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] Encapsulation resin compositions are used as materials to improve the characteristics and reliability of semiconductor devices by sealing semiconductor components such as integrated circuits (ICs), large-scale 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 components is continuing in various fields.

[0003] 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 elasticity of the cured product of the epoxy resin composition.

[0004] Conventional resin compositions for semiconductor encapsulation have adopted configurations that increase the content of inorganic fillers or use high-molecular-weight epoxy resins to impart sufficient strength to the curing agent and robustness capable of maintaining stable initial characteristics even when exposed to repeatedly changing environments (such as temperature variations) during semiconductor package operation. However, this has resulted in problems such as reduced flowability due to increased viscosity, increased curing time, degraded insulation properties, and reduced moldability. Therefore, there is a need to develop a molding epoxy resin composition that exhibits excellent strength, modulus, and toughness characteristics without compromising flowability, reducing curing time, or degrading insulation properties. The problem to be solved

[0005] The present invention provides an epoxy resin composition for molding with excellent 3PB (3 Point Bending) robustness, specifically strength, modulus, and toughness characteristics, and a semiconductor device molded using the same. means of solving the problem

[0006] The present invention provides a molding epoxy resin composition comprising an epoxy resin, a curing agent, a filler, a coupling agent, and an epoxy toughness reinforcing agent, wherein the epoxy toughness reinforcing agent is a block copolymer having an ABA structure comprising an organic compound (A) and a siloxane compound (B). Effects of the invention

[0007] The present invention provides an epoxy resin composition for molding that has excellent 3PB (3 Point Bending) robustness, specifically strength, modulus, and toughness characteristics. The epoxy resin composition for molding according to the present invention provides excellent strength, modulus, and toughness characteristics without affecting flowability, curability, hardness, glass transition temperature, and coefficient of thermal expansion (CTE). Specific details for implementing the invention

[0008] 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.

[0009] As used herein, “weight-average molecular weight” is measured by conventional methods known in the art, for example, by gel permeation chromatography (GPC). Functional groups, such as “hydroxyl groups,” are measured by conventional methods known in the art, for example, by titration. “Softening point” is measured by conventional methods known in the art, for example, by a dropping point calorimetry system DP70 from Mettler Toledo. “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.

[0011] Epoxy resin composition for molding

[0012] The molding epoxy resin composition according to the present invention comprises an epoxy resin, a curing agent, a filler, a coupling agent, and an epoxy toughness reinforcing agent. By using a block copolymer having an ABA structure comprising an organic compound (A) and a siloxane compound (B) as an epoxy toughness reinforcing agent, the present invention provides a molding epoxy resin composition having excellent strength, modulus, and toughness characteristics. As a result, it is possible to provide a molding epoxy resin composition having toughness that maintains stable characteristics from the initial manufacturing stage even when exposed to repeatedly changing environments (such as temperature changes) during semiconductor package operation, without adversely affecting flowability, curing time, or insulation properties.

[0013] 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.

[0015] Epoxy resin

[0016] 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.

[0017] 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 aralkyl-type epoxy resins, etc., and one or more of these may be included. For example, the epoxy resin may include formaldehyde, a polymer with 1,1'-biphenyl and phenol, and glycidyl ether.

[0018] 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.

[0019] The above epoxy resin may be used having a soft point of 30 to 150°C, for example, 50 to 130°C. If the soft point is below the aforementioned range, caking properties may be inferior, and if it exceeds the aforementioned range, non-uniform dispersion may occur during manufacturing.

[0020] 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.

[0022] hardener

[0023] 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.

[0024] As the 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 within 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. For example, the curing agent may include a phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl.

[0025] As the above-mentioned 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.

[0026] 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.

[0027] 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.

[0029] filling

[0030] 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.

[0031] 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.

[0032] 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.

[0033] The above filler may include two or more types of fillers with different particle sizes. 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 50 A first filler having a diameter of 5 to 20 μm, for example, 7.5 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.

[0034] Based on the total weight of the epoxy resin composition, the content of the filler may be 50 to 93 weight%, for example, 75 to 93 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.

[0036] coupling agent

[0037] The epoxy resin composition of the present invention includes a coupling agent. The coupling agent promotes the bonding between an inorganic material and an organic material and may include a coupling agent commonly used in the relevant technical field. For example, amino silane, epoxy silane, etc., may be used as the coupling agent.

[0038] The above coupling agent 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 1 weight% based on the total weight of the epoxy resin composition, but is not limited thereto.

[0040] Epoxy hardening reinforcing agent

[0041] The epoxy resin composition of the present invention includes an epoxy toughness reinforcing agent. The epoxy toughness reinforcing agent is a block copolymer with an ABA structure comprising an organic compound (A) and a siloxane compound (B), which promotes chemical bonding between oxygen and epoxy groups within the coupling agent by activating the chemical reaction between the epoxy resin and the curing agent. As a result, the curing reaction proceeds through cross-linking between the epoxy resin, the curing agent, and the coupling agent, thereby forming a solid polymer network (a truss structure between epoxy groups, phenolic groups, and coupling agent functional groups) within the epoxy resin composition for molding. Specifically, the block copolymer with an ABA structure is formed in a form that surrounds the resin produced after the curing reaction between the epoxy resin and the curing agent, thereby imparting elasticity to the composition. Consequently, the epoxy resin composition for molding according to the present invention can provide a molding material with excellent strength, modulus, and toughness without a decrease in flowability, an increase in curing time, or a decrease in insulation properties.

[0042] The above epoxy toughness reinforcing agent is an ABA block copolymer comprising an organic compound (A) and a siloxane compound (B), and has the following structure.

[0043]

[0044] The above organic compound (A) can be represented by the following chemical formula 1.

[0045] [Chemical Formula 1]

[0046]

[0047] In the above chemical formula 1,

[0048] x is an integer from 1 to 5, and

[0049] The polymer can be represented by the following chemical formula 2.

[0050] [Chemical Formula 2]

[0051]

[0052] In the above chemical formula 2,

[0053] q is an integer from 5 to 10, and

[0054] R is a hydrocarbon group having 1 to 2 carbon atoms.

[0055] For example, the organic compound (A) is a compound represented by the chemical formula 1, wherein x is an integer from 1 to 3, q ​​is an integer from 5 to 8 in the chemical formula 2, and R may be a methyl group or an ethyl group.

[0056] The above siloxane compound (B) can be represented by the following chemical formula 3.

[0057] [Chemical Formula 3]

[0058]

[0059] In the above chemical formula 3,

[0060] a is an integer from 1 to 5, and

[0061] b is an integer from 1 to 5, and

[0062] n is an integer from 2 to 5, and

[0063] m is an integer from 2 to 10.

[0064] For example, the above siloxane compound (B) is a compound represented by the above chemical formula 3, wherein a is an integer from 1 to 3, b is an integer from 1 to 3, n is an integer from 2 to 3, and m is an integer from 2 to 5.

[0065] The above epoxy toughness reinforcing agent may contain the organic compound (A) and the siloxane compound (B) in a weight ratio of 5 to 20:1. If the ratio of the organic compound (A) to the siloxane compound (B) falls outside the aforementioned range, the epoxy toughness reinforcing properties may be insufficient.

[0066] The weight-average molecular weight of the above epoxy toughness reinforcing agent may be 8,000 to 15,000 g / mol, for example, 9,000 to 12,000 g / mol. If the weight-average molecular weight falls outside the aforementioned range, the toughness reinforcing reaction may be slowed down or may not occur.

[0067] Based on the total weight of the epoxy resin composition, the content of the epoxy toughness reinforcing agent may be 0.05 to 5 weight%, for example, 0.1 to 3 weight%. If the content of the epoxy toughness reinforcing agent is less than the aforementioned range, the effect of improving strength, modulus, and toughness properties may be insufficient, and if it exceeds the aforementioned range, particles may be generated, resulting in poor surface moldability.

[0069] additives

[0070] 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, colorants, release agents, etc.

[0071] 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. Colorants are added to impart color to the resin composition, and carbon black, Bengala, etc. may be used as colorants. Release agents are added to ensure release between the EMC and the mold, and may use paraffin wax, carnauba wax, polyethylene wax, ester wax, etc.

[0072] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0078] Semiconductor Devices

[0079] 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.

[0080] A method for molding a semiconductor device 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.

[0082] 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.

[0084] [Experimental Example 1-6]

[0085] 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 experimental example.

[0087]

[0088] Epoxy resin: Formaldehyde, polymer with 1,1'-biphenyl and phenol, glycidyl ether (Cas no. 1201169-35-8, Mw 8,397 g / mol)

[0089] Curing agent: Phenol polymer with 4,4-bis(methoxymethyl)1,1-bisphenyl(Cas no. 0106466-55-1, Mw 521 g / mol)

[0090] Filler 1: Silicon dioxide(D 50 2.7 um)

[0091] Filler 2: Silicon dioxide(D 50 0.5 um)

[0092] Epoxy hardening enhancer 1: Polyether modified polydimethylsiloxane, ethylene oxide, propylene oxide-organic block copolymers (organic compound (A) with an ABA structure is represented by Chemical Formula 1 above, and siloxane compound (B) is represented by Chemical Formula 3)

[0093] Epoxy Hardness Reinforcer 2: Core Shell Rubber

[0094] Epoxy toughness enhancer 3: 4,4-(1-Methylethylidene)bisphenol polymer with 2,2-[(1-methylethylidene)bis(4,1-phenyleneoxymethylene)]bis[oxirane] + Polyethylene glycol butyl ether-amphiphilic block copolymers

[0095] Catalyst: Naphthalene-2,3-dioltetraphenylphosphanium 3-hydroxynaphthalen-2-oilate

[0096] Coupling agent 1: N-[3-(Trimethoxysilyl)propyl]benzenamine

[0097] Coupling agent 2: (3-Mercaptopropyl)trimethoxysilane

[0098] Colorant: Carbon Black

[0099] Release agents: Fatty acids, montan wax, ethylene esters, wax

[0101] [Physical Property Evaluation]

[0102] The physical properties of the epoxy resin compositions prepared in each experimental example were measured as follows, and the results are shown in Table 2 below.

[0104] Spiral flow

[0105] After molding the epoxy resin composition prepared according to each experimental example using a spiral flow mold in a heat transfer molding machine, the flowability of the manufactured product was measured. If the flowability satisfied 40 to 80 inches, it was evaluated as good, and if it deviated, it was evaluated as poor.

[0107] gelation time

[0108] A small amount of the epoxy resin composition prepared according to each experimental example was spread widely and evenly on a gel timer, and the gelation time of the composition was measured. If the gelation time was 50 to 85 seconds, it was evaluated as good, and if it fell outside the above range, it was evaluated as poor.

[0110] B / F

[0111] After molding the epoxy resin composition prepared according to each experimental example using a bleed flush mold in a heat transfer molding machine, the flowability of the product was measured. The flowability was evaluated as good if it was 1 to 10 mm under conditions of 0.25 mil (6.3 um), 0.5 mil (12.7 um), and 1 mil (25.4 um), and 80 to 130 mm under conditions of 2 mil (50.8 um), and as poor if it deviated from the above values.

[0113] H / H

[0114] After the bleed flush measurement was completed, the mold was opened, and the high-temperature surface hardness of the molding material was measured using a hardness measuring device (Shore-D). If the hardness value was between 70 and 100, it was evaluated as good, and if it fell outside the above range, it was evaluated as defective.

[0116] Shrinkage

[0117] The epoxy resin composition prepared according to each experimental example was 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 the length of the shrunken specimen was measured using Vernier calipers. A shrinkage rate (%) value of 0.1 to 0.5 was evaluated as good, and a value outside the above range was evaluated as poor.

[0119] Flexural strength (F / S)

[0120] After preparing specimens by curing the epoxy resin compositions prepared according to each experimental example at 170°C for 4 hours, the flexural strength was measured using a Universal Testing Machine. A flexural strength of 17 kgf / mm² or higher was evaluated as good, and a value outside this range was evaluated as poor.

[0122] Flexural modulus (F / M)

[0123] After preparing specimens by curing the epoxy resin compositions prepared according to each experimental example at 170°C for 4 hours, the flexural modulus was measured using a Universal Testing Machine. It was evaluated as good when the flexural modulus was 1,955 kgf / mm² or less, and as poor when it fell outside the above range.

[0125] Toughness

[0126] After preparing specimens by curing the epoxy resin compositions prepared according to each experimental example at 170°C for 4 hours, the toughness was measured using a Universal Testing Machine. A toughness value of 91 kgf·mm or higher was evaluated as good, and a value outside the above range was evaluated as poor.

[0128] TMA

[0129] After preparing specimens by curing the epoxy resin composition prepared according to each experimental example at 175 ℃ for 4 hours, the glass transition temperature was measured using a thermal mechanical analyzer (TA Instrument, Q400) under conditions of a force of 0.5 N and a heating rate of 10 ℃ / min. It was evaluated as good when the glass transition temperature was 105 to 125 ℃, a1 was 10 to 16 ppm, and a2 was 35 to 55 ppm, and as poor when it fell outside the above ranges.

[0131]

[0132] As shown in Table 2 above, the epoxy resin composition of Experimental Examples 1-3 containing the epoxy toughness reinforcing agent (epoxy toughness reinforcing agent 1) according to the present invention exhibited excellent physical properties across all measured items. In particular, it was confirmed that the epoxy resin composition of Experimental Examples 1-3 according to the present invention had excellent strength, modulus, and toughness characteristics.

[0133] On the other hand, the epoxy resin compositions of Experimental Example 4, which did not contain an epoxy toughness reinforcing agent, and Experimental Examples 5 and 6, which contained an epoxy toughness reinforcing agent outside the scope of the present invention (epoxy toughness reinforcing agents 2 and 3), showed inferior physical properties compared to Experimental Examples 1-3 across all measured items.

Claims

Claim 1 A molding epoxy resin composition comprising an epoxy resin, a curing agent, a filler, a coupling agent, and an epoxy toughness reinforcing agent, wherein the epoxy toughness reinforcing agent is a block copolymer having an ABA structure comprising an organic compound (A) and a siloxane compound (B), and the siloxane compound (B) is represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, a is an integer from 1 to 5, b is an integer from 1 to 5, n is an integer from 2 to 5, and m is an integer from 2 to 10. Claim 2 A molding epoxy resin composition according to claim 1, wherein the epoxy equivalent (EEW) of the epoxy resin is 100 to 500 g / eq and the soft point is 30 to 150 ℃, the hydroxyl equivalent of the curing agent is 90 to 300 g / eq and the soft point is 50 to 120 ℃. Claim 3 In claim 1, the molding epoxy resin composition wherein the organic compound (A) is represented by the following chemical formula 1: [Chemical Formula 1] In the above Chemical Formula 1, x is an integer from 1 to 5, and the Polymer is represented by the following Chemical Formula 2, [Chemical Formula 2] In the above chemical formula 2, q is an integer from 5 to 10, and R is a hydrocarbon group having 1 to 2 carbon atoms. Claim 4 delete Claim 5 A molding epoxy resin composition according to claim 1, wherein the epoxy toughness reinforcing agent comprises the organic compound (A) and the siloxane compound (B) in a weight ratio of 5 to 20:1, and the weight-average molecular weight of the epoxy toughness reinforcing agent is 8,000 to 15,000 g / mol. Claim 6 The molding epoxy resin composition according to claim 1, comprising, based on the total weight of the molding epoxy resin composition, 2 to 20 weight% of the epoxy resin, 2 to 20 weight% of the curing agent, 50 to 93 weight% of the filler, 0.01 to 1 weight% of the coupling agent, and 0.05 to 5 weight% of the epoxy toughness reinforcing agent. Claim 7 A semiconductor device molded using an epoxy resin composition for molding according to any one of claims 1 to 3, 5 and 6.

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