1. The epoxy molding compound composition with low dielectric constant and low warpage is characterized by comprising the following components:

(A) an epoxy resin;

(B) a phenolic resin;

(C) an inorganic filler;

(D) a silane coupling agent;

(E) a release agent;

(F) a curing accelerator;

(G) a flame retardant;

(H) gas phase silicon;

wherein the inorganic filler of the component (C) is modified hollow glass beads, or the combination of the modified hollow glass beads and modified inorganic oxide, and the mass of the modified hollow glass beads accounts for more than 50%, preferably more than 87% of the total mass of the inorganic filler of the component (C);

the modified hollow glass beads are hollow glass beads subjected to surface modification by a silane coupling agent;

the modified inorganic oxide is an inorganic oxide subjected to surface modification by a silane coupling agent.

2. The epoxy molding compound composition according to claim 1, wherein the component (A) epoxy resin is at least one selected from the group consisting of biphenyl type epoxy resin, bisphenol F type epoxy resin, 2-diphenylethylene type epoxy resin and sulfur atom containing epoxy resin, preferably epoxy resin having biphenyl group having a structure represented by formula (I),

wherein n is an integer of 0 to 3, R¹～R⁸Each independently selected from any one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and a monovalent substituted hydrocarbon group having 1 to 10 carbon atoms, and is preferably a methyl group or an ethyl group.

3. The epoxy molding compound composition according to claim 1, wherein the phenolic resin of component (B) is at least one selected from the group consisting of phenol novolac resin, cresol novolac type epoxy resin, biphenyl type novolac resin, triphenylmethane type phenolic resin, naphthol novolac resin, aralkyl phenolic resin and biphenyl novolac resin, preferably any one or a combination of aralkyl phenolic resin and biphenyl aralkyl phenolic resin.

4. The epoxy molding compound composition according to claim 1, wherein the modified hollow glass beads have an average particle size of 0.1 μm to 40 μm, preferably 0.1 μm to 10 μm; the modified inorganic oxide is modified silicon dioxide powder, the average particle size is 5-8 mu m, and the silane coupling agent used for surface modification is a methoxy silane coupling agent, preferably gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane.

5. The epoxy molding compound composition according to claim 1, wherein the component (D), the silane coupling agent, has a structure represented by the following general formula (II),

in the formula (II), m is an integer of 1-3, n is an integer of 0-3, R¹Is selected from

H₂N-

Wherein, (X)_jSelected from hydrogen atoms and alkyl groups with 1-6 carbon atoms; r²、R³Each independently selected from methyl or ethyl, and at R²OR OR³When a plurality of the compounds exist, they may be the same as or different from each other;

preferably, R¹Is composed ofn＝3；

More preferably, the silane coupling agent of the component (D) is gamma-anilinopropyltrimethoxysilane.

6. The epoxy molding compound composition according to claim 1, wherein the component (E) the mold release agent is at least one selected from the group consisting of (a) a linear saturated carboxylic acid having a number average molecular weight of 550 to 800, and (b) an oxidized polyethylene wax, preferably, the linear saturated carboxylic acid has a number average molecular weight of 600 to 800.

7. The epoxy molding compound composition of claim 1, wherein the fumed silica of component (H) is nanosilica, and the average particle size is 5-40 nm.

8. The epoxy molding compound composition according to claim 1, wherein the epoxy resin of component (A) is 5.5 to 6.5 wt% of the total epoxy molding compound composition; the phenolic resin of the component (B) accounts for 3.5 to 4.5 percent of the total epoxy molding compound composition; the equivalent ratio of the epoxy resin of the component (A) to the phenolic resin of the component (B) is 0.5-2, preferably 0.6-1.3, and more preferably 0.8-1.0;

the inorganic filler of the component (C) accounts for 60-93 wt% of the total epoxy molding compound composition, preferably 70-92 wt%;

the component (D) is 0.05 to 5 wt% of the component (C) inorganic filler, preferably 0.1 to 2.5 wt%;

the component (E) is a mold release agent accounting for 0.005-2 wt% of the total epoxy molding compound composition;

the component (F) is a curing accelerator which is 0.005 to 2 wt%, preferably 0.01 to 0.5 wt% of the total epoxy molding compound composition;

the component (G) is 0.2-3% of the total mass of the components (A) epoxy resin, (B) phenolic resin, (D) silane coupling agent, (E) release agent, (F) curing accelerator, (G) flame retardant and (F) gas phase silicon;

the gas phase silicon of the component (H) accounts for 0.2 to 0.5 weight percent of the total epoxy molding compound composition.

9. The method for preparing the epoxy molding compound composition according to any one of claims 1 to 8, comprising the steps of mixing the components of the epoxy molding compound composition according to any one of claims 1 to 8, heating and kneading, cooling, and finely pulverizing to obtain the epoxy molding compound composition.

10. Use of the epoxy molding compound composition according to any one of claims 1 to 8 in semiconductor packaging.

Background

The epoxy plastic packaging material is widely applied to the fields of semiconductor devices, integrated circuits, consumer electronics and the like due to the characteristics of simple production process, high reliability, low cost and the like, and occupies more than 97 percent of the whole microelectronic packaging material market. In recent years, electronic packaging technology has been developed to reduce the size and weight of components, and the packaging form is gradually changed from QFP (quad flat package) and SOP (small-sized package) technology to high-density pin and high-I/O-number high-precision sealing technology, such as: BGA (ball grid array), CSP (chip size package), and the like. The updating iteration of the packaging technology puts higher requirements on the performances of the epoxy plastic packaging material such as fluidity, heat dissipation, dielectric property, warping and the like.

The epoxy plastic packaging material is one of the key materials for microelectronic packaging, and mainly has the functions of protecting high-density arranged solder balls and chips and ensuring the processability, safety and weather resistance of the chips. However, in terms of dielectric properties, most of the existing epoxy molding compounds generally have high dielectric constants, so that leakage current of the whole component is increased and a capacitance effect is generated; on the other hand, the current epoxy molding compound has large warpage, which may cause peeling between the molding compound and the chip during the packaging process. Therefore, the performance of the existing epoxy molding compound can not meet the technical requirements of the packaging process.

Therefore, the preparation of the epoxy molding compound which can inhibit the generation of warpage and has a lower dielectric constant is of great significance.

Disclosure of Invention

The invention provides an epoxy molding compound composition with low dielectric constant and low warpage for semiconductor packaging, a preparation method and application thereof, aiming at the defects of the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the invention provides an epoxy molding compound composition with low dielectric constant and low warping rate, which comprises the following components: (A) an epoxy resin; (B) a phenolic resin; (C) an inorganic filler; (D) a silane coupling agent; (E) a release agent; (F) a curing accelerator; (G) a flame retardant; (F) silicon in the gas phase.

Wherein the inorganic filler of the component (C) is modified hollow glass beads, or a combination of modified hollow glass beads and modified inorganic oxide, wherein the mass of the modified hollow glass beads accounts for more than 50%, preferably more than 87%, of the total mass of the inorganic filler of the component (C); the inorganic filler of the component (C) is preferably modified hollow glass beads.

The modified hollow glass beads are hollow glass beads subjected to surface modification by a silane coupling agent.

The modified inorganic oxide is an inorganic oxide subjected to surface modification by a silane coupling agent.

In the technical scheme of the invention, the epoxy resin of the component (A) is at least one selected from biphenyl type epoxy resin, bisphenol F type epoxy resin, 2-diphenylethylene type epoxy resin and epoxy resin containing sulfur atoms, preferably epoxy resin with biphenyl groups and a structure shown in a formula (I),

wherein n is an integer of 0 to 3, R¹～R⁸Each independently selected from a hydrogen atom, a C1-10 hydrocarbon group, or a C1-10 monovalent substituted hydrocarbon group, preferably a methyl group or an ethyl group.

In the technical scheme of the invention, the component (B) is selected from at least one of phenol novolac resin, cresol novolac epoxy resin, biphenyl novolac resin, triphenylmethane phenolic resin, naphthol novolac resin, aralkyl phenolic resin and biphenyl novolac resin; preferably, any one or a combination of a phenol aralkyl resin and a biphenyl aralkyl resin is used.

In the technical scheme of the invention, the average particle size of the modified hollow glass beads is 0.1-40 μm, preferably 0.1-10 μm; the modified inorganic oxide is modified silicon dioxide powder, the average particle size is 5-8 mu m, and the silane coupling agent used for surface modification is a methoxy silane coupling agent, preferably gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane.

In the technical scheme of the invention, the component (D) silane coupling agent has a structure shown in a general formula (II),

in the formula (II), m is an integer of 1-3, n is an integer of 0-3, R¹Is selected from

Wherein, (X)_jSelected from alkyl with 1-6 hydrogen atoms and carbon atoms, R²、R³Each independently selected from methyl or ethyl, and at R²OR OR³When a plurality of the compounds exist, they may be the same as or different from each other.

Preferably, R¹Is composed ofn＝3；

More preferably, the silane coupling agent of the component (D) is gamma-anilinopropyltrimethoxysilane.

In the technical scheme of the invention, the component (E) the release agent is at least one selected from (a) linear saturated carboxylic acid with the number average molecular weight of 550-800 and (b) oxidized polyethylene wax, and preferably, the linear saturated carboxylic acid has the number average molecular weight of 600-800.

In the technical scheme of the invention, the gas phase silicon of the component (H) is nano silicon dioxide, and the average particle size is 5-40 nm.

In the technical scheme of the invention, the epoxy resin of the component (A) accounts for 5.5-6.5 wt% of the total epoxy molding compound composition; the phenolic resin of the component (B) accounts for 3.5 to 4.5 weight percent of the total epoxy molding compound composition; the equivalent ratio of the epoxy resin of the component (A) to the phenolic resin of the component (B) is 0.5-2, preferably 0.6-1.3, and more preferably 0.8-1.0;

further, the inorganic filler of the component (C) accounts for 60 to 93 weight percent of the total epoxy molding compound composition, and preferably 70 to 92 weight percent;

further, the component (D) is 0.05 to 5 wt%, preferably 0.1 to 2.5 wt% of the component (C) inorganic filler;

further, the component (E) is a mold release agent accounting for 0.005-2 wt% of the total epoxy molding compound composition;

further, the component (F) is a curing accelerator which is 0.2 to 0.5 wt%, preferably 0.01 to 0.5 wt% of the total epoxy molding compound composition;

further, the component (G) is 0.2-3% of the total mass of the components (A) epoxy resin, (B) phenolic resin, (D) silane coupling agent, (E) release agent, (F) curing accelerator, (G) flame retardant and (F) gas phase silicon;

further, the component (H) gas phase silicon is 0.2 to 0.5 wt% of the total epoxy molding compound composition.

The second aspect of the present invention provides a method for preparing the epoxy molding compound composition, comprising the following steps: mixing the components of the epoxy molding compound composition, heating, mixing, cooling and finely crushing to obtain the epoxy molding compound composition.

The third aspect of the present invention provides the use of the epoxy molding compound composition in semiconductor packaging.

The technical scheme has the following advantages or beneficial effects:

the invention provides an epoxy molding compound composition with low dielectric constant and low warpage, which comprises the following components: the coating comprises the following components of epoxy resin, phenolic resin, inorganic filler, silane coupling agent, release agent, curing accelerator, flame retardant and gas phase silicon, wherein the inorganic filler is surface modified hollow glass beads or a combination of the surface modified hollow glass beads and surface modified inorganic oxide, and the mass of the modified hollow glass beads accounts for more than 50%, preferably more than 87% of the total mass of the inorganic filler of the component (C). The beneficial effect of this application is: according to the invention, the silane coupling agent is used for carrying out surface modification on the hollow glass beads and the silicon dioxide powder, and the silane coupling agent is used as the inorganic filler of the epoxy plastic packaging material composition, so that the bonding force between the inorganic filler and a resin matrix is improved, the specific physical properties of the hollow glass bead filler are further exerted, and the composition can keep low dielectric constant, low warpage and high fluidity while achieving high filling degree by adjusting the proportion of the modified hollow glass beads and the modified silicon dioxide powder, so that the requirements of semiconductor packaging are met.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The technical scheme of the invention is to design an epoxy molding compound composition, which comprises the following components: (A) an epoxy resin; (B) a phenolic resin; (C) an inorganic filler; (D) a silane coupling agent; (E) a release agent; (F) a curing accelerator; (G) a flame retardant; (F) silicon in the gas phase. The components will be explained and explained in detail below.

Component (A) an epoxy resin;

the epoxy resin of the component (a) in the present invention is selected from encapsulating epoxy resins, and is not particularly limited. The biphenyl type epoxy resin can be selected, as shown in the following general formula (i),

(wherein n is an integer of 0 to 3, R¹～R⁸Each independently selected from a hydrogen atom, a C1-10 hydrocarbyl group, or a C1-10 monovalent substituted hydrocarbyl group, preferably a methyl group or an ethyl group. )

In the general formula (I), the hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be linear, branched or cyclic.

Examples of the biphenyl type epoxy resin represented by the above general formula (I) include epoxy resins containing 4,4 '-bis (2, 3-epoxypropoxy) biphenyl or 4, 4' -bis (2, 3-epoxypropoxy) -3,3 ', 5, 5' -tetramethylbiphenyl as a main component.

(iii) bisphenol F type epoxy resin represented by the following general formula (ii),

(wherein n is 0 ℃; E)3 is an integer of R¹～R⁸Each independently selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl or aralkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom and a methyl group. )

The bisphenol F type epoxy resin represented by the above general formula (ii) includes, for example, R¹、R³、 R⁶And R⁸Is methyl, R²、R⁴、R⁵And R⁷YSLV-80XY (manufactured by new ferrite chemical corporation) containing n ═ 0 as a main component.

③ 1, 2-diphenylethylene type epoxy resin, represented by the following general formula (iii),

(wherein n is an integer of 0 to 3, R¹～R⁸Each independently selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl or aralkyl group having 1 to 10 carbon atoms. )

As the 1, 2-diphenylethylene type epoxy resin represented by the above general formula (iii), there may be mentioned, for example, R¹、R³、R⁶And R⁸Is methyl, R²、R⁴、R⁵And R⁷ESLV-210 (manufactured by sumitomo chemical industries, ltd., trade name) which is a hydrogen atom and has n ═ 0 as a main component is commercially available.

And (iv) a sulfur atom-containing epoxy resin represented by the following general formula (iv),

(wherein n is an integer of 0 to 3, R¹～R⁸Each independently selected from the group consisting of an alkyl group having 1 to 10 hydrogen atoms or carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an aryl group or aralkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom, a methyl group and an iso-alkyl groupA butyl group. )

Examples of the sulfur atom-containing epoxy resin represented by the above general formula (iv) include R¹And R⁸Is methyl, R³And R⁶Is isobutyl, R²、R⁴、R⁵And R⁷YSLV-120TE (trade name, manufactured by new ferrite chemical corporation) which is a hydrogen atom and contains n ═ 0 as a main component is commercially available.

The epoxy resins may be used alone or in combination.

Preferably, a difunctional epoxy resin, such as an epoxy resin having a biphenyl group as shown in the general formula (i),

a component (B) a phenol resin;

in the present invention, the phenol resin as the component (B) is used as a curing agent for the epoxy resin as the component (A). Examples thereof include phenol novolac resins, cresol novolac type epoxy resins, biphenyl type novolac resins, triphenylmethane type novolac resins, naphthol novolac resins, aralkyl novolac resins, and biphenyl novolac resins; it is preferably a phenol resin having low hygroscopicity such as an aralkyl phenol resin, a biphenylaralkyl resin, and the above phenol resins may be used alone or in any combination.

The equivalent ratio of the epoxy resin as the component (A) and the phenolic resin as the component (B), that is, the ratio of the number of epoxy groups in the epoxy resin to the number of hydroxyl groups in the curing agent is not particularly limited, but is preferably set in the range of 0.5 to 2, more preferably 0.6 to 1.3, in order to increase the conversion rate of the reactant and control the reaction rate. In order to obtain an epoxy molding compound composition having excellent moldability and reflow resistance, it is more preferable to set the range of 0.8 to 1.0.

An inorganic filler as component (C);

in the invention, the inorganic filler is mainly selected from modified hollow glass beads and modified silicon dioxide powder. The hollow glass beads have low dielectric constant and low shrinkage, and can enhance the bonding property of the inorganic filler and the resin interface through pretreatment modification. The modification method comprises the following steps: after the hollow glass bead/silicon dioxide powder and the silane coupling agent are uniformly mixed, heating and stirring are carried out, excess silane coupling agent is removed by washing, and then drying is carried out. Wherein the mass ratio of the silane coupling agent to the hollow glass beads/silicon dioxide powder is 0.02-0.08: the silane coupling agent used for the modification is not particularly limited, but γ - (2, 3-glycidoxy) propyltrimethoxysilane is used in the following examples.

The modified hollow glass beads have an average particle diameter of 0.1 to 40 μm, preferably 0.1 to 10 μm, from the viewpoint of fluidity; the modified inorganic oxide is modified silicon dioxide powder, and the average particle size is 5-8 mu m. May be fused silica powder or crystalline silica powder. These inorganic fillers may be used in any form such as pulverized, spherical or subjected to a pulverization treatment.

In the present invention, when the modified hollow glass beads and the modified silica powder are used in combination as the inorganic filler of the component (C), the amount of the modified hollow glass beads to be blended is preferably 50% or more, and more preferably 87% or more, based on the weight of the modified inorganic oxide. The content of the inorganic filler of the component (C) in the present invention is set to 60 to 93% by weight of the total epoxy molding compound composition, and more preferably, 70 to 92% by weight of the total epoxy molding compound composition. When the content of the inorganic filler of the component (C) is too low, the viscosity of the epoxy molding compound composition is too low, voids are easily generated during molding, the improvement of the dielectric constant and the thermal expansion coefficient is small, and when the content of the inorganic filler of the component (C) is too high, the flowability of the epoxy molding compound composition is poor, and the defects of incomplete filling and the like are easily caused.

Component (D) a silane coupling agent;

the silane coupling agent (D) of the present invention is a silane coupling agent having a reactive group having affinity or reactivity with the epoxy resin to be used, the reactive group being selected from mercapto group, vinyl group, epoxy group, amide group, aminophenyl group, amino group, epoxy group, cyano group or methacryloxy group, and from the viewpoint of fluidity, an aminoorganosilane coupling agent having a structure represented by formula (III) is preferable,

examples of the aminoorganosilane coupling agent represented by the above general formula (III) include: gamma-anilinopropyltrimethoxysilane, gamma-anilinopropyltriethoxysilane, gamma-anilinopropylmethyldimethoxysilane, gamma-anilinopropylmethyldiethoxysilane, gamma-anilinopropylethylethyldiethoxysilane, gamma-anilinopropylethyldimethoxysilane, etc., more preferably, gamma-anilinopropyltrimethoxysilane is used. When the amino organic silane coupling agent is mixed into the epoxy plastic packaging material composition, the adhesive property of the inorganic filler and the composition can be improved, the fluidity of the composition is improved, the characteristics of low dielectric and low warpage are kept, and the bulk property of the inorganic filler is better exerted. When the aminoorganosilane is used as the silane coupling agent as the component (D), the amount thereof is 0.05 to 5% by weight, preferably 0.1 to 2.5% by weight, based on the inorganic filler as the component (C).

A component (E) a mold release agent;

in the present invention, the component (E) is at least one release agent selected from the group consisting of (a) a linear saturated carboxylic acid having a number average molecular weight of 550 to 800, and (b) an oxidized polyethylene wax. The linear saturated carboxylic acid is a compound represented by the following general formula (IV):

wherein n is 20 to 52, but in practice, the number of repetitions n should be selected so that the number average molecular weight is 550 to 800. Preferably, the linear saturated carboxylic acid has a number average molecular weight of 600 to 800. In the following examples of the present invention, linear saturated carboxylic acids such as Unicid700 manufactured by Baker petroleum co.

The proportion and the dosage of the release agent are 0.005-2% of the weight of the total epoxy molding compound composition.

Component (F) a curing accelerator;

in the present invention, a curing accelerator is further added in view of the curability of the epoxy molding composition. The curing accelerator used in the present invention is a substance generally used in epoxy resin molding compound compositions, and is not particularly limited. Specifically, the following can be used: cyclic amidine compounds: 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; ② quinone compounds: quinone compounds such as maleic anhydride, 1, 4-benzoquinone, 2, 5-toluquinone, 2, 3-dimethylbenzoquinone, 2, 6-dimethylbenzoquinone, and 2, 3-dimethoxy-5-methyl-1 are added to the cyclic amidine compound; ③ imidazole compounds: 2-methylimidazoline, 2-phenylimidazoline, 2-phenyl-4-methylimidazoline and the like and derivatives thereof; organic phosphine: tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine, and the like; intramolecular polar compounds: and compounds obtained by adding a compound having a pi-bond such as maleic anhydride, the quinone compound, phenylazomethane, or a phenol resin to the organic phosphines.

The compounding ratio of the curing accelerator as the component (F) is preferably 0.005 to 2% by weight of the epoxy molding compound composition, more preferably 0.01 to 0.5% by weight of the epoxy molding compound composition. If the amount of the curing accelerator used is less than 0.005%, curability in a short time tends to be poor; if the content is more than 2%, the hardening rate is too high, and it is difficult to obtain a molded article having a good shape.

A flame retardant of component (G);

the flame retardant used in the present invention is not particularly limited as long as it is an ester of phosphoric acid with an alcohol or an ester with phenol. Mention may be made of: trimethyl phosphate, triethyl phosphate, triphenyl phosphate, trihydroxy tolyl phosphate, trixylyl phosphate, and cresyl diphenyl phosphate.

The component (G) is preferably 0.2 to 3 wt% of the flame retardant with respect to all the components mixed with the epoxy molding compound composition except the component (C) of the inorganic filler; . If it is less than 0.2%, problems such as lead offset and mold cavity tend to occur. If it is more than 3%, moldability and moisture resistance are lowered.

Component (H) gas phase silicon;

the fumed silica used in the present invention is a substance generally used in epoxy molding compound compositions, and is not particularly limited. Preferably, the fumed silicon is nano silicon dioxide with the average particle size of 5-40 nm.

The present invention will be described in further detail with reference to examples, but the present invention is not limited to the examples.

The components used in the following examples and comparative examples are listed below:

epoxy resin: the biphenyl type epoxy resin is represented by the formula (1), wherein R is methyl (epoxy equivalent: 192, melting point: 105 ℃ C.).

Phenolic resin 1: a biphenyl aralkyl type phenol resin (MH 7851SS, manufactured by mithrasu chemical corporation) having a hydroxyl equivalent weight of: 203, softening point: and 65 ℃.

Phenolic resin 2: phenol novolac resin (TD-2093Y, manufactured by DIC corporation), hydroxyl equivalent: 104, softening point: at 60 ℃.

Silane coupling agent 1: gamma-anilinopropyltrimethoxysilane.

Silane coupling agent 2: gamma- (2, 3-glycidoxy) propyltrimethoxysilane (product name: KBM 403).

Releasing agent: CH (CH)₃-(CH₂)_n-COOH (n ═ 24 (average), Unicid700 manufactured by beck oil company, number average molecular weight: 789).

Curing accelerator: triphenylphosphine.

The flame retardant is: trimethyl phosphate.

The gas phase silicon is: the nano silicon dioxide has the average particle size of 5-40 nm and the specific surface area of 300 +/-30 m²/g。

The colorant is: a black organic dye.

Preparing modified hollow glass beads/preparing modified silicon dioxide powder:

500 parts by mass of hollow glass beads and 25 parts by mass of gamma- (2, 3-)Glycidoxy) propyltrimethoxysilane (KBM 403) was poured into a three-necked flask; 500 parts by mass of silica, 25 parts by mass of gamma- (2, 3-glycidoxy) propyl trimethoxysilane (KBM 403) were poured into another three-necked flask; and (3) stirring the two flasks for 20min at normal temperature by using a magnetic rotor, heating the mixed solution to 80 ℃ by using an oil bath, continuing to perform magnetic stirring reaction for 30min, washing the excessive silane coupling agent for 3-5 times by using 98% ethanol after the reaction is finished, and finally drying the mixture in a drying oven at 80 ℃ for 24h to obtain the modified hollow glass microspheres and the modified silicon dioxide filler. Modified SiO obtained according to the above method₂Powder: the average particle size is 5-8 μm; modified hollow glass beads: the average particle diameter is 0.1 to 10 μm.

Example 1:

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 1, 0.25 part by mass of release agent, 87.81 parts by mass of modified hollow glass microspheres, 0.3 part by mass of gas-phase silicon and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed under the condition that the extrusion temperature is 80-110 ℃, and finally the epoxy molding compound composition is obtained.

Example 2

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 1, 0.25 part by mass of release agent, 82.81 parts by mass of modified hollow glass microspheres, 5 parts by mass of modified silica, 0.3 part by mass of fumed silica and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the extrusion temperature of 80-110 ℃, and the epoxy molding compound composition is obtained.

Example 3

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 1, 0.25 part by mass of release agent, 77.81 parts by mass of modified hollow glass microspheres, 10 parts by mass of modified silica, 0.3 part by mass of fumed silica and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the mixing temperature of 80 ℃ and the extrusion temperature of 80-110 ℃ to obtain the epoxy molding compound composition.

Example 4

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 1, 0.25 part by mass of release agent, 67.81 parts by mass of modified hollow glass microspheres, 20 parts by mass of modified silica, 0.3 part by mass of fumed silica and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the extrusion temperature of 80-110 ℃, and the epoxy molding compound composition is obtained.

Example 5

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 1, 0.25 part by mass of release agent, 57.81 parts by mass of modified hollow glass microspheres, 30 parts by mass of modified silica, 0.3 part by mass of fumed silica and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the extrusion temperature of 80-110 ℃, and the epoxy molding compound composition is obtained.

Example 6

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 1, 0.25 part by mass of release agent, 47.81 parts by mass of modified hollow glass microspheres, 40 parts by mass of modified silica powder, 0.3 part by mass of fumed silica and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the extrusion temperature of 80-110 ℃, and the epoxy plastic packaging material composition is obtained.

Example 7

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 2, 0.25 part by mass of release agent, 87.81 parts by mass of modified hollow glass microspheres, 0.3 part by mass of gas-phase silicon and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the extrusion temperature of 80-110 ℃, and finally the epoxy molding compound composition is obtained.

Example 8

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 2, 0.25 part by mass of release agent, 77.81 parts by mass of modified hollow glass microspheres, 10 parts by mass of modified silica powder, 0.3 part by mass of fumed silica and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the mixing temperature of 80 ℃ and the extrusion temperature of 80-110 ℃ to obtain the epoxy molding compound composition.

Example 9

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 2, 0.25 part by mass of release agent, 67.81 parts by mass of modified hollow glass microspheres, 20 parts by mass of modified silica powder, 0.3 part by mass of fumed silica and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the extrusion temperature of 80-110 ℃, and the epoxy plastic packaging material composition is obtained.

Example 10

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 2, 0.25 part by mass of release agent, 47.81 parts by mass of modified hollow glass microspheres, 40 parts by mass of modified silica powder, 0.3 part by mass of fumed silica and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the extrusion temperature of 80-110 ℃, and the epoxy plastic packaging material composition is obtained.

Comparative example 1

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 1, 0.25 part by mass of release agent, 87.81 parts by mass of modified silica powder, 0.3 part by mass of gas-phase silicon and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the extrusion temperature of 80-110 ℃, and the epoxy molding compound composition is obtained.

Comparative example 2

6.02 parts by mass of epoxy resin, 2.78 parts by mass of phenolic resin 1, 1.19 parts by mass of phenolic resin 2, 0.28 part by mass of curing accelerator, 0.41 part by mass of flame retardant, 0.15 part by mass of silane coupling agent 1, 0.25 part by mass of release agent, 87.81 parts by mass of unmodified hollow glass microspheres, 0.3 part by mass of gas-phase silicon and 0.2 part by mass of colorant are mixed, kneaded, mixed, cooled and finely crushed at the extrusion temperature of 80-110 ℃, and the epoxy molding compound composition is obtained.

Test method

Spiral flow: the epoxy molding compound composition was molded by transfer molding using a mold for spiral flow measurement according to EMMI-1-66 under conditions of a mold temperature of 175 ℃, a molding pressure of 6.9MPa, and a curing time of 90s, and a flow distance (cm) was obtained.

Gelation time: the epoxy molding compound composition was placed on a curing pan heated to 175 ℃ and a stopwatch was used to stir the sample uniformly using the front end of the spatula until the sample gelled, which was the gelation time.

And (3) viscosity measurement: the viscosity was measured in Pa.s using Shimadzu capillary rheometer at 175 ℃.

Warpage measurement (warpage): the warpage after compression molding of the epoxy molding compound composition is determined by using the model cap: and (3) curing the FCCSP packaging device with the thickness of 400 mu m and the thickness of the substrate of 400 mu m for 3-5 min at 175 ℃ by adopting an injection molding press of TOWA, post-curing the compression-molded epoxy molding compound composition for 4h at 175 ℃, and finally testing the warpage.

And (3) dielectric constant measurement: the samples of the above examples were subjected to a dielectric constant test using a radio frequency impedance material analyzer at a test frequency of 106Hz in accordance with GB/T1409-2006 test standards.

Dielectric loss tangent measurement: the samples of the above examples were subjected to a dielectric constant test using a radio frequency impedance material analyzer at a test frequency of 106Hz in accordance with GB/T1409-2006 test standards.

The contents of the components and the sample performance parameters of the above examples and comparative examples are shown in the following table:

wherein, "major" means "medium", "major" means "good", and "major" means "major".

Through examples 1-6, it can be seen that, as the hollow glass microspheres have the characteristics of strong flowability, high filling rate, high rigidity, low dielectric constant and the like, the flowability, viscosity, warpage, dielectric constant, dielectric loss tangent and other properties of the epoxy molding compound composition are improved with the increase of the proportion of the modified hollow glass microspheres in the inorganic filler. When the mass ratio of the modified silicon dioxide powder in the filler exceeds 40 percent, the inhibiting effect of the inorganic filler on the warping and high dielectric problem of the epoxy molding compound composition is obviously weakened. As can be seen from comparative example 1, the epoxy molding compound composition has a high dielectric constant and a large warpage due to the influence of the material properties thereof, when the modified silica powder is used as the inorganic filler. Through the example 1 and the comparative example 2, the inorganic filler subjected to surface modification can increase the compatibility with the resin matrix, which is reflected in that when the modified hollow glass microspheres are used as the inorganic filler, the viscosity of the epoxy molding compound composition is obviously reduced.

Through examples 1, 3, 4, 6, and 7-10, it can be seen that the aminoorganosilane coupling agent (silane coupling agent 1) can improve the flowability of the epoxy molding compound composition and maintain the characteristics of low dielectric constant and low warpage compared to the epoxysilane (silane coupling agent 2).

In conclusion, the epoxy molding compound composition provided by the invention can realize low dielectric constant and low warpage.

The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or other related technical fields directly or indirectly are included in the scope of the present invention.