Epoxy resin composition for molding

Abstract

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

Description

Technology Field

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

[0002] Encapsulating resin compositions are used as materials to improve the characteristics and reliability of semiconductor devices by sealing semiconductor devices such as integrated circuits (ICs), large-capacity integrated circuits (LSIs), transistors, and diodes. Recently, as the high integration of semiconductors accelerates in accordance with the trends of miniaturization, lightweighting, and high performance of electronic devices, research to improve the performance of materials used for sealing semiconductor devices is being conducted in various ways. For example, Japanese Patent Publication No. 2017-197620 relates to an epoxy resin composition for semiconductor sealing comprising an epoxy resin, a phenolic resin curing agent, and a filler, and discloses a technology that improves electrical connection reliability by controlling the content of the filler and the thermal modulus of the cured product of the epoxy resin composition.

[0003] In particular, when applied to multi-layer stacked semiconductor packages, filling fine gaps is considered important, so excellent meltability is required for the epoxy resin composition. However, in the case of conventional epoxy resin compositions with increased meltability, there is a problem in that swelling occurs when the epoxy molding compound (EMC) leaks out of the mold cavity during compression molding, which is performed under high pressure in a vacuum environment.

[0004] Accordingly, there is a need to develop an epoxy resin composition for molding that has excellent meltability, thereby improving gap-filling characteristics, while also having excellent swelling inhibition characteristics. The problem to be solved

[0005] The present invention provides an epoxy resin composition for molding having excellent meltability and swelling inhibition characteristics, and a semiconductor device molded using the same. means of solving the problem

[0006] 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 having a symmetric structure having epoxy groups at both ends. Effects of the invention

[0007] The present invention provides an epoxy resin composition for molding that has excellent meltability, thereby improving gap filling characteristics, and at the same time has excellent swelling inhibition characteristics. The epoxy resin composition according to the present invention is applicable to compression molding methods, and in particular, is applicable as a granular epoxy molding compound (EMC) due to its excellent swelling inhibition characteristics. Brief explanation of the drawing

[0008] Figure 1 is a schematic diagram showing a method for evaluating the melt-ability of an epoxy resin composition. Figure 2 is a schematic diagram showing a method for evaluating the swelling characteristics of an epoxy resin composition. Specific details for implementing the invention

[0009] The present invention will be described in detail below. However, it is not limited to the following description, and each component may be modified in various ways or selectively combined as needed. Accordingly, it should be understood that the invention includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the invention.

[0010] As used herein, “softening point” is measured by conventional methods known in the art, for example, using a Mettler Toledo Dropping Point system calorimetry DP70. “Viscosity” is measured by conventional methods known in the art, for example, using a Brookfield viscometer at room temperature (25 °C). Particle size (D 50 )" is measured by conventional methods known in the relevant technical field, and can be measured, for example, by a laser particle size analyzer.

[0012] Epoxy Resin Composition

[0013] The epoxy resin composition according to the present invention comprises an epoxy resin, a curing agent, a filler, and an organosiloxane. By using a linear organosiloxane with a symmetrical structure having epoxy groups at both ends, the present invention provides a sealing epoxy resin composition that has excellent meltability, thereby improving gap filling characteristics, and at the same time having excellent swelling inhibition characteristics.

[0014] The epoxy resin composition of the present invention can be manufactured in liquid, powder, granular, or sheet form, and can be used as a sealant (EMC, epoxy molding compound) for semiconductor devices or as a molding or fixing material for various electronic components or automotive parts. For example, the molding epoxy resin composition of the present invention can be applied for sealing large-area semiconductor packages that are large in size and thin in thickness, and can be manufactured as a granular EMC applicable to compression type molding processes, C-molding processes, or lamination processes.

[0016] Epoxy resin

[0017] The epoxy resin composition of the present invention comprises an epoxy resin. The epoxy resin is used as the main resin and, by reacting with a curing agent and curing to form a three-dimensional network structure, can impart properties of strong and rigid adhesion to a substrate and heat resistance.

[0018] As the above epoxy resin, an epoxy resin commonly used in the relevant technical field may be used. Non-limiting examples of available epoxy resins include bisphenol A type epoxy resin, alicyclic epoxy resin, cresol novolak 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 novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol S novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol phenol coaxial novolak type epoxy resin, naphthol cresol coaxial novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene phenol addition type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, polyfunctional phenol resin, and naphthol. There are aracle-type epoxy resins, etc., and one or more of these may be included.

[0019] For example, the epoxy resin may include formaldehyde, a polymer with 1,1'-biphenyl and phenol, glycidyl ether, 4,4-bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl)), or a mixture thereof.

[0020] For example, the epoxy resin may include formaldehyde, a polymer of 1,1'-biphenyl and phenol, glycidyl ether, and 4,4-bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl). In this case, viscosity and flowability characteristics can be further improved while maintaining mechanical strength characteristics such as flexural strength of the epoxy resin composition.

[0021] The above epoxy resin may be used with an epoxy equivalent (EEW) of 100 to 500 g / eq, for example, 150 to 300 g / eq. If the epoxy equivalent is less than the aforementioned range, the curing density may increase, which may result in poor moisture resistance, and if it exceeds the aforementioned range, the curability may be poor.

[0022] The above epoxy resin may be used having a soft point of 30 to 150°C, for example, 50 to 110°C. If the soft point is below the aforementioned range, caking properties may be inferior, and if it exceeds the aforementioned range, uneven dispersion may occur during manufacturing.

[0023] Based on the total weight of the epoxy resin composition, the content of the epoxy resin may be 2 to 20 weight%, for example, 5 to 15 weight%. If the content of the epoxy resin is less than the aforementioned range, adhesion, flowability, and moldability may be reduced, and if it exceeds the aforementioned range, the reliability of the semiconductor may be poor due to increased moisture absorption, and the strength may be reduced due to a relative decrease in the filler content.

[0025] hardener

[0026] The epoxy resin composition of the present invention includes a curing agent. The curing agent reacts with the epoxy resin to facilitate the curing of the composition.

[0027] As the above curing agent, a curing agent known in the art for curing with an epoxy resin may be used, and the curing agent may be a phenolic compound having two or more phenolic hydroxyl groups in one molecule. Non-limiting examples of usable curing agents include phenol novolak resin, cresol novolak resin, phenol aralkyl resin, polyfunctional phenolic compounds, etc., and may include one or more of these.

[0028] For example, the curing agent may include a phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl, a phenol polymer with formaldehyde, or a mixture thereof.

[0029] For example, the curing agent may include a phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl and a phenol polymer with formaldehyde. In this case, viscosity and meltability properties can be further improved while maintaining mechanical strength properties such as flexural strength of the epoxy resin composition.

[0030] As the above curing agent, a hydroxyl group equivalent of 90 to 300 g / eq, for example 100 to 200 g / eq, may be used. If the hydroxyl group equivalent is less than the aforementioned range, the moisture resistance reliability may be inferior, and if it exceeds the aforementioned range, the curability may be inferior.

[0031] As the above curing agent, a softening point of 50 to 120°C, for example 55 to 90°C, may be used. If the softening point is below the aforementioned range, caking properties may be inferior, and if it exceeds the aforementioned range, fluidity may be inferior.

[0032] Based on the total weight of the epoxy resin composition, the content of the curing agent may be 2 to 20 weight%, for example, 2 to 10 weight%. If the content of the curing agent is less than the aforementioned range, curability and moldability may be reduced, and if it exceeds the aforementioned range, the reliability of the semiconductor may be poor and strength may be reduced due to increased moisture absorption.

[0034] filling

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

[0036] As the above filler, inorganic fillers commonly used in the field of electronic materials can be used without special restrictions. For example, inorganic fillers such as silica, silica nitride, alumina, aluminum nitride, and boron nitride can be used, and these can be used individually or in combination of two or more types.

[0037] The shape of the above-mentioned filler is not particularly limited, and both angular and spherical forms can be used. Non-limiting examples of fillers that can be used in the present invention include natural silica, synthetic silica, fused silica, etc., and, for example, spherical silica particles can be used.

[0038] The above filler may include two or more types of fillers 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 above filler has an average particle size (D 50A first filler having a particle size of 3.5 to 20 μm, for example, 3.5 to 15 μm, and an average particle size (D 50 It may include a second filler having a thickness of 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 may be 50 to 90 weight%, for example, 70 to 90 weight%. If the content of the filler is less than the aforementioned range, the moisture absorption of the cured product increases, which may reduce the reliability of the semiconductor device, and if it exceeds the aforementioned range, the fluidity decreases, which may result in poor moldability.

[0041] Organic siloxane

[0042] The epoxy resin composition of the present invention includes an organosiloxane to improve dispersibility. The organopolysiloxane is a linear organosiloxane with a symmetric structure having epoxy groups at both ends. By using an organopolysiloxane with such a structure, it is possible to provide a sealing epoxy resin composition that has excellent meltability, thereby improving gap-filling characteristics, and at the same time has excellent swelling inhibition characteristics.

[0043] The above organosiloxane has a symmetric linear molecular structure, thereby possessing high compatibility with epoxy resin compositions, particularly those containing biphenyl-based epoxy resins. Furthermore, by having reactive epoxy groups at both ends, the organosiloxane can effectively disperse the epoxy resin composition by participating in the cross-linking curing reaction between the epoxy resin and the phenol curing agent as a reactive diluent. As a result, by lowering the surface tension of the molten epoxy resin composition, the swelling of internal bubbles within the cured epoxy resin composition can be suppressed, and moldability can be improved by lowering the viscosity of the molten epoxy resin composition. Additionally, the organosiloxane can maintain the adhesion of the epoxy resin composition while simultaneously improving meltability and swelling inhibition characteristics.

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

[0045] [Chemical Formula 1]

[0046]

[0047] In the above formula,

[0048] EP is an epoxy group, and

[0049] R1 is hydrogen, or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms, and

[0050] R2 is hydrogen, or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms, and

[0051] a is an integer from 1 to 5, and

[0052] n is an integer from 1 to 5.

[0053] For example, in the above formula, EP is an epoxy group, R1 is hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, R2 is hydrogen or a 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.

[0054] For example, in the above formula, EP is an epoxy group, R1 is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, R2 is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a is an integer from 1 to 3, and n is an integer from 1 to 3.

[0055] For 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.

[0056] The above organosiloxane may be used having 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. When using an organosiloxane with a low molecular weight and low viscosity within the aforementioned ranges, it is advantageous for mixing the epoxy resin composition and can exhibit high dispersibility. If the molecular weight or viscosity exceeds the aforementioned ranges, the compatibility between the epoxy resin composition and the organosiloxane decreases, which may result in reduced dispersibility and appearance defects such as the occurrence of flow marks.

[0057] Based on the total weight of the epoxy resin composition, the content of the organosiloxane may be 0.05 to 5 weight%, for example, 0.1 to 3 weight%. If the content of the organosiloxane is below the aforementioned range, the effect of improving meltability and suppressing swelling may be limited, and if it exceeds the aforementioned range, the reliability and strength of the epoxy resin composition may be reduced.

[0059] additives

[0060] The epoxy resin composition of the present invention may additionally include additives commonly used in molding compositions. Non-limiting examples of usable additives include catalysts, coupling agents, ion catchers, colorants, release agents, etc.

[0061] The catalyst promotes the curing reaction and may use imidazole-based compounds, naphthalene-based latent catalysts, amine-based compounds, organometallic compounds, organophosphorus compounds, boron compounds, etc. The coupling agent promotes the bonding between inorganic and organic materials and may use amino silanes, epoxy silanes, etc. The ion catcher reduces corrosion by capturing and removing impurity ions and may use inorganic ion exchangers such as magnesium aluminum hydroxide carbonate hydrate. The coloring agent is added to impart color to the resin composition and may use carbon black, Bengala, etc. The release agent is added to ensure release between the cured epoxy resin composition and the mold and may use paraffin wax, carnauba wax, polyethylene wax, ester wax, etc.

[0062] 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 weight% each with respect to the total weight of the epoxy resin composition, but are not limited thereto.

[0064] The epoxy resin composition according to the present invention can be manufactured by a melt mixing method using conventional methods known in the art, such as a Banbury mixer, a kneader, a roll, a single-screw or twin-screw extruder, and a conider.

[0065] 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 a granule form and applied to a compression molding method.

[0066] For example, in the case of powder or granular epoxy resin compositions, each component as described above can be uniformly mixed, then melt-mixed using a heat kneader at a temperature of 80 to 130°C, cooled to room temperature, then ground into a powder, and then subjected to a sieving process to be manufactured, but is not limited thereto.

[0068] Semiconductor Devices and Automotive Parts

[0069] The present invention provides a semiconductor device molded using the aforementioned epoxy resin composition. The semiconductor device may be a transistor, a diode, a microprocessor, a semiconductor memory, a power semiconductor, etc.

[0070] In addition, the present invention provides a vehicle part molded using the aforementioned epoxy resin composition. For example, the aforementioned epoxy resin composition can be used as a molding material to fix and seal a component within a vehicle part. Specifically, a permanent magnet can be inserted into a void space formed within the rotor core of a vehicle motor, and the epoxy resin composition of the present invention can be filled between the void space and the permanent magnet to fix the permanent magnet within the rotor core.

[0071] 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 conventional methods in the relevant technical field, such as transfer molding, compression molding, injection molding, etc.

[0073] The present invention will be explained in more detail below through examples. However, the following examples are intended only to aid in understanding the present invention and do not imply that the scope of the present invention is limited to these examples in any way.

[0075] [Examples 1-4]

[0076] After mixing each component according to the composition listed in Table 1 below, the mixture was melt-mixed using a kneader at a temperature of 100 to 130°C, cooled to room temperature, ground into a powder, and then subjected to a sieving process to prepare the granular epoxy resin composition of each example.

[0078] [Comparative Example 1-7]

[0079] Granular epoxy resin compositions of each comparative example were prepared in the same manner as the examples, except for the compositions listed in Table 2 below.

[0081]

[0082]

[0083] Epoxy resin 1: Polyfunctional epoxy resin (Formaldehyde, polymer with 1,1'-biphenyl and phenol, glycidyl ether, Cas no. 1201169-35-8)

[0084] Epoxy resin 2: Biphenyl-based epoxy resin (4,4-Bis(2,3-epoxypropoxy)-3,3,5,5-tetramethyl(1,1-biphenyl))

[0085] Curing agent 1: Polyfunctional phenolic resin (Phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl, Cas no. 0106466-55-1)

[0086] Curing agent 2: Phenol novolak resin (Phenol polymer with hydroxybenzaldehyde, Cas no. 0205830-20-2)

[0087] Filler: Silicon dioxide

[0088] Organosiloxane 1: 1,3-Bis(3-(2,3-epoxypropoxy)propyl) 1,1,3,3-tetramethyldisiloxane

[0089] Organosiloxane 2: Organosiloxane having amino groups at both ends (Dual-end type / Amino-modified Silicone Fluids, viscosity (25 ℃) 25 mm 2 / s, Mw 1,600 g / mol, amine value 70 mgKOH / g)

[0090] Organosiloxane 3: 3-[2-(3,4-epoxycyclohexyl)ethyl]-heptamethyltrisiloxane

[0091] Organosiloxane 4: Modified siloxane containing epoxy and polyether groups in the side chain (Epoxy and polyether modified silicone polymer, Cas no. 0101810-98-4, kinematic viscosity (25 ℃) 2,200 mm² / s, epoxy equivalent 5,200 g / mol)

[0092] Ion Catcher: (Carbonato)hexadecahydroxydialuminum-hexamagnesium

[0093] Catalyst: 5-Methyl-2-phenylimidazole-4-methanol

[0094] Coupling agent: (3-Mercaptopropyl)trimethoxysilane

[0095] Colorant: Carbon Black

[0096] Release agent: Ester wax

[0098] [Physical Property Evaluation]

[0099] 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.

[0101] Spiral flow

[0102] The epoxy resin compositions prepared according to each example and comparative example were molded using a spiral flow mold in a heat transfer molding machine (pressure 16 kgf / ㎠, temperature 175 ℃, curing time 120 sec) and the flowability of the manufactured product was measured.

[0104] gelation time

[0105] A small amount of the epoxy resin composition prepared 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.

[0107] Flexural strength

[0108] Measurements were taken according to ASTM D638, D256, and D790.

[0110] Flexural modulus

[0111] The epoxy resin compositions prepared according to each example and comparative example were molded using a specimen mold (width 125 mm, length 12.5 mm, thickness 6 mm) in a heat transfer molding machine (pressure 70 kg / ㎠, temperature 175 ℃, curing time 120 sec), then post-cured in an oven at 175 ℃ for 4 hours, and then measured with a Universal Testing Machine (UTM).

[0113] meltability

[0114] As shown in FIG. 1, an epoxy resin composition (6.0 g) prepared according to each example and comparative example was dispensed over a narrow area onto a release film, and then compression molded using a compression molding machine at a temperature of 175 °C, a maximum pressure of 30 ton, a compression time of 25 s (time to reach maximum pressure), and a cure time of 120 s. After compression molding, the spreading area of ​​the melted epoxy resin composition was measured. The meltability of the epoxy resin composition was evaluated by calculating the spreading area ratio using the following formula.

[0115]

[0117] Swelling

[0118] As shown in FIG. 2, 2.0 g of the epoxy resin composition prepared according to each example and comparative example was weighed into a vial, and the weighed vial was placed on a hot plate under vacuum conditions of 175°C and 640°F (torr) for 5 minutes, after which the height of swelling of the sample was measured. The swelling characteristics were evaluated by calculating the rate of change using the following formula.

[0119]

[0120] H O : Height before heating

[0121] △H: Height after heating - H O

[0123]

[0124]

[0125] As shown in Tables 3 and 4 above, the epoxy resin compositions of Examples 1-4 containing the organosiloxane (organosiloxane 1) according to the present invention, which has a symmetric linear structure having epoxy groups at both ends, exhibited excellent physical properties across all measured items.

[0126] On the other hand, the epoxy resin compositions of Comparative Examples 1-4, which did not use organosiloxane, showed inferior meltability or swelling inhibition properties. In addition, the epoxy resin compositions of Comparative Example 5, which used an organosiloxane having amino groups at both ends (organosiloxane 2), Comparative Example 6, which used an organosiloxane containing an epoxy group in a non-terminal side chain (organosiloxane 3), and Comparative Example 7, which used an organosiloxane containing an epoxy group and a polyether group in a non-terminal side chain (organosiloxane 4), instead of the organosiloxane according to the present invention, showed inferior meltability or swelling inhibition properties.

Claims

Claim 1 An epoxy resin composition comprising an epoxy resin, a curing agent, a filler, and an organosiloxane, wherein the organosiloxane is a linear organosiloxane having a symmetric structure having epoxy groups at both ends, and the organosiloxane is an epoxy resin composition represented by the following chemical formula 1, wherein the epoxy resin composition comprises 0.05 to 5 weight% of the organosiloxane based on the total weight of the epoxy resin composition: [Chemical Formula 1] In the above formula, EP is an epoxy group, R1 is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms, R2 is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms, a is an integer from 1 to 5, and n is an integer from 1 to 5. Claim 2 An epoxy resin composition according to claim 1, wherein the soft point of the epoxy resin is 30 to 150 ℃ and the soft point of the curing agent is 50 to 120 ℃. Claim 3 delete Claim 4 An epoxy resin composition according to claim 1, wherein the molecular weight of the organosiloxane is 300 to 800 g / mol and the viscosity (25 ℃) is 0.005 to 1 Pa·s. Claim 5 An epoxy resin composition according to claim 1, comprising 2 to 20 weight% of the epoxy resin, 2 to 20 weight% of the curing agent, and 50 to 90 weight% of the filler, based on the total weight of the epoxy resin composition. Claim 6 A semiconductor device molded using an epoxy resin composition according to any one of claims 1, 2, 4 and 5.

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