Epoxy resin composition for molding

Abstract

The present invention relates to an epoxy resin composition for molding and a semiconductor device molded using same.

Description

Epoxy resin composition for molding

[0001] The present invention relates to an epoxy resin composition for molding and a semiconductor device molded using the same.

[0002]

[0003] A resin composition for sealing is used as a material to seal semiconductor devices such as integrated circuits (ICs), large scale integrated circuits (LSIs), transistors, and diodes, thereby improving the characteristics and reliability of semiconductor devices. Recently, with the trend toward miniaturization, weight reduction, and higher performance of electronic devices, the integration of semiconductors has accelerated, and research is continuing in various fields to improve the performance of materials used for sealing semiconductor devices. For example, Japanese Patent Application Laid-Open No. 2017-197620 relates to an epoxy resin composition for semiconductor sealing, which includes an epoxy resin, a phenol resin curing agent, and a filler, and discloses a technology for improving electrical connection reliability by controlling the content of the filler and the thermoelastic modulus of the cured product of the epoxy resin composition.

[0004] In particular, to provide an epoxy resin composition with high heat dissipation properties, it is necessary to include a high content of filler to increase thermal conductivity. However, this leads to the problem of poor dispersibility. Therefore, there is a need to develop an epoxy resin composition for molding with excellent dispersibility, flowability, and thermal conductivity.

[0005]

[0006] The present invention provides an epoxy resin composition for molding having excellent dispersibility, flowability and thermal conductivity, and a semiconductor device molded using the same.

[0007]

[0008] The present invention provides an epoxy resin composition comprising an epoxy resin, a curing agent, a filler, and a siloxane, wherein the siloxane is a symmetrical disiloxane having an alicyclic epoxy group at both terminals.

[0009]

[0010] The present invention provides an epoxy resin composition for molding, which exhibits excellent dispersibility, flowability, and thermal conductivity. Furthermore, the epoxy resin composition according to the present invention exhibits excellent physical properties, such as strength and glass transition temperature. The epoxy resin composition according to the present invention exhibits excellent thermal conductivity, making it applicable as a molding compound with high heat dissipation properties.

[0011]

[0012] The present invention will be described in detail below. However, it is not limited to the following description, and each component may be modified or selectively mixed as needed. Therefore, it should be understood that all modifications, equivalents, and alternatives included within the spirit and technical scope of the present invention are included.

[0013] The “softening point” used herein is measured by a conventional method known in the art, and can be measured, for example, with a dropping point meter (Dropping Point system calorimetry DP70) from Mettler Toledo. The “viscosity” is measured by a conventional method known in the art, and can be measured, for example, using a Brookfield viscometer at room temperature (25°C). The “particle size (D50)” is measured by a conventional method known in the art, and can be measured, for example, with a laser particle size analyzer.

[0014]

[0015] Epoxy resin composition

[0016] An epoxy resin composition according to the present invention comprises an epoxy resin, a curing agent, a filler, and a siloxane. The present invention provides an epoxy resin composition for encapsulating semiconductor devices, which has excellent dispersibility, flowability, and thermal conductivity, by using a symmetrical disiloxane having alicyclic epoxy groups at both terminals as the siloxane.

[0017] The epoxy resin composition of the present invention can be manufactured in a liquid, powder, granule, or sheet form, and can be used as a sealant (EMC, epoxy molding compound) for semiconductor devices or as a molding material or fixing material for various electronic components and automotive components. For example, the epoxy resin composition for molding of the present invention can be applied for sealing a large-area semiconductor package that is large in size and thin in thickness, and can be manufactured as a granule-type EMC applicable to a compression type molding process, a C-molding process, or a lamination process.

[0018]

[0019] epoxy resin

[0020] The epoxy resin composition of the present invention comprises an epoxy resin. The epoxy resin is used as a main resin, and by reacting with a curing agent and curing, forms a three-dimensional network structure, thereby imparting strong and solid adhesion properties to an adherend and heat resistance.

[0021] As the above epoxy resin, an epoxy resin commonly used in the relevant technical field can be used. Non-limiting examples of usable epoxy resins include bisphenol A type epoxy resins, alicyclic epoxy resins, cresol novolac epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, anthracene epoxy resins, tetramethyl biphenyl type epoxy resins, phenol novolac epoxy resins, bisphenol A novolac epoxy resins, bisphenol S novolac epoxy resins, biphenyl novolac epoxy resins, naphthol novolac epoxy resins, naphthol phenol cocondensed novolac epoxy resins, naphthol cresol cocondensed novolac epoxy resins, aromatic hydrocarbon formaldehyde resin modified phenol resin epoxy resins, triphenyl methane type epoxy resins, tetraphenyl ethane type epoxy resins, dicyclopentadiene type epoxy resins, dicyclopentadiene phenol addition reaction epoxy resins, biphenyl type epoxy resins, phenol aralkyl type epoxy resins, multifunctional phenol resins, and naphthol. There are aralkyl type epoxy resins, etc., and one or more of these may be included.

[0022] For example, the epoxy resin may include 4,4-bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl). In this case, the viscosity of the epoxy resin composition can be more effectively reduced and the flowability can be increased.

[0023] The above epoxy resin may be used having an epoxy equivalent weight (EEW) of 100 to 500 g / eq, for example, 150 to 300 g / eq. If the epoxy equivalent weight is less than the above-mentioned range, the curability, flowability, and moldability may be reduced, and if it exceeds the above-mentioned range, the strength and adhesion may be reduced.

[0024] The above epoxy resin may be used having a softening point of 30 to 150°C, for example, 50 to 110°C. If the softening point is below the above-mentioned range, the curing properties, flowability, and moldability may be reduced, and if it exceeds the above-mentioned range, the reactivity may be delayed, resulting in reduced dispersibility.

[0025] Based on the total weight of the epoxy resin composition, the content of the epoxy resin may be 1 to 20 wt%, for example, 1.5 to 10 wt%. If the content of the epoxy resin is less than the above-mentioned range, adhesion, flowability, and moldability may be reduced, and if it exceeds the above-mentioned range, the reliability of the semiconductor may be deteriorated due to an increase in moisture absorption, and the strength may be reduced due to a relative decrease in the filler content.

[0026]

[0027] hardener

[0028] The epoxy resin composition of the present invention includes a curing agent. The curing agent reacts with the epoxy resin to promote curing of the composition.

[0029] The curing agent may be any curing agent known in the art that undergoes a curing reaction with an epoxy resin. The curing agent may be a phenol-based compound having two or more phenolic hydroxyl groups in one molecule. Non-limiting examples of usable curing agents include phenol novolac resins, cresol novolac resins, phenol aralkyl resins, and multifunctional phenol compounds, and the curing agent may include one or more of these.

[0030] For example, the curing agent may include a phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl, a phenol polymer with 1,4-bis(methoxymethyl)benzene, or a mixture thereof. For example, the curing agent may include a phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl and a phenol polymer with 1,4-bis(methoxymethyl)benzene. In this case, further improved dispersibility and reliability can be secured.

[0031] The above-mentioned hardener may be used having a hydroxyl equivalent of 90 to 300 g / eq, for example, 100 to 200 g / eq. If the hydroxyl equivalent is less than the above-mentioned range, the curing properties, flowability, and moldability may be reduced, and if it exceeds the above-mentioned range, the adhesion may be reduced.

[0032] The above-mentioned hardener may be one having a softening point of 50 to 120°C, for example, 55 to 90°C. If the softening point is below the above-mentioned range, the hardening property, flowability, and moldability may be reduced, and if it exceeds the above-mentioned range, the reaction may be delayed, resulting in reduced dispersibility.

[0033] Based on the total weight of the epoxy resin composition, the content of the curing agent may be 1 to 20 wt%, for example, 1 to 10 wt%. If the content of the curing agent is less than the above-mentioned range, curability and formability may be reduced, and if it exceeds the above-mentioned range, the reliability of the semiconductor may be deteriorated and the strength may be reduced due to an increase in moisture absorption.

[0034]

[0035] filling

[0036] The epoxy resin composition of the present invention includes a filler. The filler improves the mechanical properties (e.g., strength) of the epoxy resin composition and reduces moisture absorption.

[0037] As the filler, any inorganic filler commonly used in the field of electronic materials can be used without any particular limitation. For example, inorganic fillers such as silica, silica nitride, alumina, aluminum nitride, and boron nitride can be used, and these can be used alone or in combination of two or more. For example, the filler can include alumina and silica, and for example, can include alumina and silica in a weight ratio of 9:1. In this case, the curability of the epoxy resin composition can be further enhanced.

[0038] The shape of the above filler is not particularly limited, and both angular and spherical shapes can be used. Non-limiting examples of fillers that can be used in the present invention include natural silica, synthetic silica, and fused silica, and for example, spherical silica particles can be used.

[0039] The above filler may include two or more types of fillers having different particle sizes. In this case, the moldability and workability of the epoxy resin composition can be further improved. For example, the filler may include a first filler having an average particle size (D50) of 3.5 to 20 um, for example, 3.5 to 15 um, and a second filler having an average particle size (D50) of 0.1 to 3 um, for example, 0.1 to 1 um.

[0040] Based on the total weight of the epoxy resin composition, the content of the filler may be 50 to 95 wt%, for example, 70 to 95 wt%. If the content of the filler is less than the above-mentioned range, the moisture absorption of the cured product may increase, which may lower the reliability of the semiconductor device. If the content exceeds the above-mentioned range, the fluidity may be reduced, resulting in poor formability.

[0041]

[0042] Siloxane

[0043] The epoxy resin composition of the present invention includes siloxane. The siloxane is a symmetrical disiloxane having alicyclic epoxy groups at both ends. By using a siloxane having such a structure, an epoxy resin composition for encapsulating semiconductor devices can be provided with excellent dispersibility, flowability, and thermal conductivity. The epoxy groups included in the siloxane structure participate in the curing reaction between epoxy and phenol, thereby reducing side effects such as strength reduction and flow mark formation that occur when adding conventional siloxane compounds. In particular, by including alicyclic epoxy groups, the phenomenon of a lower glass transition temperature when using a siloxane with a linear structure can be prevented. In addition, the symmetrical siloxane has a structural similarity to a crystalline epoxy resin, enabling crosslinking with the epoxy resin. This increases dispersibility, enabling a higher filler content formulation design, thereby improving the thermal conductivity of the EMC.

[0044] The above siloxane can be represented by the following chemical formula 1.

[0045] [Chemical Formula 1]

[0046]

[0047] In the above formula,

[0048] R1 is an alicyclic epoxy having 5 to 10 carbon atoms,

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

[0050] R3 is hydrogen, a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms,

[0051] a is an integer from 1 to 10.

[0052] For example, in the above formula, R1 is an alicyclic epoxy having 5 to 10 carbon atoms, R2 is hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, R3 is hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and a is an integer of 1 to 10.

[0053] For example, in the above formula, R1 is an alicyclic epoxy having 5 to 7 carbon atoms, R2 is hydrogen, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, R3 is hydrogen, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and a is an integer of 1 to 5.

[0054] For example, in the above formula, R1 is an alicyclic epoxy having 6 carbon atoms, R2 is a methyl group, R3 is a methyl group, and a is 2.

[0055] For example, the siloxane may be represented by the following chemical formula 2.

[0056] [Chemical Formula 2]

[0057]

[0058] The above siloxane may be used having a molecular weight of 200 to 800 g / mol, for example, 250 to 450 g / mol, and a viscosity (at 25°C) of 5 to 1,000 mPa·s, for example, 10 to 200 mPa·s. If the molecular weight is less than the above-mentioned range, the moldability may be reduced, and if it exceeds the above-mentioned range, the flowability may be reduced. If the viscosity exceeds the above-mentioned range, the flowability may be reduced.

[0059] Based on the total weight of the epoxy resin composition, the content of the siloxane may be 0.1 to 10 wt%, for example, 0.1 to 3 wt%. If the content of the siloxane is less than the above-mentioned range, dispersibility may be reduced, and if it exceeds the above-mentioned range, formability and strength may be reduced.

[0060]

[0061] additives

[0062] The epoxy resin composition of the present invention may additionally include additives commonly used in such compositions. Non-limiting examples of usable additives include catalysts, coupling agents, colorants, and release agents.

[0063] The catalyst promotes the curing reaction, and examples of the catalyst include imidazole compounds, naphthalene-based latent catalysts, amine compounds, organometallic compounds, organophosphorus compounds, and boron compounds. The coupling agent promotes the bonding between inorganic and organic substances, and examples of the coupling agent include amino silane and epoxy silane. The coloring agent is added to impart color to the resin composition, and examples of the coloring agent include carbon black and Bengala. The releasing agent is added to secure releasability between the EMC and the mold, and examples of the releasing agent include paraffin wax, carnauba wax, polyethylene wax, and ester wax.

[0064] The above additives may be added within a content range known in the relevant technical field, and for example, may be included in an amount of 0.01 to 5 wt%, respectively, based on the total weight of the epoxy resin composition, but is not limited thereto.

[0065]

[0066] The epoxy resin composition according to the present invention can be produced by a conventional method known in the art, for example, a melt mixing method using a semi-bar mixer, a kneader, a roll, a single-screw or twin-screw extruder, and a con-kneader.

[0067] The epoxy resin composition of the present invention can be manufactured in powder form, granule form, etc. In particular, the epoxy resin composition according to the present invention has excellent swelling inhibition properties, so it can be manufactured in granule form and applied to a compression molding method.

[0068] For example, in the case of a powder-type or granular epoxy resin composition, the components as described above are uniformly mixed, melted and mixed at a temperature of 80 to 130°C using a heat kneader, cooled to room temperature, pulverized into a powder state, and then subjected to a sieving process, but the present invention is not limited thereto.

[0069]

[0070] Semiconductor devices and automotive components

[0071] The present invention provides a semiconductor device molded using the epoxy resin composition described above. The semiconductor device may be a transistor, a diode, a microprocessor, a semiconductor memory, a power semiconductor, or the like.

[0072] In addition, the present invention provides a vehicle component molded using the epoxy resin composition described above. For example, the epoxy resin composition described above can be used as a molding material to fix and seal components within the vehicle component. Specifically, a permanent magnet can be inserted into a hollow space formed within a rotor core of a vehicle motor, and the epoxy resin composition of the present invention can be filled between the hollow space and the permanent magnet to fix the permanent magnet within the rotor core.

[0073] A method for molding a semiconductor device or a vehicle part using the epoxy resin composition of the present invention can be appropriately selected and performed according to a conventional method in the relevant technical field, such as transfer molding, compression molding, or injection molding.

[0074]

[0075] Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended only to aid understanding of the present invention and are not intended to limit the scope of the present invention in any way.

[0076]

[0077] [Example 1-2]

[0078] After mixing each component according to the composition described in Table 1 below, the mixture was melt-mixed at a temperature of 100 to 130°C using a melt kneader, cooled to room temperature, pulverized into a powder state, and then subjected to a sieving process to produce a granular epoxy resin composition of each example.

[0079]

[0080] [Comparative Example 1-6]

[0081] Each granular epoxy resin composition of each comparative example was prepared in the same manner as in the examples, except that the compositions were as described in Table 1 below.

[0082]

[0083]

[0084]

[0085] Epoxy resin: 4,4-Bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl)

[0086] Curing agent 1: Phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl (Cas no. 0205830-20-2, viscosity (150 ℃) 90 mPa.s, EW (Equivalent Weight) 210 g / eq)

[0087] Curing agent 2: Phenol polymer with 1,4-bis(methoxymethyl)benzene (Cas no. 0026834-02-6, Mw 580 g / mol)

[0088] Filler: Aluminum oxide 90 wt% + Silicon dioxide 10 wt% (DENKA, DAB-10FC)

[0089] Siloxane 1: (bis-epoxycyclohexyl disiloxane)

[0090] Siloxane 2: Allyl phthalimide trisiloxane

[0091] Siloxane 3:

[0092] Siloxane 4: 3-[2-(3,4-epoxycyclohexyl)ethyl]-heptamethyltrisiloxane

[0093] Siloxane 5:

[0094] Siloxane 6: 1,3-Bis(3-(2,3-epoxypropoxy)propyl) 1,1,3,3-tetramethyldisiloxane

[0095] Catalyst: Triphenylphosphine

[0096] Coupling agent: Silane, trimethoxy[3-(oxiranylmethoxy)propyl]-

[0097] Colorant: Carbon Black

[0098] Release agent: Ethene homopolymer, oxidized

[0099]

[0100] [Physical property evaluation]

[0101] The physical properties of the epoxy resin compositions manufactured in each example and comparative example were measured as follows, and the results are shown in Table 2 below.

[0102]

[0103] spiral flow

[0104] The epoxy resin compositions manufactured according to each example and comparative example were molded using a spiral flow mold in a heat transfer molding machine (pressure 70 kg / cm2, temperature 175°C, curing time 120 seconds), and then the flowability of the product was measured.

[0105]

[0106] gelation time

[0107] A small amount of the epoxy resin composition manufactured according to each example and comparative example was spread widely and evenly on a gel timer, and the gelation time of the composition was measured.

[0108]

[0109] TMA

[0110] The epoxy resin compositions manufactured according to each example and comparative example were molded in a heat transfer molding machine (pressure 70 kg / cm2, temperature 175 ℃, curing time 120 sec) and PMC (post mold cure, 175 ℃, 4 hours) to produce specimens measuring 6 x 6 x 6 ㎣. Using a TMA (Thermomechanical Analyzer), the glass transition temperature and linear expansion coefficient of each specimen were measured while the temperature was increased from 25 ℃ to 300 ℃ at a heating rate of 10 ℃ / min.

[0111]

[0112] UTM

[0113] The epoxy resin compositions manufactured according to each example and comparative example were molded in a heat transfer molding machine (pressure 70 kg / cm2, temperature 175 ℃, curing time 120 sec) and PMC (post mold cure, 175 ℃, 4 hours) to produce specimens measuring 125 x 12.5 x 6 ㎣. The flexural strength of each specimen was measured at a test speed of 2.6 mm / min under 3-point bending conditions using a UTM (Universal Testing Machine).

[0114]

[0115] Thermal conductivity

[0116] The epoxy resin compositions manufactured according to each example and comparative example were molded in a heat transfer molding machine (pressure 70 kg / cm2, temperature 175°C, curing time 120 sec) and PMC (post mold cure, 175°C, 4 hours) to produce specimens with a diameter of 3 mm x a thickness of 2 mm. The thermal conductivity of each specimen was measured using a thermal conductivity meter using the MTPS (Modified Transient Plane Source) method.

[0117]

[0118] MGP mold

[0119] The epoxy resin compositions manufactured according to each example and comparative example were molded in an MGP mold (pressure 70 kg / cm2, temperature 175°C, curing time 120 seconds) to produce specimens with a chip thickness of 200 μm, and then the occurrence of flow marks on the surface was visually observed. The absence of flow marks was evaluated as excellent, and the occurrence of flow marks was evaluated as poor.

[0120]

[0121]

[0122]

[0123] As shown in Table 2 above, the epoxy resin compositions of Examples 1 and 2 including the siloxane (siloxane 1) according to the present invention, which is a symmetrical disiloxane having alicyclic epoxy groups at both ends, exhibited excellent physical properties across all measured items.

[0124] On the other hand, the epoxy resin compositions of Comparative Example 1 that did not include siloxane, Comparative Examples 2, 3, and 5 that used siloxanes that did not include epoxy groups at the terminals (siloxanes 2, 3, and 5), Comparative Example 4 that used siloxanes that included alicyclic epoxy groups in the side chains rather than at both terminals (siloxane 4), and Comparative Example 6 that used siloxanes that had epoxy groups instead of alicyclic epoxy groups at the terminals (siloxane 6) showed generally inferior physical properties compared to the epoxy resin compositions of Examples 1 and 2.

[0125]

[0126] The present invention provides an epoxy resin composition for molding having excellent dispersibility, flowability and thermal conductivity, and a semiconductor device molded using the same.

Claims

1. Contains epoxy resin, hardener, filler and siloxane, An epoxy resin composition wherein the above siloxane is a symmetrical disiloxane having an alicyclic epoxy group at both terminals.

2. An epoxy resin composition according to claim 1, wherein the epoxy resin has an epoxy equivalent (EEW) of 100 to 500 g / eq and a softening point of 30 to 150°C, and the curing agent has a hydroxyl equivalent of 90 to 300 g / eq and a softening point of 50 to 120°C.

3. In the first paragraph, the siloxane is an epoxy resin composition represented by the following chemical formula 1: [Chemical Formula 1] In the above formula, R1 is an alicyclic epoxy having 5 to 10 carbon atoms, R2 is hydrogen, a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms, R3 is hydrogen, a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms, a is an integer from 1 to 10.

4. An epoxy resin composition in the first paragraph, wherein the molecular weight of the siloxane is 200 to 800 g / mol and the viscosity (25°C) is 5 to 1,000 mPa·s.

5. An epoxy resin composition comprising, based on the total weight of the epoxy resin composition in paragraph 1, 1 to 20 wt% of the epoxy resin, 1 to 20 wt% of the curing agent, 50 to 95 wt% of the filler, and 0.1 to 10 wt% of the siloxane.

6. A semiconductor device molded using an epoxy resin composition according to any one of claims 1 to 5.

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