Epoxy resin composition for molding

Abstract

The present invention relates to an epoxy resin composition and a semiconductor device molded using the same, in which the epoxy resin composition comprises an epoxy resin, a curing agent, a filler, and an organosiloxane, and the organosiloxane is a linear organosiloxane having a symmetrical structure having epoxy groups at both ends thereof.

Description

Technical Field

[0001] This invention relates to an epoxy resin composition for molding and semiconductor devices molded therefrom. Background Technology

[0002] Encapsulation resin compositions are used to improve the characteristics and reliability of semiconductor devices, such as integrated circuits (ICs), large-scale integrated circuits (LSIs), transistors, and diodes. Recently, with the trend towards miniaturization, lightweighting, and high performance in electronic devices, the process of high integration in semiconductors is accelerating, and research aimed at improving the performance of materials used for sealing semiconductor components is ongoing in many aspects. As an example, Japanese Patent Publication No. 2017-197620 discloses an epoxy resin composition for semiconductor encapsulation comprising epoxy resin, a phenolic resin curing agent, and a filler material. It discloses a technique for improving electrical connection reliability by adjusting the content of the filler material and the thermoelastic modulus of the cured epoxy resin composition.

[0003] In particular, when applied to multilayer stacked semiconductor packages, the focus is on filling fine gaps, thus requiring epoxy resin compositions with excellent meltability. However, with existing epoxy resin compositions that have improved meltability, there is a problem of swelling, where epoxy molding compound (EMC) swells outside the mold cavity, during compression molding under high pressure in a vacuum environment.

[0004] Therefore, there is a need to develop an epoxy resin composition for molding that has excellent meltability, improves gap-filling properties, and has excellent swelling inhibition properties. Summary of the Invention

[0005] The problem that the invention aims to solve

[0006] The present invention provides an epoxy resin composition for molding with excellent meltability and swelling inhibition properties, and a semiconductor device molded therefrom.

[0007] The measures taken to solve the problem

[0008] The present invention provides an epoxy resin composition comprising an epoxy resin, a curing agent, a filler, and an organosiloxane, wherein the organosiloxane is a linear organosiloxane with a symmetrical structure having epoxy groups at both ends.

[0009] The effects of the invention

[0010] This invention provides an epoxy resin composition for molding that exhibits excellent melt properties, improving gap-filling characteristics while also possessing excellent expansion inhibition properties. The epoxy resin composition according to the invention is suitable for compression molding, and in particular, its excellent expansion inhibition properties make it suitable for use as granular epoxy molding compounds (EMC). Attached Figure Description

[0011] Figure 1 This is a schematic diagram illustrating a method for evaluating the meltability of an epoxy resin composition.

[0012] Figure 2 This is a schematic diagram illustrating a method for evaluating the swelling properties of epoxy resin compositions. Detailed Implementation

[0013] The present invention will now be described in detail. However, the present invention is not limited to the following description, and the constituent elements may be used in various modifications or selective combinations as needed. Therefore, it should be understood that all modifications, equivalents, and substitutions included within the spirit and technical scope of the present invention are applicable.

[0014] The term "softening point" as used in this specification is determined using conventional methods known in the art, for example, it can be measured using a Mettler Toledo Dropping Point System Calorimetry DP70. The term "viscosity" is determined using conventional methods known in the art, for example, it can be measured at room temperature (25°C) using a Brookfield viscometer. The term "particle size (D...)" is also used. 50 ")" is determined by conventional methods known in the art, for example, it can be determined by using a laser particle size analyzer.

[0015] <Epoxy Resin Composition>

[0016] The epoxy resin composition according to the present invention comprises an epoxy resin, a curing agent, a filler, and an organosiloxane. The present invention uses a linear organosiloxane with a symmetrical structure having epoxy groups at both ends, thereby providing a sealing epoxy resin composition with excellent melt properties, improved gap-filling characteristics, and excellent expansion-inhibiting properties.

[0017] The epoxy resin composition of the present invention can be formulated into liquid, powder, granule, or sheet form, and can be used as a sealing material (EMC, epoxy molding compound) for semiconductor components or as a molding or fixing material for various electronic components and automotive parts. As an example, the epoxy resin composition for molding of the present invention is suitable for sealing large-area semiconductor packages with large dimensions and thin thickness, and can be formulated into granule-like EMC suitable for compression molding, C-molding, or lamination processes.

[0018] Epoxy resin

[0019] The epoxy resin composition of the present invention comprises epoxy resin. The epoxy resin is used as the main resin, and after curing with a curing agent, it forms a three-dimensional network structure, thereby imparting strong and firm adhesive properties and heat resistance to the substrate.

[0020] As the epoxy resin mentioned above, epoxy resins commonly used in this technical field can be used. Non-limiting examples of epoxy resins that can be used include bisphenol A type epoxy resin, alicyclic type epoxy resin, cresolnovolac type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, anthracene epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol S novolac type epoxy resin, biphenyl novolac type epoxy resin, and naphthol novolac type epoxy resin. Epoxy resins include: naphthol phenol co-condensed novolac type epoxy resin, naphthol cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenylmethane type epoxy resin, tetraphenyl ethane type epoxy resin, and dicyclopentadiene type epoxy resin.The epoxy resin may include, among others, dicyclopentadiene phenol addition reaction type epoxy resin, biphenyl type epoxy resin, phenolaralkyl type epoxy resin, polyfunctional phenol resin, and naphthol aralkyl type epoxy resin, and may contain one or more of these epoxy resins.

[0021] As an example, the epoxy resin described above may contain formaldehyde, a polymer with 1,1ˊ-biphenyl and phenol, glycidyl ether, 4,4-bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl) or mixtures thereof.

[0022] As an example, the aforementioned epoxy resin may contain formaldehyde, a polymer with 1,1ˊ-biphenyl and phenol, glycidyl ether, and 4,4-bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl). In this case, the viscosity and flowability properties can be further improved while maintaining the mechanical strength properties of the epoxy resin composition, such as flexural strength.

[0023] As the aforementioned epoxy resin, an epoxy equivalent (EEW) of 100 to 500 g / eq, for example, 150 to 300 g / eq, can be used. When the epoxy equivalent is lower than the range described above, the cured density will increase and the moisture resistance reliability will decrease; when it exceeds the range described above, the curing performance will deteriorate.

[0024] As the aforementioned epoxy resin, an epoxy resin with a softening point of 30 to 150°C, for example, 50 to 110°C, can be used. If the softening point is below the range described above, the agglomeration property will deteriorate; if it exceeds the range described above, uneven dispersion will occur during preparation.

[0025] Based on the total weight of the epoxy resin composition, the content of the epoxy resin can be 2 to 20% by weight, for example, 5 to 15% by weight. When the content of epoxy resin is lower than the range described above, the adhesion, flowability, and moldability will decrease. When it exceeds the range described above, the increased moisture absorption will lead to poor semiconductor reliability, and the relatively reduced content of filler material will lead to reduced strength.

[0026] curing agent

[0027] The epoxy resin composition of the present invention includes a curing agent. The curing agent functions to react with the epoxy resin to cure the composition.

[0028] As the aforementioned curing agent, it undergoes a curing reaction with epoxy resin. The curing agent can be any curing agent known in the art, and can be a phenolic compound having two or more phenolic hydroxyl groups within one molecule. Non-limiting examples of usable curing agents include linear phenolic resins, linear cresol phenolic resins, aralkylphenol resins, and polyfunctional phenolic compounds, and may include one or more of these.

[0029] As an example, the curing agent described above may contain a phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl, a phenol polymer with formaldehyde, or a mixture thereof.

[0030] As an example, the aforementioned curing agent may comprise a phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl and a phenol polymer with formaldehyde. In this case, the viscosity and meltability properties can be further improved while maintaining the mechanical strength properties of the epoxy resin composition, such as flexural strength.

[0031] As the curing agent mentioned above, a curing agent with a hydroxyl equivalent of 90 to 300 g / eq, for example, 100 to 200 g / eq, can be used. When the hydroxyl equivalent is below the range described above, the moisture resistance reliability deteriorates; when it exceeds the range described above, the curing performance deteriorates.

[0032] As the aforementioned curing agent, a curing agent with a softening point of 50 to 120°C, for example, 55 to 90°C, can be used. If the softening point is below the aforementioned range, the agglomeration property will deteriorate; if it exceeds the aforementioned range, the flowability will deteriorate.

[0033] Based on the total weight of the epoxy resin composition, the content of the curing agent can be 2 to 20% by weight, for example, 2 to 10% by weight. When the content of the curing agent is lower than the range described above, the curability and moldability will decrease. When it exceeds the range described above, the increased moisture absorption will lead to poor semiconductor reliability and reduced strength.

[0034] Filler material

[0035] The epoxy resin composition of the present invention includes a filler material. The filler material serves to improve the mechanical properties (e.g., strength) of the epoxy resin composition and reduce its moisture absorption.

[0036] As the aforementioned filler material, inorganic filler materials commonly used in the field of electronic materials can be used without particular restriction. For example, inorganic filler materials such as silicon dioxide, silicon nitride, aluminum oxide, aluminum nitride, and boron nitride can be used, either alone or in combination of two or more.

[0037] The shape of the filler material is not particularly limited, and both angular and spherical shapes can be used. Non-limiting examples of filler materials that can be used in this invention include natural silica, synthetic silica, fused silica, etc. For example, spherical silica particles can be used.

[0038] The aforementioned filler material may contain two or more filler materials with different particle sizes to improve mechanical properties. In this case, the moldability and workability of the epoxy resin composition can be further improved. For example, the aforementioned filler material may contain an average particle size (D... 50 The first filler material has a particle size of 3.5 to 20 μm, for example, 3.5 to 15 μm, and an average particle size (D). 50 The second filler material is 0.1 to 3 μm, for example, 0.1 to 1 μm.

[0039] Based on the total weight of the epoxy resin composition, the content of the filler material is 50 to 90% by weight, for example, 70 to 90% by weight. When the content of the filler material is lower than the range described above, the moisture absorption of the cured product increases, thereby reducing the reliability of the semiconductor device. When it exceeds the range described above, the flowability decreases, resulting in poor moldability.

[0040] organosiloxanes

[0041] The epoxy resin composition of the present invention contains an organosiloxane to improve dispersibility. The aforementioned organopolysiloxane is a linear organosiloxane with a symmetrical structure having epoxy groups at both ends. Due to the use of organopolysiloxanes with this structure, excellent meltability is achieved, thereby improving gap-filling properties, and an epoxy resin composition for sealing with excellent expansion inhibition properties can be provided.

[0042] The aforementioned organosiloxanes possess a symmetrical linear molecular structure, thus exhibiting high compatibility with epoxy resin compositions, particularly those containing biphenyl-based epoxy resins. Furthermore, these organosiloxanes have reactive epoxy groups at both ends, thus acting as reactive diluents in the cross-linking curing reaction between the epoxy resin and the phenol curing agent, effectively dispersing the epoxy resin composition. Consequently, the surface tension of the molten epoxy resin composition is reduced, suppressing the expansion of internal bubbles in the cured epoxy resin composition and lowering the viscosity of the molten epoxy resin composition, thereby improving moldability. Additionally, the aforementioned organosiloxanes can improve melt flow and expansion suppression properties while maintaining the adhesiveness of the epoxy resin composition.

[0043] The aforementioned organosiloxane can be represented by the following chemical formula 1.

[0044] [Chemical Formula 1]

[0045]

[0046] In the above formula,

[0047] EP stands for epoxy group.

[0048] R1 is a hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms.

[0049] R2 is a hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms.

[0050] a is an integer from 1 to 5.

[0051] n is an integer from 1 to 5.

[0052] As an example, in the above formula, EP is an epoxy group, R1 is a hydrogen or substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, R2 is a hydrogen or substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a is an integer from 1 to 5, and n is an integer from 1 to 5.

[0053] As an example, in the above formula, EP is an epoxy group, R1 is a substituted or unsubstituted alkyl group with 1 to 3 carbon atoms, R2 is a substituted or unsubstituted alkyl group with 1 to 3 carbon atoms, a is an integer from 1 to 3, and n is an integer from 1 to 3.

[0054] As an example, in the above formula, EP is an epoxy group, R1 is a methyl group, R2 is a methyl group, a is 1, and n is 3.

[0055] As the aforementioned organosiloxane, organosiloxanes with a molecular weight of 300 to 800 g / mol, for example 300 to 500 g / mol, and a viscosity (25°C) of 0.005 to 1 Pa∙s, for example 0.05 to 0.1 Pa∙s, can be used. Using organosiloxanes with low molecular weight and low viscosity within the aforementioned range is beneficial for mixing the epoxy resin composition, thereby exhibiting high dispersibility. When the molecular weight or viscosity exceeds the aforementioned range, the compatibility between the epoxy resin composition and the organosiloxane decreases, thus reducing the dispersibility effect and causing appearance defects such as flow marks.

[0056] Based on the total weight of the epoxy resin composition, the content of the aforementioned organosiloxane can be from 0.05% to 5% by weight, for example, from 0.1% to 3% by weight. When the content of organosiloxane is below the range described above, the improvement in melt properties and the swelling inhibition effect will be limited; when it exceeds the range described above, the reliability and strength of the epoxy resin composition will decrease.

[0057] additive

[0058] The epoxy resin composition of the present invention may further include additives commonly used in molding compositions. Non-limiting examples of additives that can be used include catalysts, coupling agents, ion catchers, colorants, and release agents.

[0059] Catalysts promote the curing reaction and can include imidazole compounds, naphthalene-based latent catalysts, amine compounds, organometallic compounds, organophosphorus compounds, boron compounds, etc. Coupling agents promote the bonding between inorganic and organic substances and can include aminosilanes, epoxysilanes, etc. Ion scavengers capture and remove impurity ions to reduce corrosion and can include inorganic ion exchangers such as magnesium aluminum carbonate hydrate. Colorants are added to impart color to the resin composition and can include carbon black, iron oxide red, etc. Release agents are added to ensure the release of the cured epoxy resin composition from the metal mold and can include paraffin wax, carnauba wax, polyethylene wax, ester wax, etc.

[0060] The above-mentioned additives can be added within the content range known in the art. As an example, they can each contain 0.01 to 5% by weight relative to the total weight of the epoxy resin composition, but are not limited thereto.

[0061] The epoxy resin composition according to the present invention can be prepared by conventional methods known in the art, for example, by melt mixing methods using a Banbury mixer, kneader, roller, single-shaft or twin-shaft extruder and compounding extruder.

[0062] The epoxy resin composition of the present invention can be formulated into powder, granules, etc. In particular, the epoxy resin composition according to the present invention has excellent swelling inhibition properties, and therefore can be formulated into granules for compression molding.

[0063] For example, in the case of powdered or granular epoxy resin compositions, the components described above are uniformly mixed, then melt-mixed at a temperature of 80 to 130°C using a heat kneader and cooled to room temperature, then pulverized into powder, and then prepared by a sieving process, but not limited to this.

[0064] <Semiconductor components and automotive parts>

[0065] This invention provides a semiconductor element molded using the epoxy resin composition described above. The semiconductor element can be a transistor, diode, microprocessor, semiconductor memory, power semiconductor, etc.

[0066] Furthermore, the present invention provides a vehicle accessory molded using the aforementioned epoxy resin composition. As an example, by using the aforementioned epoxy resin composition as a molding material, components within the vehicle accessory can be fixed and sealed. Specifically, a permanent magnet is inserted into a vacant space formed within the rotor core of a vehicle electric motor, and the vacant space and the permanent magnet are filled with the epoxy resin composition of the present invention to fix the permanent magnet within the rotor core.

[0067] The method of molding semiconductor elements or vehicle parts using an epoxy resin composition according to the present invention can be performed by appropriately selecting conventional methods in this technical field, such as transfer molding, compression molding, injection molding, etc.

[0068] Methods of implementing the invention

[0069] The present invention will now be described in more detail through embodiments. However, the embodiments described below are merely illustrative of the invention and are not intended to limit the scope of the invention in any way to the embodiments.

[0070] [Examples 1-4]

[0071] According to the composition described in Table 1 below, the components were combined and melt-mixed at a temperature of 100 to 130°C using a melt mixer, cooled to room temperature, and then pulverized into powder. The granular epoxy resin compositions of each embodiment were prepared by sieving.

[0072] [Comparative Examples 1-7]

[0073] In addition to the compositions described in Table 2 below, the granular epoxy resin compositions of each comparative example were prepared using the same method as those in the examples.

[0074] [Table 1]

[0075]

[0076] [Table 2]

[0077]

[0078] Epoxy Resin 1: Multifunctional epoxy resin (formaldehyde, polymer with 1,1ˊ-biphenyl and phenol, glycidyl ether, Cas No. 1201169-35-8)

[0079] Epoxy Resin 2: Biphenyl-based epoxy resin (4,4-bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl))

[0080] Curing agent 1: Multifunctional phenolic resin (a phenolic polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl, Cas No. 0106466-55-1)

[0081] Curing agent 2: Phenol linear phenolic resin (phenol polymer with hydroxybenzaldehyde, Cas No. 0205830-20-2)

[0082] Filler material: Silicon dioxide

[0083] Organosiloxane 1: 1,3-Bis(3-(2,3-epoxypropoxy)propyl)1,1,3,3-tetramethyldisiloxane (1,3-Bis(3-(2,3-epoxypropoxy)propyl)1,1,3,3-tetramethyldisiloxane)

[0084] Organosiloxane 2: Organosiloxanes with amino groups at both ends (dual-end type / Amino-modified silicone fluids), viscosity (at 25°C) is 25 mm. 2 / s, Mw is 1,600g / mol, amine value is 70mgKOH / g)

[0085] Organosiloxane 3: 3-[2-(3,4-epoxycyclohexyl)ethyl]-heptamethyltrisiloxane

[0086] Organosiloxane 4: Modified siloxanes containing epoxy and polyether groups in the side chain (Epoxy and polyether modified silicone polymer, Cas No. 0101810-98-4, with a kinematic viscosity (at 25°C) of 2,200 mmHg). 2 / s, epoxy equivalent is 5,200 g / mol)

[0087] Ion scavenger: (Carbonato) hexadecahydroxydialuminum-hexamagnesium

[0088] Catalyst: 5-Methyl-2-phenylimidazole-4-methanol

[0089] Coupling agent: (3-mercaptopropyl)trimethoxysilane

[0090] Colorant: Carbon Black

[0091] Release agent: Ester wax

[0092] [Physical Property Evaluation]

[0093] The physical properties of the epoxy resin compositions prepared in each example and comparative example were measured as follows, and the results are shown in Tables 3 and 4 below.

[0094] Spiral flow

[0095] The flowability of the epoxy resin compositions prepared according to the various examples and comparative examples was measured after molding them in a heated conveyor molding machine (pressure 16 kgf / cm², temperature 175°C, curing time 120 seconds) using a spiral flow mold.

[0096] gelation time

[0097] The gelation time of small amounts of epoxy resin compositions prepared according to the various examples and comparative examples was determined after uniform spreading in a gel timer.

[0098] Flexural strength

[0099] The measurements were performed according to ASTM D638, D256, and D790.

[0100] Flexural modulus

[0101] The epoxy resin compositions prepared according to the various examples and comparative examples were molded using a specimen mold (125 mm wide, 12.5 mm high, and 6 mm thick) in a heated conveyor molding machine (pressure 70 kg / cm², temperature 175 °C, curing time 120 seconds), cured in an oven at 175 °C for 4 hours, and then measured using a universal testing machine (UTM).

[0102] Meltability

[0103] like Figure 1As shown, epoxy resin compositions (6.0 g) prepared according to the various examples and comparative examples were dispensed onto a release film with a narrow area and compressed using a compression molding apparatus under the conditions of a temperature of 175°C, a maximum pressure of 30 tons, a compression time of 25 seconds (time to reach maximum pressure), and a curing time of 120 seconds. The spreading area of ​​the melted epoxy resin composition was then measured. The meltability of the epoxy resin composition was evaluated by calculating the spreading area ratio using the following formula.

[0104]

[0105] Swelling

[0106] like Figure 2 As shown, 2.0 g of the epoxy resin composition prepared according to each example and comparative example was metered into a vial. After placing the metered vial on a hot plate at 175°C and 640 torr under vacuum for 5 minutes, the height of the sample expansion was measured. The rate of change was calculated using the following formula to evaluate the expansion characteristics.

[0107]

[0108] Height before heating

[0109] Height after heating - Ho

[0110] [Table 3]

[0111]

[0112] [Table 4]

[0113]

[0114] As shown in Tables 3 and 4 above, the epoxy resin compositions of Examples 1-4, which contain an organosiloxane (organosiloxane 1) of the present invention with a symmetrical linear structure having epoxy groups at both ends, exhibited excellent physical properties throughout the test items.

[0115] Conversely, the epoxy resin compositions of Comparative Examples 1-4, which did not use organosiloxanes, exhibited poor melt properties or swelling inhibition properties. Furthermore, the epoxy resin compositions of Comparative Example 5, which used an organosiloxane with amino groups at both ends (organosiloxane 2) instead of the organosiloxane according to the present invention; Comparative Example 6, which used an organosiloxane with epoxy groups in the non-terminal side chains (organosiloxane 3); and Comparative Example 7, which used an organosiloxane with epoxy and polyether groups in the non-terminal side chains (organosiloxane 4), all exhibited poor melt properties or swelling inhibition properties.

[0116] Industrial availability

[0117] The present invention provides an epoxy resin composition for molding that has excellent melt properties, improves gap filling properties, and has excellent expansion inhibition properties.

Claims

1. An epoxy resin composition, characterized in that, It contains epoxy resin, curing agent, filler, and organosiloxane. The aforementioned organosiloxanes are linear organosiloxanes with a symmetrical structure having epoxy groups at both ends.

2. The epoxy resin composition according to claim 1, characterized in that, The softening point of the epoxy resin is 30 to 150°C, and the softening point of the curing agent is 50 to 120°C.

3. The epoxy resin composition according to claim 1, characterized in that, The above-mentioned organosiloxanes are represented by the following chemical formula 1: [Chemical Formula 1] ; In the above chemical formula, EP stands for epoxy group. R1 is a hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms. R2 is a hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms. a is an integer from 1 to 5. n is an integer from 1 to 5.

4. The epoxy resin composition according to claim 1, characterized in that, The aforementioned organosiloxanes have a molecular weight of 300 to 800 g / mol and a viscosity of 0.005 to 1 Pa∙s at 25°C.

5. The epoxy resin composition according to claim 1, characterized in that, Based on the total weight of the epoxy resin composition, it comprises 2 to 20% by weight of the epoxy resin, 2 to 20% by weight of the curing agent, 50 to 90% by weight of the filler, and 0.05 to 5% by weight of the organosiloxane.

6. A semiconductor element, characterized in that, The semiconductor element is molded using an epoxy resin composition according to any one of claims 1 to 5.

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