkylene glycol epoxy resin and alicyclic epoxy resin.

9. The epoxy resin composition according to claim 8, characterized in that The bisphenol F epoxy resin has an epoxy equivalent of 155-165 g / eq; and / or The bisphenol A epoxy resin has an epoxy equivalent of 172-176 g / eq; and / or The epoxy equivalent of the naphthalene ring epoxy resin is 136-150 g / eq; and / or The cycloaliphatic epoxy resin has an epoxy equivalent of 129-131 g / eq; and / or By mass, the epoxy resin includes bisphenol F type epoxy resin, bisphenol A type epoxy resin, naphthalene ring epoxy resin and alicyclic epoxy resin, and the bisphenol F type epoxy resin: the bisphenol A type epoxy resin: the naphthalene ring epoxy resin: the alicyclic epoxy resin is (1.35 to 1.41): (1.5 to 1.6): (1.18 to 1.25): (0.79 to 0.85).

10. A packaging material, characterized in that: The packaging material is formed by curing the epoxy resin composition according to any one of claims 1 to 9.

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