A low dielectric constant epoxy molding compound and its preparation method and application

Abstract

The present invention discloses a low-dielectric-constant epoxy molding compound, a preparation method thereof, and applications thereof. The epoxy molding compound comprises the following components: an epoxy resin; a phenolic resin; an inorganic filler; a silane coupling agent; a release agent comprising at least one of the following: (α) a linear saturated carboxylic acid having a number-average molecular weight of 550 to 800; (β) an oxidized polyethylene wax; a curing accelerator; a flame retardant; and fumed silicon. The epoxy resin comprises a fluorinated epoxy resin and / or the inorganic filler comprises a fluorinated modified inorganic filler. The epoxy molding compound of the present invention has both a low dielectric constant and good processability and can be used for packaging semiconductor devices.

Description

Technical Field

[0001] The invention belongs to the technical field of electronic packaging materials and relates to an epoxy molding compound with a low dielectric constant and a preparation method and application thereof. Background Art

[0002] Epoxy molding compounds, due to their high reliability, low cost, and simple production process, are widely used in semiconductor devices, integrated circuits, consumer electronics, and other fields, accounting for over 97% of the total microelectronics packaging material market. In recent years, electronic packaging technology has evolved towards smaller and lighter components. Package formats have gradually shifted from QFP (quad flat package) and SOP (small outline package) to high-precision packaging technologies with high pin density and high I / O counts, such as BGA (ball grid array) and CSP (chip size package). These technological advancements have placed higher demands on epoxy molding compounds for their fluidity, heat dissipation, dielectric properties, and warpage.

[0003] Epoxy molding compound is a key material for microelectronics packaging. Its primary function is to protect high-density solder balls and chips, while ensuring chip processability, safety, and weather resistance. However, in terms of dielectric properties, most epoxy molding compounds currently have high dielectric constants, which increase leakage current throughout the component and generate capacitance effects. Consequently, the performance of existing epoxy molding compounds is no longer sufficient to meet the rapid development of packaging technology. Summary of the Invention

[0004] In order to solve the problems raised in the above background technology, the present invention aims to provide a low-dielectric-constant epoxy molding compound, its preparation method, and its application. In order to reduce the dielectric constant of the epoxy molding compound, the present invention selects a low-viscosity, low-water-absorption fluorinated epoxy resin as a resin system component and / or selects a fluorinated modified inorganic filler as the main filler. The epoxy molding compound protected by this application has the advantages of low dielectric constant, low water absorption, and high fluidity, thereby providing the encapsulated components with higher electrical insulation and structural reliability.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: a low dielectric constant epoxy molding compound, comprising the following components:

[0006] (A) Epoxy resin;

[0007] (B) phenolic resin;

[0008] (C) inorganic fillers;

[0009] (D) a silane coupling agent;

[0010] (E) a release agent comprising at least one of the following (α) and (β): (α) a linear saturated carboxylic acid having a number average molecular weight of 550 to 800, (β) an oxidized polyethylene wax;

[0011] (F) a curing accelerator;

[0012] (G) flame retardants;

[0013] (H) Fumed silicon;

[0014] The epoxy resin in the composition comprises a fluorine-containing epoxy resin, and / or the inorganic filler comprises a fluorinated modified inorganic filler.

[0015] Furthermore, the content of the epoxy resin is 4%-25% by weight of the epoxy molding compound; when the epoxy resin comprises a fluorine-containing epoxy resin, the content of the fluorine-containing epoxy resin is 0.5%-6.5% by weight of the epoxy molding compound;

[0016] Preferably, the content of the phenolic resin is 3%-15% by weight of the epoxy molding compound;

[0017] Preferably, the content of the inorganic filler is 60%-93% by weight of the epoxy molding compound, more preferably 70%-92%; (if the content of the inorganic filler is too low, the viscosity of the epoxy molding compound is too low, voids are easily generated during molding, and the dielectric constant and thermal expansion coefficient are only slightly improved; conversely, if the content of the inorganic filler is too high, the fluidity of the epoxy molding compound is poor, and defects such as incomplete filling are easily formed).

[0018] Preferably, the content of the silane coupling agent is 0.05%-0.5% by weight of the inorganic filler, preferably 0.1%-2.5%;

[0019] Preferably, the content of the release agent is 0.005%-2% by weight of the epoxy molding compound;

[0020] Preferably, the content of the curing accelerator is 0.005% to 2% by weight of the epoxy molding compound, preferably 0.01% to 0.5%; (If the amount of curing accelerator is less than 0.005%, the curing property tends to deteriorate in a short time; if it exceeds 2%, the curing speed is too fast, making it difficult to obtain a molded product with a good shape).

[0021] Preferably, the flame retardant is an ester of a compound of phosphoric acid and an alcohol or a compound of phosphoric acid and a phenol, and the flame retardant is present in an amount of 0.2% to 0.5% by weight of the epoxy molding compound, calculated as phosphorus atoms. (If the content is less than 0.2%, problems such as lead offset and mold cavity are likely to occur, and if the content is greater than 0.5%, moldability and moisture resistance are reduced.)

[0022] Preferably, the content of the fumed silicon is 0.2%-0.5% by weight of the epoxy molding compound.

[0023] Furthermore, the epoxy resin includes at least one of epoxy resin A1 and fluorine-containing epoxy resin A2. When the epoxy resin includes A1 and A2, the mass of A2 is 0.05 to 0.85 of the mass of the total epoxy resin, preferably set to the range of 0.05 to 0.7, and more preferably set to the range of 0.3 to 0.7.

[0024] Furthermore, the molecular structure of the fluorine-containing epoxy resin A2 is shown in formula (1), wherein R is a F-containing structure:

[0025]

[0026] Preferably, the fluorinated epoxy resin A2 is selected from the preparation method reference of formula (1-1) "Ding JP, Tao ZQ, Fan L, et al. Synthesis and properties of fluorinated biphenyl-type epoxyresin [J]. Journal of Applied Polymer Science, 2009, 113 (3). ", the preparation method reference of formula (1-2) "Ge, ZY, et al. Synthesis and properties of novel fluorinated epoxy resins [J]. Journal of Applied Polymer Science, 2011, 120 (1). ", the preparation method reference of formula (1-3) "Jiang, J., et al. Porous Epoxy Film for Low Dielectric Constant Chip Substrates and Boards. 2018." and the preparation method reference of formula (1-4) "Tian MA, Jm A, Jz A, et al. Curing behaviors and properties of epoxy resins with para-hexatomic ring blocks: Excellent comprehensive performances of At least one of the compounds shown in tetrafluorophenyl[J].Polymer,206.”:

[0027]

[0028] Furthermore, the epoxy resin A1 is a generally used epoxy resin molding compound for packaging, and is not particularly limited; the epoxy resin A1 includes phenol novolac epoxy resin, o-cresol novolac epoxy resin, phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and the like, which are condensed or co-condensed with aldehyde-containing compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and the like under an acidic catalyst to obtain a phenolic resin; alkyl-substituted or non-substituted diglycidyl ether epoxy resin; 1,2-diphenyl Ethylene-type epoxy resins; epoxy resins containing sulfur atoms; hydroquinone-type epoxy resins; glycidyl ester-type epoxy resins obtained by reacting polyacids such as phthalic acid and dimer acid with epichlorohydrin; glycidylamine-type epoxy resins obtained by reacting polyamines such as diaminodiphenylmethane and isocyanic acid with epichlorohydrin; epoxides of co-condensation resins of dicyclopentadiene with phenols and / or naphthols; epoxy resins containing naphthalene rings; phenol-aralkyl resins; epoxides of aralkyl-type phenol resins such as naphthol-aralkyl resins; trimethylolpropane-type epoxy resins; ester ring epoxy resins, etc., which may be used alone or in combination of two or more.

[0029] Preferably, a bifunctional epoxy resin is used, preferably an epoxy resin having a biphenyl group represented by the following general formula (2):

[0030] In formula (2), R 1 to R 8 Each is independently selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer from 0 to 3;

[0031] In the above general formula, the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms may be a saturated or unsaturated hydrocarbon group. In addition, the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms may be linear, branched or cyclic, but is particularly preferably a methyl group or an ethyl group.

[0032] Furthermore, the phenolic resin has a function as a curing agent for the epoxy resin. The phenolic resin includes one or more of phenol novolac resin, biphenyl aralkyl phenolic resin, cresol novolac epoxy resin, biphenyl novolac resin, triphenylmethane phenolic resin, naphthol novolac resin and aralkyl phenolic resin; preferably, the phenolic resin includes one or both of low hygroscopic resins such as biphenyl aralkyl phenolic resin and phenol novolac resin.

[0033] Furthermore, the equivalent ratio of the epoxy resin to the phenolic resin, i.e., the ratio of the number of epoxy groups in the epoxy resin to the number of hydroxyl groups in the phenolic resin, is not particularly limited. However, to minimize the amount of unreacted portions of each, the ratio is preferably set in the range of 0.5 to 2, more preferably in the range of 0.6 to 1.3. To obtain an encapsulating epoxy resin molding compound with excellent moldability and reflow resistance, the ratio is more preferably set in the range of 0.8 to 1.0.

[0034] Furthermore, the inorganic filler includes one or more of a fluorinated inorganic filler (the inorganic filler is fluorinated to reduce the dielectric constant) and an unmodified inorganic filler; the inorganic filler can be used in any form such as crushed, spherical or ground form;

[0035] Preferably, the inorganic filler comprises a fluorinated modified inorganic filler and an unmodified inorganic filler; more preferably, the inorganic filler comprises a fluorinated modified silica and silica;

[0036] Preferably, in view of fluidity, the average particle size of the inorganic filler is 0.1 to 45 μm, preferably 0.1 to 10 μm.

[0037] Furthermore, the fluorinated modifier used in the fluorinated inorganic filler is a fluorinated silane coupling agent, the general formula of which is shown in formula (3), wherein R is a fluorinated structure:

[0038]

[0039] Preferably, the fluorinated modifier includes one or more of heptafluorodecyltrimethoxysilane, perfluorooctyltriethoxysilane, tridecafluorooctyltrimethoxysilane, pentafluorophenyltriethoxysilane, 3-(heptafluoroisopropoxy)propyltriethoxysilane, monofluorotriethoxysilane, methyl (3,3,3-trifluoropropyl)diethoxysilane, and 3-trifluoroacetoxypropyltrimethoxysilane;

[0040] More preferably, the fluorinated modifier comprises pentafluorophenyltriethoxysilane Methyl(3,3,3-trifluoropropyl)diethoxysilane 3-(Heptafluoroisopropoxy)propyltriethoxysilane One or more of .

[0041] Furthermore, the preparation method 1 of the fluorinated modified inorganic filler comprises the following steps: mixing the inorganic filler and the fluorinated silane coupling agent evenly using magnetic stirring, then heating the mixed solution and continuing magnetic stirring for a period of time, finally washing the filler, and drying the filler in an oven to obtain a fluorinated silane coupling agent modified inorganic filler for standby use; preferably, the mass ratio of the fluorinated silane coupling agent to the inorganic filler is 0.02-0.08:1.

[0042] The preparation method 2 of the fluorinated modified inorganic filler comprises the following steps: adding the inorganic filler into a heating mixer, adding the fluorinated silane coupling agent into the mixer at a certain frequency and content during the stirring process, stirring the mixer for a period of time, and obtaining the fluorinated silane coupling agent modified inorganic filler for standby use; preferably, the mass ratio of the fluorinated silane coupling agent to the inorganic filler is 0.02-0.08:1.

[0043] The preparation method 3 of the fluorinated modified inorganic filler comprises the following steps: adding the inorganic filler into the reactor, bringing the prepared fluorinated silane coupling agent into the reactor through the gas line, generating plasma in the form of dielectric barrier discharge, thereby obtaining the fluorinated silane coupling agent modified inorganic filler for standby use; preferably, the mass ratio of the fluorinated silane coupling agent to the inorganic filler is 0.02-0.08:1.

[0044] Furthermore, the general formula of the silane coupling agent is shown in formula (4):

[0045]

[0046] In formula (4), m is an integer from 1 to 3; n is an integer from 0 to 3; R 1 Selected from:

[0047] H2N-, HS-

[0048] Among them, (X) j is selected from hydrogen atoms and alkyl groups having 1 to 6 carbon atoms; R 2 、R 3 Each independently selected from methyl or ethyl, and in R 2 OR 3 When there are multiple, they may be the same or different from each other;

[0049] In some specific embodiments, the silane coupling agent represented by formula (4) can be listed as follows: γ-(2,3-epoxypropoxy)propyltrimethoxysilane, trimethyloxyphenylsilane, 3-aminopropyltriethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, (3-aminopropyl)triethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, γ- A mixture of one or more of anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, etc.;

[0050] Preferably, in view of fluidity, the silane coupling agent is selected from one or more aminoorganosilane coupling agents represented by formula (4-1);

[0051]

[0052] In formula (4-1), m is an integer from 1 to 3; n is an integer from 0 to 3; (X) j is selected from hydrogen atoms and alkyl groups having 1 to 6 carbon atoms; R 2 、R 3 Each independently selected from methyl or ethyl, and in R 2 OR 3 When there are multiple, they may be the same or different from each other;

[0053] Examples of the aminoorganosilane coupling agent represented by formula (4-1) include γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, and γ-anilinopropylethyldimethoxysilane.

[0054] More preferably, the silane coupling agent is γ-anilinopropyltrimethoxysilane;

[0055] When the aminoorganosilane 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.

[0056] Furthermore, the linear saturated carboxylic acid with a number average molecular weight of 550 to 800 in the release agent is a compound represented by formula (5):

[0057]

[0058] More preferably, the number average molecular weight of the linear saturated carboxylic acid is 600 to 800.

[0059] Furthermore, considering the curability of epoxy molding compound, a curing accelerator is further added in the present invention. The curing accelerator used in the present invention is a substance generally used in epoxy resin molding compound for packaging, and there is no special restriction on it; the curing accelerator includes cyclic amidine compounds such as 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, 5,6-dibutylamino-1,8-diaza-bicyclo[5.4.0]undecene-7, and maleic anhydride, 1,4-benzoquinone, 2,5-toluenequinone, 2,3-dimethylbenzoquinone added to these compounds. Quinone compounds such as 2,6-dimethylbenzoquinone and 2,3-dimethoxy-5-methyl-1, imidazolines such as 2-methylimidazoline, 2-phenylimidazoline and 2-phenyl-4-methylimidazoline and their derivatives, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tri(4-methylphenyl)phosphine, diphenylphosphine and phenylphosphine, and compounds with intramolecular polarity formed by adding maleic anhydride, the above-mentioned quinone compounds, phenylazomethane, phenol resin and the like to these phosphines to form compounds with π-bonds.

[0060] Furthermore, the flame retardant used in the present invention can be any ester of a compound of phosphoric acid and alcohol or a compound of phosphoric acid and phenol, without any particular limitation. The flame retardant includes trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dihydroxycresyl phosphate, trixyl phosphate, etc. Among them, considering the hydrolysis resistance, it is preferred to use an aromatic condensed phosphate ester represented by formula (6), wherein R represents an active group having affinity or reaction ability with the epoxy resin, and R is selected from any one of mercapto, vinyl, epoxy, amide, aminophenyl, amino, epoxy, cyano or methacryloxy, and they can be the same or different;

[0061]

[0062] Furthermore, the fumed silicon used in the present invention is the fumed silicon dioxide commonly used in epoxy resin compositions for encapsulation, and is not particularly limited. Preferably, the average particle size of the fumed silicon is in the range of 5 to 40 nm.

[0063] On the other hand, the present invention provides a method for preparing any of the above-mentioned low dielectric constant epoxy molding compounds, comprising mixing epoxy resin, phenolic resin, inorganic filler, silane coupling agent, release agent, curing accelerator, flame retardant, and vapor-phase silicon, kneading and mixing at an extrusion temperature of 80 to 110°C, cooling, and finely grinding to obtain the low dielectric constant epoxy molding compound.

[0064] In another aspect, the present invention provides a use of any of the aforementioned low dielectric constant epoxy molding compounds in semiconductor device packaging.

[0065] The beneficial effect of the present application is that conventional resin systems and filler modification methods cannot achieve high filling while maintaining low dielectric constant. The present invention selects fluorinated epoxy resin as a resin system component and / or selects fluorinated modified inorganic filler as the main filler, thereby achieving epoxy molding compound with high filling while maintaining low dielectric constant. DETAILED DESCRIPTION

[0066] In order to better understand the content of the present invention, the present invention is described below with reference to the following examples and comparative examples, but the present invention should not be construed as being limited to these examples.

[0067] The epoxy resins used in the following examples and comparative examples are listed below:

[0068] Epoxy resin 1: by the general formula

[0069] Represented by biphenyl type epoxy resin, wherein R 1 to R 8 is a methyl group, and n is 0 (epoxy equivalent: 192, melting point: 105° C., available from Mitsubishi Chemical Corporation, brand name YX4000K).

[0070] Epoxy resin 2: fluorinated epoxy resin (Epoxy equivalent weight: 181, melting point: 34°C, homemade).

[0071] The phenolic resins used in the following examples and comparative examples are listed below:

[0072] Phenolic resin 1: biphenyl aralkyl type phenolic resin (hydroxyl equivalent: 203, softening point: 65° C., purchased from Meiwa Chemicals Co., Ltd., brand MEH-7851SS).

[0073] Phenolic resin 2: phenol novolac resin (hydroxyl equivalent: 104, softening point: 60° C., purchased from Sumitomo Bakelite Co., Ltd., brand PR-HF-3).

[0074] The fillers used in the following examples and comparative examples are listed as follows: fluorinated modified SiO2 powder and SiO2 powder, with an average particle size of 5 to 8 μm and a cut-off point particle size of 45 μm.

[0075] Fluorinated modifier 1: pentafluorophenyltriethoxysilane

[0076] Fluorinated modifier 2: methyl (3,3,3-trifluoropropyl) diethoxysilane

[0077] Fluorinated modifier 3: 3-(heptafluoroisopropoxy)propyltriethoxysilane

[0078] The silane coupling agents used in the following examples and comparative examples are listed below:

[0079] Silane coupling agent 1: γ-anilinopropyltrimethoxysilane.

[0080] The release agents used in the following examples and comparative examples are listed as follows: CH3-(CH2) n -COOH (n=24), Nikko Carnauba, purchased from Nikko Fine Co., Ltd.

[0081] The curing accelerator used in the following examples and comparative examples is triphenylphosphine.

[0082] The flame retardant used in the following examples and comparative examples is trimethyl phosphate.

[0083] The fumed silicon used in the following examples and comparative examples is: nano-silicon dioxide with an average particle size of 5 to 40 nm and a specific surface area of ​​300 ± 30 m 2 / g.

[0084] The colorant used in the following examples and comparative examples is: black organic dye.

[0085] Example 1

[0086] 6.02 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 87.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 110° C., cooled and finely pulverized to obtain an epoxy molding compound for a low dielectric constant.

[0087] Example 2

[0088] 500 parts by mass of silicon dioxide and 25 parts by mass of pentafluorophenyltriethoxysilane were poured into a three-necked flask; the mixture was stirred at room temperature for 20 minutes using a magnetic rotor, and then the mixed solution was heated to 80°C using an oil bath and continued to react with magnetic stirring for 30 minutes. After the reaction was completed, the excess silane coupling agent was washed 3 to 5 times with 98% ethanol, and finally dried in a drying oven at 80°C for 24 hours to obtain a fluorinated modified filler 1.

[0089] 6.02 parts by mass of epoxy resin 1, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 87.61 parts by mass of a fluorinated modified filler 1, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0090] Example 3

[0091] 6.02 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 87.81 parts by mass of a fluorinated modified silica filler 1, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0092] Example 4

[0093] 2.107 parts by mass of epoxy resin 1, 3.913 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 40 parts by mass of a fluorinated modified filler 1, 47.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0094] Example 5

[0095] 2.107 parts by mass of epoxy resin 1, 3.913 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 50 parts by mass of a fluorinated modified filler 1, 37.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0096] Example 6

[0097] 2.107 parts by mass of epoxy resin 1, 3.913 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 60 parts by mass of a fluorinated modified filler 1, 27.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0098] Example 7

[0099] 500 parts by mass of silicon dioxide and 25 parts by mass of methyl (3,3,3-trifluoropropyl) diethoxysilane were poured into a three-necked flask; the mixture was stirred at room temperature for 20 minutes using a magnetic rotor, and then the mixed solution was heated to 80°C using an oil bath and continued to react with magnetic stirring for 30 minutes. After the reaction was completed, the excess silane coupling agent was washed 3 to 5 times with 98% ethanol, and finally dried in a drying oven at 80°C for 24 hours to obtain a fluorinated modified filler 2.

[0100] 2.107 parts by mass of epoxy resin 1, 3.913 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 2, 0.25 parts by mass of a release agent, 40 parts by mass of a fluorinated modified filler 2, 47.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0101] Example 8

[0102] 2.107 parts by mass of epoxy resin 1, 3.913 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 2, 0.25 parts by mass of a release agent, 50 parts by mass of a fluorinated modified filler 2, 37.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0103] Example 9

[0104] 2.107 parts by mass of epoxy resin 1, 3.913 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 2, 0.25 parts by mass of a release agent, 60 parts by mass of a fluorinated modified filler 2, 27.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0105] Example 10

[0106] 2.107 parts by mass of epoxy resin 1, 3.913 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 3, 0.25 parts by mass of a release agent, 40 parts by mass of a fluorinated modified filler 3, 47.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0107] Example 11

[0108] 500 parts by mass of silica and 25 parts by mass of 3-(heptafluoroisopropoxy)propyltriethoxysilane were poured into a three-necked flask; the mixture was stirred at room temperature for 20 minutes using a magnetic rotor, and then the mixed solution was heated to 80°C using an oil bath, and the magnetic stirring reaction was continued for 30 minutes. After the reaction was completed, the excess silane coupling agent was washed 3 to 5 times with 98% ethanol, and finally dried in a drying oven at 80°C for 24 hours to obtain a fluorinated modified filler 3.

[0109] 2.107 parts by mass of epoxy resin 1, 3.913 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 3, 0.25 parts by mass of a release agent, 50 parts by mass of a fluorinated modified filler 3, 37.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0110] Example 12

[0111] 2.107 parts by mass of epoxy resin 1, 3.913 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 3, 0.25 parts by mass of a release agent, 60 parts by mass of a fluorinated modified filler 3, 27.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0112] Comparative Example 1

[0113] 6.02 parts by mass of epoxy resin 1, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 87.81 parts by mass of modified silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0114] Comparative Example 2

[0115] 5.418 parts by mass of epoxy resin 1, 0.602 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 87.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0116] Comparative Example 3

[0117] 5.719 parts by mass of epoxy resin 1, 0.301 parts by mass of epoxy resin 2, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 87.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0118] Comparative Example 4

[0119] 6.02 parts by mass of epoxy resin 1, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 10 parts by mass of a fluorinated modified filler 1, 77.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0120] Comparative Example 5

[0121] 6.02 parts by mass of epoxy resin 1, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 parts by mass of a curing accelerator, 0.41 parts by mass of a flame retardant, 0.15 parts by mass of a silane coupling agent 1, 0.25 parts by mass of a release agent, 20 parts by mass of a fluorinated modified filler 1, 67.81 parts by mass of silicon dioxide, 0.3 parts by mass of fumed silicon and 0.2 parts by mass of a colorant are mixed, kneaded and mixed at an extrusion temperature of 80° C., cooled and finely pulverized to obtain an epoxy molding compound with a low dielectric constant.

[0122] Test Method

[0123] Spiral Flow: The epoxy resin composition was transferred molded using a spiral flow measurement mold according to EMMI-1-66 under the structural conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds to determine the flow distance (cm).

[0124] Gel time: Place the epoxy resin composition on a curing plate heated to 175°C, use a stopwatch to time, and use the front end of a spatula to evenly stir the sample. Stop the timer when the sample gels. This time is the gel time.

[0125] Viscosity measurement: The viscosity was measured using a Shimadzu capillary rheometer at 175°C with a load of 10 kgf. The viscosity unit is Pa.s.

[0126] Dielectric constant determination: Use radio frequency impedance material analyzer, test frequency 10 6 Hz, according to the GB / T1409-2006 test standard, the above-mentioned example samples were subjected to dielectric constant testing.

[0127] Dielectric loss tangent measurement: Use RF impedance material analyzer, test frequency 10 6 Hz, according to the GB / T1409-2006 test standard, the above-mentioned example samples were subjected to a dielectric loss tangent test.

[0128] The contents of the various components and sample performance parameters of the above examples and comparative examples are shown in Table 1:

[0129] Table 1

[0130]

[0131]

[0132]

[0133]

[0134]

[0135] Can find by embodiment, the introduction of fluorine-containing resin and fluorine-containing filler can reduce the dielectric constant and dielectric loss of plastic packaging material, for the increase of fluorine-containing chain length and fluorine content of fluorinated modifier, it is more effective to reducing dielectric constant, but viscosity and fluidity have certain sacrifice. By embodiment 1-3, can know that the introduction of low-viscosity fluorinated resin can reduce system viscosity, improve flow length, can reduce the sacrifice of fluorine-containing filler to viscosity, and reduce dielectric property simultaneously.Wherein the fluorinated modifier containing benzene ring reduces equivalent dielectric constant compared with long-chain fluorinated modifier, and its sacrifice to viscosity is less.This is mainly relevant with the unique electronic effect of fluorinated phenyl group, can obtain the dielectric constant and dielectric loss reduction that are similar to more systems with fluorine content when fluorine content is less.

[0136] In summary, the epoxy resin molding compound provided by the present invention can achieve high filling and low dielectric.

[0137] The above description is only a specific embodiment of the present invention, not all embodiments. Any equivalent transformation of the technical solution of the present invention made by ordinary technicians in this field after reading the specification of the present invention is covered by the claims of the present invention.

Claims

1. A low dielectric constant epoxy molding compound, characterized in that: Contains the following ingredients: (A) Epoxy resin; (B) phenolic resin; (C) inorganic fillers; (D) silane coupling agent; (E) a release agent comprising at least one of the following (α) and (β); (α) a linear saturated carboxylic acid having a number average molecular weight of 550 to 800, and (β) an oxidized polyethylene wax; (F) curing accelerator; (G) flame retardants; (H) Fumed silicon; The epoxy resin is at least one of the fluorine-containing epoxy resins A2; the content of the epoxy resin is 4% to 6.5% by weight of the epoxy molding compound; the molecular structure of the fluorine-containing epoxy resin A2 is shown in formula (1), wherein R is a F-containing structure: （1）； The fluorine-containing epoxy resin A2 is selected from at least one of the epoxy resins represented by formula (1-2), formula (1-3) and formula (1-4); （1-2）； （1-3）； （1-4）； The inorganic filler includes one or more of a fluorinated modified inorganic filler and an unmodified inorganic filler.

2. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The content of the phenolic resin is 3%-15% of the weight of the epoxy molding compound.

3. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The content of the inorganic filler is 60%-93% of the weight of the epoxy molding compound.

4. The low dielectric constant epoxy molding compound according to claim 3, characterized in that: The content of the inorganic filler is 70%-92% of the weight of the epoxy molding compound.

5. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The content of the silane coupling agent is 0.05%-0.5% by weight of the inorganic filler.

6. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The content of the release agent is 0.005%-2% of the weight of the epoxy molding compound.

7. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The content of the curing accelerator is 0.005%-2% of the weight of the epoxy molding compound.

8. The low dielectric constant epoxy molding compound according to claim 7, characterized in that: The content of the curing accelerator is 0.01% to 0.5% of the weight of the epoxy molding compound.

9. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The flame retardant is an ester of a compound of phosphoric acid and alcohol or a compound of phosphoric acid and phenol, and the content of phosphorus atoms in the flame retardant is 0.2% to 0.5% of the weight of the epoxy molding compound excluding the inorganic filler.

10. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The content of the fumed silicon is 0.2%-0.5% by weight of the epoxy molding compound.

11. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The phenolic resin includes one or more of phenol novolac resin, biphenyl aralkyl phenolic resin, cresol novolac epoxy resin, biphenyl novolac resin, triphenylmethane phenolic resin, naphthol novolac resin, and aralkyl phenolic resin.

12. The low dielectric constant epoxy molding compound according to claim 11, characterized in that: The phenolic resin includes one or more of a biphenyl aralkyl type phenolic resin and a phenol novolac resin.

13. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The inorganic filler includes a fluorinated modified inorganic filler and an unmodified inorganic filler.

14. The low dielectric constant epoxy molding compound according to claim 13, characterized in that: The inorganic filler includes fluorinated modified silica and silica.

15. The low dielectric constant epoxy molding compound according to claim 13, characterized in that: The average particle size of the inorganic filler is 0.1-45 μm.

16. The low dielectric constant epoxy molding compound according to claim 15, characterized in that: The average particle size of the inorganic filler is 0.1-10 μm.

17. The low dielectric constant epoxy molding compound according to claim 13, characterized in that: The fluorinated modifier used in the fluorinated modified inorganic filler includes one or more of heptafluorodecyltrimethoxysilane, perfluorooctyltriethoxysilane, tridecafluorooctyltrimethoxysilane, pentafluorophenyltriethoxysilane, 3-(heptafluoroisopropoxy)propyltriethoxysilane, monofluorotriethoxysilane, methyl (3,3,3-trifluoropropyl)diethoxysilane, and 3-trifluoroacetoxypropyltrimethoxysilane.

18. The low dielectric constant epoxy molding compound according to claim 17, characterized in that: The fluorinated modifier includes one or more of pentafluorophenyltriethoxysilane, methyl (3,3,3-trifluoropropyl) diethoxysilane, and 3-(heptafluoroisopropoxy)propyltriethoxysilane.

19. The low dielectric constant epoxy molding compound according to claim 1, wherein: The silane coupling agent is selected from one or more silane coupling agents represented by formula (4): （4） In formula (4), m is an integer of 1 to 3; n is an integer of 0 to 3; R1 is selected from: ； Among them, (X) j is selected from hydrogen atoms and alkyl groups having 1 to 6 carbon atoms; R 2 、R 3 Each independently selected from methyl or ethyl, and in R 2 OR 3 When there are multiple ones, they may be the same as or different from each other.

20. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The silane coupling agent is selected from one or more amino organic silane coupling agents represented by formula (4-1); （4-1）； In formula (4-1), m is an integer from 1 to 3; n is an integer from 0 to 3; (X) j is selected from hydrogen atoms and alkyl groups having 1 to 6 carbon atoms; R 2 、R 3 Each independently selected from methyl or ethyl, and in R 2 OR 3 When there are multiple ones, they may be the same as or different from each other.

21. The low dielectric constant epoxy molding compound according to claim 19, wherein: The silane coupling agent is γ-anilinopropyltrimethoxysilane.

22. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The linear saturated carboxylic acid with a number average molecular weight of 550 to 800 in the release agent is a compound represented by formula (5): （5）。 23. The low dielectric constant epoxy molding compound according to claim 1, characterized in that: The number average molecular weight of the linear saturated carboxylic acid is 600 to 800.

24. The method for preparing the low dielectric constant epoxy molding compound according to any one of claims 1 to 23, characterized in that: Epoxy resin, phenolic resin, inorganic filler, silane coupling agent, release agent, curing accelerator, flame retardant and fumed silicon are mixed, kneaded and mixed at an extrusion temperature of 80-110° C., cooled and finely pulverized to obtain the epoxy molding compound with a low dielectric constant.

25. Use of the low dielectric constant epoxy molding compound according to any one of claims 1 to 23 in semiconductor device packaging.

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