Self-repairing epoxy plastic packaging material, preparation method and application thereof

Abstract

The application provides a self-repairing epoxy plastic sealing material and a preparation method and application thereof. The self-repairing epoxy plastic sealing material comprises a curing agent, and the curing agent comprises isocyanate modified phenolic resin and / or anhydride curing agent. The isocyanate modified phenolic resin contains ester bonds, hydroxyl groups and secondary amine groups. The anhydride curing agent can also generate ester bonds, hydroxyl groups and secondary amine groups by reacting with epoxy resin. By introducing the ester bonds, hydroxyl groups and secondary amine groups as dynamic bond exchange sites into the epoxy plastic sealing material, the epoxy plastic sealing material has self-repairing property. Meanwhile, the self-repairing epoxy plastic sealing material also comprises a heat-conducting filler, so that the epoxy plastic sealing material has self-repairing property and high thermal conductivity. The self-repairing epoxy plastic sealing material has the advantages of self-repairing, high thermal conductivity, excellent comprehensive performance and good continuous forming property through the joint action of raw materials such as epoxy resin, curing agent and heat-conducting filler.

Description

Technical Field

[0001] This invention relates to the field of electronic packaging materials technology, and in particular to a self-healing epoxy molding compound, its preparation method, and its application. Background Technology

[0002] To address the global energy resource crisis, global energy conservation and energy transformation are driving demand in downstream applications such as new energy vehicles, photovoltaics, and wind power, making power devices (power semiconductors) a focus of attention. Simultaneously, the 5G era requires high-voltage, high-frequency high-power components. Therefore, the development of high-conversion-efficiency compound semiconductors such as silicon carbide (SiC) and gallium nitride (GaN) has become a new competitive research direction. Compared to traditional Si components, SiC and GaN components have the characteristics of high voltage resistance and high operating temperature. During use, electronic devices may experience defects such as microcracks due to thermal stress and mechanical damage, reducing their lifespan. If epoxy molding compounds have high thermal conductivity, or can automatically heal or repair micro-damage generated inside and outside the material under external stimuli (such as temperature), the safety of the molding compound during use can be effectively improved and its lifespan extended.

[0003] Currently, there are few reports on the research and development of epoxy molding compounds with self-healing functions. Therefore, there is an urgent need to develop self-healing epoxy molding compounds with high thermal conductivity, so that new epoxy molding compounds can have high thermal conductivity and self-healing properties while taking into account good comprehensive performance and processability to meet application requirements. Summary of the Invention

[0004] In view of this, the present invention proposes a self-healing epoxy molding compound, its preparation method and application, in order to solve or partially solve the problems existing in the prior art.

[0005] In a first aspect, the present invention provides a self-healing epoxy molding compound, comprising the following raw materials: epoxy resin, curing agent, thermally conductive filler, curing accelerator, silane coupling agent, and stress-relieving agent;

[0006] The curing agent includes isocyanate-modified phenolic resin or a mixture of isocyanate-modified phenolic resin and an acid anhydride curing agent.

[0007] Preferably, the self-healing epoxy molding compound is prepared by means of: dissolving phenolic resin in an organic solvent, then adding isocyanate, and reacting at 35-45°C to obtain isocyanate-modified phenolic resin.

[0008] The molar ratio of the ester group in the isocyanate to the hydroxyl group in the phenolic resin is 1:(1-8).

[0009] Preferably, in the self-healing epoxy molding compound, the isocyanate-modified phenolic resin includes at least one of phenolic varnish resin, biphenyl aryl phenolic resin, cresol phenolic varnish epoxy resin, biphenyl phenolic varnish resin, triphenylmethane phenolic resin, naphthol phenolic varnish resin, and aryl phenolic resin.

[0010] And / or, the anhydride curing agent includes at least one of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, maleic anhydride, glutaric anhydride, polyazelaic anhydride, pyromellitic dianhydride, trimellitic anhydride, halogen-containing anhydride, tung oil anhydride, and maleimide tung oil anhydride;

[0011] And / or, the epoxy resin includes at least one of the following: phenolic phenolic epoxy resin, o-cresol phenolic epoxy resin, alkyl-substituted or unsubstituted diglycidyl ether epoxy resin, 1,2-stilbene epoxy resin, sulfur-containing epoxy resin, hydroquinone epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, epoxide of dicyclopentadiene cocondensed with phenol and / or naphthol resin, naphthalene-containing epoxy resin, phenol arachidonic resin, epoxide of arachidonic phenol resin, trimethylolpropane epoxy resin, and ester cyclic epoxy resin;

[0012] And / or, the thermally conductive filler includes inorganic thermally conductive fillers and / or inorganic thermally conductive fillers modified with coupling agents;

[0013] The inorganic thermally conductive filler includes at least one of silicon dioxide, aluminum oxide, aluminum nitride, boron nitride, zircon, calcium silicate, calcium carbonate, and barium titanate.

[0014] And / or, the average particle size of the inorganic thermally conductive filler is 0.1–53 μm;

[0015] And / or, the curing accelerator includes at least one of cycloamidinium compounds, quinone compounds, imidazoline compounds and their derivatives, organophosphorus compounds, and compounds with intramolecular polarity.

[0016] Preferably, the self-healing epoxy molding compound comprises at least one of 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, and 5,6-dibutylamino-1,8-diaza-bicyclo[5.4.0]undecene-7;

[0017] And / or, the quinone compound is a quinone compound formed by adding at least one of maleic anhydride, 1,4-benzoquinone, 2,5-toluenequinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, and 2,3-dimethoxy-5-methyl-1 to the cycloamidinium compound;

[0018] And / or, the imidazoline compounds include at least one of 2-methylimidazoline, 2-phenylimidazoline, and 2-phenyl-4-methylimidazoline;

[0019] And / or, the organophosphorus compounds include at least one of tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tri(4-methylphenyl)phosphine, diphenylphosphine, and phenylphosphine;

[0020] And / or, the intramolecularly polar compound is an intramolecularly polar compound formed by the addition of at least one of the organophosphorus compound, maleic anhydride, the quinone compound, benzoazomethane, and phenolic resin.

[0021] Preferably, in the self-healing epoxy molding compound, the silane coupling agent comprises a compound represented by general formula (1) or (2);

[0022] The structural formula of the compound represented by general formula (1) is as follows:

[0023]

[0024] Where m is an integer between 1 and 3; n is an integer between 0 and 3; R 1 Selected from H2N-、 HS-、 One of them;

[0025] b is an integer between 1 and 3; a is an integer between 0 and 3;

[0026] (X) j Selected from any one of hydrogen atoms and alkyl groups having 1 to 6 carbon atoms;

[0027] R 2 R 3 Each is independently selected from methyl or ethyl;

[0028] R 4 R 5 Each is independently selected from methyl or ethyl.

[0029] Preferably, the self-healing epoxy molding compound comprises a silane coupling agent of formula (1) including γ-(2,3-epoxypropoxy)propyltrimethoxysilane, trimethyloxyphenylsilane, 3-aminopropyltriethoxysilane, 3-(isobutenoyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, (3-aminopropyl)triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and γ-anilinepropyltrimethoxysilane. At least one of the following: silane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, and γ-anilinomethylethyldimethoxysilane;

[0030] And / or, the silane coupling agent of formula (2) includes at least one of γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, and γ-anilinopropylethyldimethoxysilane.

[0031] Preferably, the self-healing epoxy molding compound further includes a release agent, a colorant, a flame retardant, and fumed silica;

[0032] The release agent comprises linear saturated carboxylic acid and / or oxidized polyethylene wax;

[0033] And / or, the flame retardant includes at least one of trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dihydroxymethyl phosphate, and tridimethylmethyl phosphate;

[0034] And / or, the fumed silicon is fumed silicon dioxide.

[0035] Preferably, the self-healing epoxy molding compound comprises, by mass fraction, the following raw materials: 4-25% epoxy resin, 3-15% curing agent, 60-90% thermally conductive filler, 0.05-2% curing accelerator, 0.05-5% silane coupling agent, 0.5-2% stress release agent, 0.005-2% mold release agent, 0.1-0.6% colorant, 0.1-0.5% flame retardant, and 0.2-0.5% fumed silica;

[0036] And / or, the number-average molecular weight of the oxidized polyethylene wax is 550 to 1200;

[0037] And / or, the average particle size of fumed silicon is 5–40 nm;

[0038] And / or, the molar ratio of the epoxy groups in the epoxy resin to the hydroxyl groups in the curing agent, or the molar ratio of the epoxy groups in the epoxy resin to the anhydride groups in the curing agent, is 0.5 to 2.

[0039] Secondly, the present invention also provides a method for preparing the aforementioned self-healing epoxy molding compound, comprising the following steps:

[0040] The self-healing epoxy molding compound is obtained by mixing epoxy resin, curing agent, inorganic filler, curing accelerator, silane coupling agent, stress relief agent, optional release agent, optional colorant, optional flame retardant, and optional fumed silica, and then kneading and mixing them.

[0041] Thirdly, the present invention also provides an application of the self-healing epoxy molding compound or the self-healing epoxy molding compound prepared by the preparation method described above in semiconductor device packaging.

[0042] The self-healing epoxy molding compound and its preparation method of the present invention have the following technical advantages over the prior art:

[0043] 1. The self-healing epoxy molding compound of the present invention includes a curing agent, which includes isocyanate-modified phenolic resin and / or anhydride curing agent, wherein the isocyanate-modified phenolic resin contains ester bonds, hydroxyl groups and secondary amine groups; and the anhydride curing agent can also generate ester bonds, hydroxyl groups and secondary amine groups by reacting with the epoxy resin; by introducing ester bonds, hydroxyl groups and secondary amine groups as dynamic bond exchange sites into the epoxy molding compound, the epoxy molding compound has self-healing properties; at the same time, the self-healing epoxy molding compound of the present invention also includes a thermally conductive filler, so that the epoxy molding compound has both self-healing properties and a high thermal conductivity.

[0044] 2. The self-healing epoxy molding compound of the present invention is an isocyanate-modified phenolic resin, the reactants of which are isocyanate and phenolic resin, and the molar ratio of ester groups in isocyanate to hydroxyl groups in phenolic resin is 1:(1-8); as the molar ratio of hydroxyl groups to isocyanate groups in the isocyanate-modified phenolic resin raw material increases, the flexural strength, Tg, and repair effect of the epoxy molding compound are all improved. The flexural strength repair rate of the secondary repair sample is about 75%. Considering both processability and economy, it is believed that the modified phenolic resin can balance performance, processability, and economy.

[0045] 3. The self-healing epoxy molding compound of the present invention has little effect on Tg and flexural strength with the increase of modified thermally conductive filler content, but it does affect the repair rate. Compared with the unmodified thermally conductive filler system, the repair rate is increased to 87%, and the flexural strength (secondary) can reach 95.7 MPa. The introduction of isocyanate modified phenolic resin is the main factor that enables the epoxy molding compound to have repair properties. The acid anhydride curing agent and the modified thermally conductive filler have a synergistic effect, and they do not have repair properties when used alone. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0047] The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0048] To better understand the invention and not to limit its scope, all figures indicating amounts, percentages, and other numerical values ​​used in this application should, in all cases, be understood to be modified by the word "approximately." Therefore, unless specifically stated otherwise, the numerical parameters listed in the specification and appended claims are approximate values ​​and may vary depending on the desired properties being sought. Each numerical parameter should at least be considered as obtained based on reported significant figures and through conventional rounding methods.

[0049] It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of embodiments. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has 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., and single digits within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0050] This application provides a self-healing epoxy molding compound, comprising the following raw materials: epoxy resin, curing agent, thermally conductive filler, curing accelerator, silane coupling agent, and stress-relieving agent;

[0051] The curing agent includes isocyanate-modified phenolic resin or a mixture of isocyanate-modified phenolic resin and acid anhydride curing agent.

[0052] It should be noted that the self-healing epoxy molding compound of the present invention includes a curing agent, which includes isocyanate-modified phenolic resin and / or anhydride curing agent. The isocyanate-modified phenolic resin contains ester bonds, hydroxyl groups, and secondary amine groups. Similarly, the anhydride curing agent reacts with the epoxy resin to generate ester bonds and hydroxyl groups. By introducing ester bonds, hydroxyl groups, and secondary amine groups into the epoxy molding compound as dynamic bond exchange sites, the epoxy molding compound acquires self-healing properties. Furthermore, the self-healing epoxy molding compound of the present invention also includes a thermally conductive filler, enabling the epoxy molding compound to possess both self-healing properties and a high thermal conductivity. In summary, the self-healing epoxy molding compound of the present invention, through the combined action of epoxy resin, curing agent, and thermally conductive filler, achieves advantages such as self-healing, high thermal conductivity, excellent overall performance, and good continuous molding properties.

[0053] In some embodiments, the isocyanate-modified phenolic resin (B2) is prepared by reacting isocyanates (including monoisocyanates, diisocyanates, and polyisocyanates, etc.) and phenolic resin. Specifically, the preparation method of isocyanate-modified phenolic resin is as follows: phenolic resin is dissolved in an organic solvent, then isocyanate is added, and the reaction is carried out at 35-45°C to obtain isocyanate-modified phenolic resin.

[0054] The molar ratio of the ester group in the isocyanate to the hydroxyl group in the phenolic resin is 1:(1-8), preferably 1:(2-4); specifically, the organic solvent includes, but is not limited to, acetone.

[0055] Specifically, isocyanates include toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), etc.

[0056] Specifically, the reaction mechanism between the acid anhydride curing agent and epoxy resin is as follows:

[0057]

[0058] Among them, the acid anhydride curing agent is R y Including but not limited to benzene rings, benzyl groups, or other cyclic compounds; epoxy resin is... Rx Including but not limited to alkyl groups; This indicates that hydroxyl groups are generated after the epoxy resin ring is opened, and these hydroxyl groups can also participate in the reaction.

[0059] Specifically, isocyanate (TDI) and phenolic resin (NR) undergo the following reaction to obtain isocyanate-modified phenolic resin (B2):

[0060]

[0061] It is clear from the above chemical reaction formula that isocyanate-modified phenolic resin contains ester bonds, hydroxyl groups and secondary amine groups.

[0062] In some embodiments, the isocyanate-modified phenolic resin (B2) contains phenolic resin (B1) comprising one or more of phenolic varnish resin, biphenyl aryl phenolic resin, cresol phenolic varnish epoxy resin, biphenyl phenolic varnish resin, triphenylmethane phenolic resin, naphthol phenolic varnish resin, and aryl phenolic resin; preferably, the phenolic resin comprises one or two of low hygroscopic resins such as biphenyl aryl phenolic resin and phenolic varnish resin.

[0063] In some embodiments, the anhydride curing agent (B3) includes at least one of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, maleic anhydride, glutaric anhydride, polyazelaic anhydride, pyromellitic dianhydride, trimellitic anhydride, halogenated anhydride, tung oil anhydride, and maleimide tung oil anhydride.

[0064] In some embodiments, epoxy resin (A) is a commonly used encapsulating epoxy resin without particular limitation; specifically, epoxy resin (A) includes products obtained by condensing or co-condensing phenolic resins such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, and bisphenol F, primarily phenolic phenolic resins and o-cresol phenolic phenolic resins, with aldehyde-containing compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst to obtain phenolic resins; alkyl-substituted or non-substituted diglycidyl ether type epoxy resins; 1,2-di Styrene-type epoxy resins; epoxy resins containing sulfur atoms; hydroquinone-type epoxy resins; glycidyl ester-type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acids with epichlorohydrin; glycidylamine-type epoxy resins obtained by reacting polyamines such as diaminodiphenylmethane and isocyanate with epichlorohydrin; epoxides of dicyclopentadiene co-condensed with phenols and / or naphthols; epoxides containing naphthalene rings; phenol aryl alkyl resins; epoxides of aryl alkyl phenol resins such as naphthol aryl alkyl resins; trimethylolpropane-type epoxy resins; ester cyclic epoxy resins, etc. The above epoxy resins can be used alone or in combination of two or more.

[0065] Preferably, the epoxy resin (A) can be one or a combination of two of the following general formulas (I) to (II):

[0066]

[0067] In this context, R is independently selected from hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, and n represents an integer between 0 and 3.

[0068] In some embodiments, the thermally conductive filler (C) includes one or more of conventionally known inorganic thermally conductive fillers (C1) and surface-treated inorganic thermally conductive fillers (C2); specifically, the inorganic thermally conductive filler (C1) includes at least one of crystalline silica, fused silica, synthetic silica, alumina, aluminum nitride, boron nitride, zircon, calcium silicate, calcium carbonate, barium titanate, etc.

[0069] From the perspective of fluidity and high thermal conductivity, the inorganic thermally conductive filler can be mainly composed of spherical alumina or a mixture of spherical alumina and molten spherical silica; preferably, from the perspective of fluidity, the average particle size of the inorganic thermally conductive filler is 0.1 to 53 μm, and more preferably 0.1 to 40 μm.

[0070] In some embodiments, the surface-treated inorganic filler (C2) is an inorganic thermally conductive filler treated with an aniline coupling agent.

[0071] In some embodiments, considering the curing properties of epoxy molding compounds, a curing accelerator (D) is further added to the epoxy molding compound of the present invention. The curing accelerator (D) used in the present invention is a substance commonly used in epoxy resin molding compounds for encapsulation, and there are no particular limitations on it. Specifically, the curing accelerator (D) includes at least one of cycloamidinium compounds, quinone compounds, imidazoline compounds and their derivatives, organophosphorus compounds, and compounds with intramolecular polarity.

[0072] In some embodiments, the cycloamidinium compounds include at least one of 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, and 5,6-dibutylamino-1,8-diaza-bicyclo[5.4.0]undecene-7.

[0073] In some embodiments, the quinone compound is a quinone compound formed by adding at least one of maleic anhydride, 1,4-benzoquinone, 2,5-toluenequinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, and 2,3-dimethoxy-5-methyl-1 to the above-mentioned cycloamidinium compounds.

[0074] In some embodiments, imidazoline compounds include at least one of 2-methylimidazoline, 2-phenylimidazoline, and 2-phenyl-4-methylimidazoline.

[0075] In some embodiments, organophosphorus compounds include at least one of tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tri(4-methylphenyl)phosphine, diphenylphosphine, and phenylphosphine.

[0076] In some embodiments, the intramolecularly polar compound is an intramolecularly polar compound formed by adding maleic anhydride, the quinone compound, benzoazomethane, or phenol resin to the organophosphorus compound described above.

[0077] Preferably, the curing accelerator (D) is an organophosphorus compound, and the mass of the organophosphorus catalyst is 0.05%-0.6% of the mass of the epoxy molding compound.

[0078] In some embodiments, the silane coupling agent (E) comprises compounds represented by general formula (1) and / or (2):

[0079]

[0080] Where m is an integer between 1 and 3; n is an integer between 0 and 3; R 1 Selected from H2N-、 HS-、 One of them; (X)j Selected from any one of hydrogen atoms and alkyl groups having 1 to 6 carbon atoms; R 2 R 3 Each is independently selected from methyl or ethyl, and in R 2 OR 3 When multiple instances exist, they can be the same or different from each other.

[0081] Preferably, considering flowability, the silane coupling agent is a compound represented by general formula (2):

[0082]

[0083] Where b is an integer between 1 and 3; a is an integer between 0 and 3; (X) j Selected from any one of hydrogen atoms and alkyl groups having 1 to 6 carbon atoms; R 4 R 5 Each is independently selected from methyl or ethyl, and in R 4 OR 5 When multiple instances exist, they can be the same or different from each other.

[0084] Preferably, the silane coupling agent having the formula (1) includes γ-(2,3-epoxypropoxy)propyltrimethoxysilane, trimethyloxyphenylsilane, 3-aminopropyltriethoxysilane, 3-(isobutenoyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, (3-aminopropyl)triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, γ-anilinepropyltrimethoxysilane, γ-aniline At least one of the following: γ-aminopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, and γ-anilinomethylethyldimethoxysilane;

[0085] Preferably, the amino organosilane coupling agent having the formula (2) includes at least one of γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, and γ-anilinopropylethyldimethoxysilane;

[0086] More preferably, the silane coupling agent is γ-anilinopropyltrimethoxysilane. When the above-mentioned amino-organosilane coupling agent is mixed into the epoxy resin composition, it can improve the adhesion between the filler and the resin and better exert the bulk properties of the filler.

[0087] In some embodiments, the stress-relieving agent (F) is a known stress-relieving agent, and preferably, the content of stress-relieving agent (F) is 0.5%-2% of the weight of the epoxy molding compound.

[0088] In some embodiments, the self-healing epoxy molding compound further includes a release agent (G), a colorant (H), a flame retardant (I), and fumed silica (J).

[0089] In some embodiments, the release agent (G) comprises linear saturated carboxylic acid and / or oxidized polyethylene wax, wherein the number-average molecular weight of the oxidized polyethylene wax is 550 to 1200, preferably, the number-average molecular weight of the oxidized polyethylene wax is 800 to 1000.

[0090] In some embodiments, the colorant (H) is a known colorant, preferably a carbon black colorant, and the content of the colorant is 0.2%-0.5% of the weight of the epoxy molding compound.

[0091] In some embodiments, the flame retardant (I) may be an esterification of a compound of phosphoric acid and an alcohol or a compound of phenol, without particular limitation; specifically, the flame retardant (I) includes trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dihydroxymethyl phosphate, tridimethylmethyl phosphate, etc. Among these, considering hydrolysis resistance, aromatic condensed phosphates represented by general formula (3) are preferred:

[0092]

[0093] The amount of flame retardant (I) added is 0.1% to 0.5% of the weight of the epoxy molding compound, preferably 0.2% to 0.5%. If it is less than 0.2%, problems such as lead wire misalignment and molding cavities are likely to occur. If it is more than 3%, the moldability and moisture resistance will decrease.

[0094] In some embodiments, the fumed silicon (J) is fumed silica, a substance commonly used in encapsulation epoxy resin compositions without particular limitation. Preferably, the average particle size of the fumed silicon is in the range of 5 to 40 nm, and preferably, the content of fumed silicon is 0.2% to 0.5% of the weight of the epoxy molding compound.

[0095] In some embodiments, the equivalent ratio of epoxy resin (A) to curing agent (B), i.e., the molar ratio of epoxy groups in the epoxy resin to hydroxyl groups in the curing agent (if the curing agent is an isocyanate-modified phenolic resin), or the molar ratio of the number of epoxy groups in the epoxy resin to the molar ratio of anhydride groups in the curing agent (if the curing agent is an anhydride curing agent), is not particularly limited. To minimize unreacted portions, this ratio is preferably set in the range of 0.5 to 2, more preferably in the range of 0.6 to 1.3. For obtaining epoxy resin molding compounds for encapsulation with excellent moldability and melt resistance, a range of 0.8 to 1.0 is more preferred.

[0096] In some embodiments, the epoxy resin content is 4%-25% of the epoxy molding compound by weight.

[0097] In some embodiments, the curing agent content is 3%-15% of the epoxy molding compound by weight; when the curing agent contains isocyanate-modified phenolic resin, the isocyanate-modified phenolic resin content is 0.5%-4.5% of the epoxy molding compound by weight; when the curing agent contains acid anhydride, the acid anhydride content is 0.5%-4.5% of the epoxy molding compound by weight.

[0098] In some embodiments, the content of inorganic filler is 60%-93% of the weight of epoxy molding compound, preferably 70%-92%, and more preferably 60%-90%; (if the content of inorganic filler is too small, the viscosity of epoxy molding compound is too low, voids are easily generated during molding, and the improvement of dielectric constant and coefficient of thermal expansion is small; conversely, if the content of inorganic filler is too large, the flowability of epoxy molding compound is poor, and defects such as incomplete filling are easily formed).

[0099] In some embodiments, the content of the curing accelerator is 0.05%-2% of the weight of the epoxy molding compound, preferably 0.1%-0.5%; (if the amount of curing accelerator is less than 0.05%, the curing properties tend to deteriorate in a short time; once it is higher than 2%, the curing speed is too fast, and it is difficult to obtain a molded part with a good shape.)

[0100] In some embodiments, the content of the silane coupling agent is 0.05%-0.5% of the weight of the inorganic filler, preferably 0.1%-2.5%.

[0101] In some embodiments, the content of the release agent is 0.005%-2% of the weight of the epoxy molding compound.

[0102] In some embodiments, the colorant content is 0.2%-0.5% of the epoxy molding compound by weight.

[0103] In some embodiments, the flame retardant content is 0.1%-0.5% of the epoxy molding compound by weight.

[0104] In some embodiments, the content of fumed silica is 0.2%-0.5% of the weight of the epoxy molding compound.

[0105] In some embodiments, the self-healing epoxy molding compound comprises, by mass fraction, the following raw materials: 4-25% epoxy resin, 3-15% curing agent, 60-90% thermally conductive filler, 0.05-2% curing accelerator, 0.05-5% silane coupling agent, 0.5-2% stress release agent, 0.005-2% mold release agent, 0.1-0.6% colorant, 0.1-0.5% flame retardant, and 0.2-0.5% fumed silica.

[0106] In some embodiments, the self-healing epoxy molding compound of the present invention may also contain components such as ion trapping agents.

[0107] Based on the same inventive concept, the present invention also provides a method for preparing the above-mentioned self-healing epoxy molding compound, comprising the following steps:

[0108] The self-healing epoxy molding compound is obtained by mixing epoxy resin, curing agent, inorganic filler, curing accelerator, silane coupling agent, stress relief agent, optional release agent, optional colorant, optional flame retardant, and optional fumed silica, and then kneading and mixing them.

[0109] Specifically, epoxy resin, curing agent, inorganic filler, curing accelerator, silane coupling agent, stress relief agent, optional release agent, optional colorant, optional flame retardant, and optional fumed silica are mixed and kneaded at an extrusion temperature of 100-140°C to obtain self-healing epoxy molding compound.

[0110] Based on the same inventive concept, the present invention also provides an application of the above-mentioned self-healing epoxy molding compound in semiconductor device packaging.

[0111] The following detailed embodiments further illustrate the self-healing epoxy molding compound and its preparation method. This section further explains the invention with reference to specific embodiments, but should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods, and equipment used in this invention are conventional reagents, methods, and equipment in the art.

[0112] The epoxy resin (A) used in the following examples and comparative examples is listed below:

[0113] Epoxy resin (A1-1) is derived from the general formula:

[0114] The epoxy resin indicated is (purchased from Japan Epoxy Resin Inc., brand name YX-4000H).

[0115] Epoxy resin (A1-2) is derived from the general formula: The indicated phenylaryl type epoxy resin (epoxy equivalent: 285, softening point: 63℃, purchased from Nippon Kayaku, grade NC-3000).

[0116] The curing agent (B) used in the following examples and comparative examples is listed below:

[0117] Curing agent (B1-1): Biphenyl aryl phenolic resin (hydroxyl equivalent: 203, softening point: 65℃, purchased from Meiwa Chemical Co., Ltd., grade MEH-7851SS).

[0118] Hardener (B1-2): Phenolic varnish resin (hydroxyl equivalent: 104, softening point: 60℃, purchased from Sumitomo Bakelite Co., Ltd., grade PR-HF-3).

[0119] Curing agent (B2-1): Isocyanate-modified phenolic resin. Raw materials used: Isocyanate selected from... The toluene diisocyanate (TDI) and phenolic resin are phenolic varnish resin (hydroxyl equivalent: 104, softening point: 60℃, purchased from Sumitomo Bakelite Co., Ltd., brand name PR-HF-3). The preparation method of the isocyanate modified phenolic resin is as follows: 100g of phenolic resin is dissolved in 30g of acetone and stirred at room temperature until a transparent stock solution is formed. Then, a certain amount of TDI is added (the mass of TDI is determined by the molar ratio of ester groups in toluene diisocyanate (TDI) to hydroxyl groups in phenolic resin. The molar ratio of ester groups in toluene diisocyanate to hydroxyl groups in phenolic resin is 1:(2~8). In this example, the molar ratio of ester groups in toluene diisocyanate to hydroxyl groups in phenolic resin is 1:8). The mixture is stirred at 40℃ until gelation (about 1h). The gel-like mixture is then placed in a vacuum oven and dried at 40℃ until a constant weight is reached, which is the curing agent (B2-1).

[0120] Curing agent (B2-2): Isocyanate modified phenolic resin, which is prepared in the same way as curing agent (B2-1), except that the molar ratio of ester group in toluene diisocyanate to hydroxyl group in phenolic resin is 1:4.

[0121] Curing agent (B2-3): Isocyanate modified phenolic resin, the preparation method of which is the same as that of curing agent (B2-1), the difference being that the molar ratio of ester group in toluene diisocyanate to hydroxyl group in phenolic resin is 1:1.

[0122] Anhydride curing agent (B3-1): (Formula omitted) The indicated methylnadic anhydride (molecular weight: 178, purchased from Nippon Kayaku, brand name KAYAHARD MCD).

[0123] The packing material (C) used in the following examples and comparative examples is listed below:

[0124] The thermally conductive filler (C1) is Al2O3 powder with an average particle size of 5-8 μm and a cut-off particle size of 53 μm, purchased from Denka.

[0125] The thermally conductive filler (C2) is a filler that has been pretreated with an aniline coupling agent. Specifically, in this embodiment, the aniline coupling agent is 3-anilinepropyltrimethoxysilane.

[0126] The curing accelerator (D) used in the following examples and comparative examples is triphenylphosphine.

[0127] The silane coupling agent (E) used in the following examples and comparative examples is listed below: the silane coupling agent is γ-anilinopropyltrimethoxysilane.

[0128] The stress-relieving agent (F) used in the following examples and comparative examples is: organosilicon compound, KF-6123, purchased from Shin-Etsu Chemical Co., Ltd.

[0129] The release agent (G) used in the following examples and comparative examples is: oxidized polyethylene wax HW-4252E with a number average molecular weight of 1000, purchased from Mitsui Chemicals Co., Ltd.

[0130] The colorant (H) used in the following examples and comparative examples is: carbon black colorant, MA-600, purchased from Mitsubishi Chemical Corporation.

[0131] The flame retardant (I) used in the following examples and comparative examples is trimethyl phosphate.

[0132] The fumed silica (J) used in the following examples and comparative examples is: nano-silica with an average particle size of 5–40 nm and a specific surface area of ​​300 ± 30 m². 2 / g.

[0133] Example 1

[0134] This application provides a self-healing epoxy molding compound comprising the following raw materials in parts by weight: 5.93 parts by weight of epoxy resin (A1-1), 7.74 parts by weight of epoxy resin (A1-2), 1.48 parts by weight of biphenyl aryl phenolic resin (B1-1), 1.52 parts by weight of phenolic varnish resin (B1-2), 6.33 parts by weight of isocyanate modified phenolic resin (B2-1), 74.5 parts by weight of spherical alumina thermally conductive filler (C1), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress-relieving agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0135] The preparation method of the above self-healing epoxy molding compound includes the following steps:

[0136] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain self-healing epoxy sealant.

[0137] Example 2

[0138] This application provides a self-healing epoxy molding compound comprising the following raw materials in parts by weight: 5.69 parts by weight of epoxy resin (A1-1), 7.40 parts by weight of epoxy resin (A1-2), 1.48 parts by weight of biphenyl aryl phenolic resin (B1-1), 1.52 parts by weight of phenolic varnish resin (B1-2), 6.91 parts by weight of isocyanate modified phenolic resin (B2-2), 74.5 parts by weight of spherical alumina thermally conductive filler (C1), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress-relieving agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0139] The preparation method of the above self-healing epoxy molding compound includes the following steps:

[0140] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain self-healing epoxy sealant.

[0141] Example 3

[0142] This application provides a self-healing epoxy molding compound, comprising the following raw materials in parts by weight: 5.43 parts by weight of epoxy resin (A1-1), 7.07 parts by weight of epoxy resin (A1-2), 1.48 parts by weight of biphenyl aryl phenolic resin (B1-1), 1.52 parts by weight of phenolic varnish resin (B1-2), 7.51 parts by weight of isocyanate modified phenolic resin (B2-3), 74.5 parts by weight of spherical alumina thermally conductive filler (C1), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress-relieving agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0143] The preparation method of the above self-healing epoxy molding compound includes the following steps:

[0144] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain self-healing epoxy sealant.

[0145] Example 4

[0146] This application provides a self-healing epoxy molding compound, comprising the following raw materials in parts by weight: 5.51 parts by weight of epoxy resin (A1-1), 7.18 parts by weight of epoxy resin (A1-2), 1.48 parts by weight of biphenyl aryl phenolic resin (B1-1), 1.52 parts by weight of phenolic varnish resin (B1-2), 6.21 parts by weight of isocyanate-modified phenolic resin (B2-3), and 1.10 parts by weight of acid anhydride solids. The composition includes: curing agent (B3-1), 74.5 parts by weight of spherical alumina thermally conductive filler (C1), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress-relieving agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silicon (J).

[0147] The preparation method of the above self-healing epoxy molding compound includes the following steps:

[0148] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain self-healing epoxy sealant.

[0149] Example 5

[0150] This application provides a self-healing epoxy molding compound, comprising the following raw materials in parts by weight: 5.53 parts by weight of epoxy resin (A1-1), 7.20 parts by weight of epoxy resin (A1-2), 1.48 parts by weight of biphenyl aryl phenolic resin (B1-1), 1.52 parts by weight of phenolic varnish resin (B1-2), 5.96 parts by weight of isocyanate-modified phenolic resin (B2-3), and 1.31 parts by weight of acid anhydride solids. The composition includes: curing agent (B3-1), 74.5 parts by weight of spherical alumina filler (C1), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress-relieving agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0151] The preparation method of the above self-healing epoxy molding compound includes the following steps:

[0152] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain self-healing epoxy sealant.

[0153] Example 6

[0154] This application provides a self-healing epoxy molding compound, comprising the following raw materials in parts by weight: 5.43 parts by weight of epoxy resin (A1-1), 7.07 parts by weight of epoxy resin (A1-2), 1.48 parts by weight of biphenyl aryl phenolic resin (B1-1), 1.52 parts by weight of phenolic varnish resin (B1-2), 7.51 parts by weight of isocyanate modified phenolic resin (B2-3), 49.5 parts by weight of spherical alumina filler (C1), 25 parts by weight of thermally conductive filler (C2), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress-relieving agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0155] The preparation method of the above self-healing epoxy molding compound includes the following steps:

[0156] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain self-healing epoxy sealant.

[0157] Example 7

[0158] This application provides a self-healing epoxy molding compound comprising the following raw materials in parts by weight: 5.43 parts by weight of epoxy resin (A1-1), 7.07 parts by weight of epoxy resin (A1-2), 1.48 parts by weight of biphenyl aryl phenolic resin (B1-1), 1.52 parts by weight of phenolic varnish resin (B1-2), 7.51 parts by weight of isocyanate modified phenolic resin (B2-3), 24.5 parts by weight of spherical alumina filler (C1), 50 parts by weight of thermally conductive filler (C2), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress-relieving agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0159] The preparation method of the above self-healing epoxy molding compound includes the following steps:

[0160] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain self-healing epoxy sealant.

[0161] Example 8

[0162] This application provides a self-healing epoxy molding compound, comprising the following raw materials in parts by weight: 5.43 parts by weight of epoxy resin (A1-1), 7.07 parts by weight of epoxy resin (A1-2), 1.48 parts by weight of biphenyl aryl phenolic resin (B1-1), 1.52 parts by weight of phenolic varnish resin (B1-2), 7.51 parts by weight of isocyanate modified phenolic resin (B2-3), 74.5 parts by weight of thermally conductive filler (C2), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress-relieving agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0163] The preparation method of the above self-healing epoxy molding compound includes the following steps:

[0164] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain self-healing epoxy sealant.

[0165] Example 9

[0166] This application provides a self-healing epoxy molding compound, comprising the following raw materials in parts by weight: 5.53 parts by weight of epoxy resin (A1-1), 7.20 parts by weight of epoxy resin (A1-2), 1.48 parts by weight of biphenyl aryl phenolic resin (B1-1), 1.52 parts by weight of phenolic varnish resin (B1-2), 5.96 parts by weight of isocyanate-modified phenolic resin (B2-3), and 1.31 parts by weight of... Anhydride curing agent (B3-1), 74.5 parts by weight of thermally conductive filler (C2), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress-relieving agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0167] The preparation method of the above self-healing epoxy molding compound includes the following steps:

[0168] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain self-healing epoxy sealant.

[0169] Comparative Example 1

[0170] This application provides an epoxy molding compound comprising the following raw materials in parts by weight: 5.69 parts by weight of epoxy resin (A1-1), 7.41 parts by weight of epoxy resin (A1-2), 6.28 parts by weight of biphenyl aryl phenolic resin (B1-1), 3.63 parts by weight of phenolic varnish resin (B1-2), 74.5 parts by weight of spherical alumina filler (C1), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress release agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0171] The preparation method of the above-mentioned epoxy molding compound includes the following steps:

[0172] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain epoxy molding compound.

[0173] Comparative Example 2

[0174] This application provides an epoxy molding compound comprising the following raw materials in parts by weight: 5.69 parts by weight of epoxy resin (A1-1), 7.41 parts by weight of epoxy resin (A1-2), 6.28 parts by weight of biphenyl aryl phenolic resin (B1-1), 3.63 parts by weight of phenolic varnish resin (B1-2), 74.5 parts by weight of thermally conductive filler (C2), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress-relieving agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0175] The preparation method of the above-mentioned epoxy molding compound includes the following steps:

[0176] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain epoxy molding compound.

[0177] Comparative Example 3

[0178] This application provides an epoxy molding compound comprising the following raw materials in parts by weight: 5.54 parts by weight of epoxy resin (A1-1), 7.83 parts by weight of epoxy resin (A1-2), 5.58 parts by weight of biphenyl aryl phenolic resin (B1-1), 3.05 parts by weight of phenolic varnish resin (B1-2), 1.00 parts by weight of acid anhydride curing agent (B3-1), 74.5 parts by weight of spherical alumina filler (C1), 0.50 parts by weight of triphenylphosphine curing accelerator (D), 0.40 parts by weight of γ-anilinepropyltrimethoxysilane (E), 0.40 parts by weight of stress release agent (F), 0.10 parts by weight of mold release agent (G), 0.30 parts by weight of colorant (H), 0.30 parts by weight of flame retardant (I), and 0.50 parts by weight of fumed silica (J).

[0179] The preparation method of the above-mentioned epoxy molding compound includes the following steps:

[0180] After mixing the above-mentioned raw materials by weight, kneading, mixing, cooling, and fine pulverizing are carried out at an extrusion temperature of 120°C to obtain epoxy molding compound.

[0181] Performance testing

[0182] Test methods

[0183] For the glass transition temperature, please refer to GB / T 40564-2021 for specific methods.

[0184] For bending strength, please refer to GB / T 40564-2021 for specific methods.

[0185] For thermal conductivity, please refer to GB / T 40564-2021 for specific methods.

[0186] The weight parts and performance parameters of each raw material of the epoxy molding compound in Examples 1 to 4 are shown in Table 1 below.

[0187] Table 1 - Weight parts and properties of each raw material in the epoxy molding compounds of Examples 1-4

[0188]

[0189]

[0190] The weight parts and performance parameters of each raw material of the epoxy molding compound in Examples 5 to 8 are shown in Table 2 below.

[0191] Table 2 - Weight parts and properties of each raw material in the epoxy molding compounds of Examples 5-8

[0192]

[0193]

[0194] The weight parts and performance parameters of each raw material of the epoxy molding compound in Examples 9 and Comparative Examples 1 to 3 are shown in Table 3 below.

[0195] Table 3 - Weight parts and properties of each raw material in the epoxy molding compounds of Examples 9 and Comparative Examples 1-3

[0196]

[0197]

[0198] Where A represents "Excellent" in continuous molding performance and economy, B represents "Good" in continuous molding performance and economy, and C represents "Average" in continuous molding performance and economy. Specifically, continuous molding up to 300 times without mold stains is considered "Excellent"; continuous molding up to 300 times with mold stains is considered "Good"; continuous molding less than 300 times is considered "Average". Bending strength (secondary) refers to testing the epoxy molding compound of different embodiments after bending strength testing (i.e., the bending strength (first time) mentioned above), then pulverizing the epoxy molding compound and re-preparing it (understandably, the epoxy molding compound structure is destroyed after pulverization), and then testing it again. Thermal conductivity (secondary) refers to testing the thermal conductivity of the epoxy molding compound of different embodiments after thermal conductivity testing (i.e., the thermal conductivity (first time) mentioned above), then pulverizing the epoxy molding compound and re-preparing it, and then testing it again.

[0199] As can be seen from Tables 1-3, through Examples 1-3 and Comparative Example 1, it can be found that the introduction of isocyanate-modified phenolic resin into epoxy molding compound has repair properties. As the molar ratio of hydroxyl groups to isocyanate groups in the isocyanate-modified phenolic resin raw material decreases, the flexural strength, Tg, and repair effect of the epoxy molding compound are all improved. The flexural strength repair rate of the secondary repair sample is about 75%. Considering both processability and economy, it is believed that modified phenolic resin can balance performance, processability, and economy.

[0200] Based on Examples 3-5, the effects of introducing anhydride curing agents on the performance and repair efficiency of epoxy molding compounds were explored. With the introduction of anhydride curing agents, Tg and flexural strength were further improved, and the flexural strength repair rate was approximately 84%.

[0201] Based on Examples 3 and 6-8, the effects of modified thermally conductive filler on the performance and repair efficiency of epoxy molding compound were explored. With the increase of modified thermally conductive filler content, the effect on Tg and flexural strength was not significant, but the repair rate was affected. Compared with the unmodified filler system, the repair rate was increased to 87%, and the flexural strength (secondary) could reach 95.7 MPa.

[0202] Based on Examples 1-9 and Comparative Examples 1-3, it can be seen that the introduction of isocyanate-modified phenolic resin is the main factor that enables epoxy molding compounds to have repair properties. Anhydride curing agents and modified thermally conductive fillers have a synergistic effect, and they do not have repair properties when used alone.

[0203] Based on Examples 1-9, the repair has little impact on thermal conductivity, and the thermal conductivity of all examples is higher than that of conventional molding compounds (around 0.9 W / m·K).

[0204] In summary, the epoxy resin composition of the present invention can achieve self-healing and high thermal conductivity while also taking into account good processability and economy.

[0205] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A self-healing epoxy molding compound, characterized in that, The self-healing epoxy molding compound comprises, by mass fraction, the following raw materials: 4-25% epoxy resin, 3-15% curing agent, 60-90% thermally conductive filler, 0.05-2% curing accelerator, 0.05-5% silane coupling agent, 0.5-2% stress release agent, 0.005-2% mold release agent, 0.1-0.6% colorant, 0.1-0.5% flame retardant, and 0.2-0.5% fumed silica; The curing agent includes isocyanate-modified phenolic resin or a mixture of isocyanate-modified phenolic resin and an acid anhydride curing agent. The method for preparing the isocyanate-modified phenolic resin is as follows: dissolve the phenolic resin in an organic solvent, then add isocyanate, and react at 35~45℃ to obtain the isocyanate-modified phenolic resin. Wherein, the molar ratio of isocyanate groups in the isocyanate to hydroxyl groups in the phenolic resin is 1:(1~8); In the isocyanate-modified phenolic resin, the isocyanate is toluene diisocyanate, and the phenolic resin is phenolic varnish resin. The thermally conductive filler includes inorganic thermally conductive fillers and / or inorganic thermally conductive fillers modified with coupling agents; The inorganic thermally conductive filler includes at least one of silicon dioxide, aluminum oxide, aluminum nitride, boron nitride, zircon, calcium silicate, calcium carbonate, and barium titanate. The curing accelerator includes at least one of cycloamidinium compounds, quinone compounds, imidazoline compounds and their derivatives, and organophosphorus compounds; The release agent comprises linear saturated carboxylic acid and / or oxidized polyethylene wax; The flame retardant includes at least one of trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dihydroxytolyl phosphate, and tris(xyl) phosphate.

2. The self-healing epoxy molding compound as described in claim 1, characterized in that, The anhydride curing agent includes at least one of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, maleic anhydride, glutaric anhydride, polyazelaic anhydride, pyromellitic dianhydride, trimellitic anhydride, halogen-containing anhydride, tung oil anhydride, and maleimide tung oil anhydride. And / or, the epoxy resin includes at least one of the following: phenolic phenolic epoxy resin, o-cresol phenolic epoxy resin, alkyl-substituted or unsubstituted diglycidyl ether epoxy resin, 1,2-stilbene epoxy resin, sulfur-containing epoxy resin, hydroquinone epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, epoxide of dicyclopentadiene cocondensed with phenol and / or naphthol resin, naphthalene-containing epoxy resin, phenol arachidonic resin, epoxide of arachidonic phenol resin, trimethylolpropane epoxy resin, and ester cyclic epoxy resin; And / or, the average particle size of the inorganic thermally conductive filler is 0.1~53μm.

3. The self-healing epoxy molding compound as described in claim 2, characterized in that, The cycloamidinium compounds include at least one of 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, and 5,6-dibutylamino-1,8-diaza-bicyclo[5.4.0]undecene-7; And / or, the quinone compound is a quinone compound formed by adding at least one of 1,4-benzoquinone, 2,5-toluenequinone, 2,3-dimethylbenzoquinone, and 2,6-dimethylbenzoquinone to the cycloamidinium compound; And / or, the imidazoline compounds include at least one of 2-methylimidazoline, 2-phenylimidazoline, and 2-phenyl-4-methylimidazoline; And / or, the organophosphorus compounds include at least one of tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tri(4-methylphenyl)phosphine, diphenylphosphine, and phenylphosphine.

4. The self-healing epoxy molding compound as described in claim 1, characterized in that, The silane coupling agent includes compounds represented by general formula (1) or (2); The structural formula of the compound represented by general formula (1) is as follows: （1）； （2）； Where m is an integer between 1 and 3; n is an integer between 0 and 3; R 1 Selected from , H2N- , , HS- One of them; b is an integer between 1 and 3; a is an integer between 0 and 3; (X) j Selected from any one of hydrogen atoms and alkyl groups having 1 to 6 carbon atoms; R 2 R 3 Each is independently selected from methyl or ethyl; R 4 R 5 Each is independently selected from methyl or ethyl.

5. The self-healing epoxy molding compound as described in claim 4, characterized in that, Silane coupling agents having the formula (1) include γ-(2,3-epoxypropoxy)propyltrimethoxysilane, trimethyloxyphenylsilane, 3-aminopropyltriethoxysilane, 3-(isobutenoyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, (3-aminopropyl)triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, γ-anilinepropyltrimethoxysilane, γ-anilinepropyltrimethoxysilane, etc. At least one of the following: γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylmethyltrimethoxysilane, γ-aminopropylmethyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylethyldiethoxysilane, and γ-aminopropylmethylethyldimethoxysilane; And / or, the silane coupling agent having the formula (2) includes at least one of γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, and γ-anilinopropylethyldimethoxysilane.

6. The self-healing epoxy molding compound as described in any one of claims 1 to 5, characterized in that, The fumed silicon is fumed silicon dioxide.

7. The self-healing epoxy molding compound as described in claim 1, characterized in that, The number-average molecular weight of the oxidized polyethylene wax is 550~1200; And / or, the average particle size of fumed silicon is 5~40 nm; And / or, the molar ratio of the epoxy groups in the epoxy resin to the hydroxyl groups in the curing agent, or the molar ratio of the epoxy groups in the epoxy resin to the anhydride groups in the curing agent, is 0.5 to 2.

8. A method for preparing a self-healing epoxy molding compound as described in any one of claims 1 to 7, characterized in that, Includes the following steps: The self-healing epoxy molding compound is obtained by mixing epoxy resin, curing agent, inorganic filler, curing accelerator, silane coupling agent, stress relief agent, optional release agent, optional colorant, optional flame retardant, and optional fumed silica, and then kneading and mixing them.

9. The application of a self-healing epoxy molding compound as described in any one of claims 1 to 7 or a self-healing epoxy molding compound prepared by the preparation method described in claim 8 in semiconductor device packaging.

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