WO2023128247A1 - Granular epoxy resin composition - Google Patents

Granular epoxy resin composition Download PDF

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Publication number
WO2023128247A1
WO2023128247A1 PCT/KR2022/017535 KR2022017535W WO2023128247A1 WO 2023128247 A1 WO2023128247 A1 WO 2023128247A1 KR 2022017535 W KR2022017535 W KR 2022017535W WO 2023128247 A1 WO2023128247 A1 WO 2023128247A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
resin composition
granular
granular epoxy
molding
Prior art date
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PCT/KR2022/017535
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French (fr)
Korean (ko)
Inventor
김대진
김승택
이은한
심명택
공병선
Original Assignee
주식회사 케이씨씨
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Application filed by 주식회사 케이씨씨 filed Critical 주식회사 케이씨씨
Priority to CN202280069985.6A priority Critical patent/CN118119660A/en
Publication of WO2023128247A1 publication Critical patent/WO2023128247A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic

Definitions

  • the present invention relates to a granular epoxy resin composition and a semiconductor device sealed using the same.
  • Epoxy resin composition (EMC, epoxy mold compound) is being used.
  • the thickness of the encapsulant on the semiconductor device means the thickness of the encapsulant sealing the opposite surface of the lead frame or circuit board mounting surface of the semiconductor device, and when one or more semiconductor devices are stacked and mounted on the lead frame or circuit board, the lead frame or It means the thickness of the sealing material that seals the surface of the semiconductor element on the uppermost surface on the opposite side of the circuit board mounting surface.
  • the encapsulation method of semiconductor devices has been mainly a transfer molding method using a tablet in which a solid epoxy resin composition is compressed into a cylindrical shape. As , the compression mold method is widely applied.
  • the conventional epoxy resin composition has a problem in that it is difficult to secure flowability suitable for compression molding, fine gap-filling characteristics, and swelling/leakage prevention characteristics. Accordingly, there is a need to develop a resin composition for encapsulating a semiconductor device in a granular form having workability and moldability suitable for compression molding.
  • the present invention provides a granular epoxy resin composition having excellent flowability and filling properties when sealing a semiconductor device, excellent moldability of EMC, and improved anti-swelling property during molding.
  • the present invention controls the swelling change rate of the granular epoxy resin composition, so that when sealing a semiconductor chip using the same, the leakage of the molten epoxy resin composition to the outside of the mold is significantly reduced, resulting in excellent moldability and reliability of the molding material.
  • a granular epoxy resin composition capable of producing this excellent semiconductor package is provided.
  • the present invention provides a semiconductor device sealed with the granular epoxy resin composition.
  • the present invention provides a granular epoxy resin composition
  • a granular epoxy resin composition comprising an epoxy resin, a curing agent and a filler, and having a swelling change rate of less than 15% under vacuum and molding temperature.
  • the granular epoxy resin composition of the present invention has a swelling change rate of less than 15% under vacuum and molding temperature, and it is used to prevent swelling in the compression molding process performed under high temperature and pressure during semiconductor chip molding, thereby preventing swelling. It is possible to improve the fillability and moldability of the manufactured semiconductor molding material while minimizing equipment failure caused by leakage of the molten epoxy resin composition to the outside of the substrate or mold.
  • the rheological properties that is, the swelling change rate, measured from the granular epoxy resin composition specimens to less than 15%, whether it corresponds to the granular epoxy resin composition having excellent moldability and filling properties as a molding material is preliminarily determined. can be screened on.
  • the granular epoxy resin composition of the present invention can provide high reliability when applied to thin-film semiconductor devices and integrated semiconductor devices by improving fine gap filling characteristics.
  • the present invention controls the swelling change rate of the granular epoxy resin composition to less than 15% under vacuum and molding temperature, so that voids occur in the manufactured epoxy molding material when molding a semiconductor chip using the granular epoxy resin composition. It is possible to improve flowability, formability and filling property at the same time as suppressing the As a result, the leakage of the molten epoxy resin composition during the process is prevented from leaking out of the mold, thereby improving reliability, reducing the occurrence of errors in process equipment, and minimizing contamination of process equipment, thereby increasing the mold replacement cycle and equipment cleaning cycle. productivity can be improved.
  • the granular epoxy resin composition according to the present invention has a swelling change rate under vacuum and molding temperature of less than 15%, for example less than 10%, in another example less than 3%.
  • the swelling change rate was determined by the following formula.
  • the epoxy resin composition leaks between molds during compression molding, contaminating equipment, and causing defects in molded products.
  • the temperature during the measurement is a molding temperature during compression molding, and may be, for example, 145 to 165 °C, for example 145 to 155 °C. It may be heated to the molding temperature until the granular epoxy resin composition no longer swells, for example, for 3 to 10 minutes. It is not limited to using a specific measuring device as long as the vacuum and molding temperature conditions can be met, for example, measuring using a device including a hot plate in a sealing device that can be made into a vacuum state. can do. For example, it may be evaluated after heating for 5 minutes on a hot plate at 150 ° C. under a vacuum of less than 640 torr.
  • the granular epoxy resin composition of the present invention is a granular epoxy resin composition in which, when a semiconductor chip is molded using a compression molding machine, the amount of cured material that is not formed as an epoxy molding material and escapes out of the substrate is discharged onto the substrate for compression molding. may be less than 3% relative to the amount of
  • the molding conditions are a molding temperature of 145 to 165 °C, a compression pressure of 10 to 50 ton, and a vacuum degree of 10 to 800 torr. For example, it may be evaluated after molding under a molding temperature of 155 ° C., a compression pressure of 30 ton, and a vacuum degree of 70 torr.
  • the granular epoxy resin composition according to the present invention includes an epoxy resin, a curing agent and a filler, and, if necessary, an anionic polymer, a curing catalyst, a coupling agent, a colorant, a release agent, a modifier, One or more additives commonly used in the art, such as a flame retardant, a stress reducing agent, and an antifoaming agent, may be further included.
  • the granular epoxy resin composition of the present invention may contain an epoxy resin as a main resin.
  • the epoxy resin reacts with a curing agent to form a three-dimensional network structure after being cured, thereby imparting strong and robust adhesion and heat resistance to an adherend.
  • any epoxy resin commonly used in the art may be used without particular limitation.
  • usable epoxy resins include bisphenol A type epoxy resins, alicyclic epoxy resins, cresol novolac type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, Tetramethyl Biphenyl 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 Furnace Rockfish type epoxy resin, naphthol cresol coaxial novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenyl methane type epoxy resin, tetraphenyl ethane type epoxy resin, dicyclopentad
  • an epoxy resin having a softening point of 40 to 75 °C, for example, 50 to 65 °C may be used.
  • the epoxy resin has an epoxy equivalent weight (EEW) of 100 to 400 g/eq, for example, 180 to 350 g/eq, and another example of 250 to 300 g/eq, and a viscosity (based on 150 °C) of 0.01 to 300 g/eq. 50 poise, for example 0.01 to 10 poise, another example 0.01 to 2 poise may be used.
  • EW epoxy equivalent weight
  • 50 poise for example 0.01 to 10 poise, another example 0.01 to 2 poise
  • the above-described epoxy resin composition can secure flowability and fluidity even when a high content of filler is included, and can be easily kneaded to improve dispersibility, thereby having excellent moldability.
  • the content of the epoxy resin may be 2 to 20% by weight, for example 5 to 15% by weight.
  • the content of the epoxy resin is less than the above-mentioned range, the viscosity of the composition increases and flowability and moldability decrease, which may cause a problem of insufficient filling of the epoxy resin composition in a semiconductor device and degrade workability.
  • the content of the epoxy resin exceeds the above range, the reliability of the semiconductor becomes poor due to the increase in moisture absorption, and the strength of the epoxy molding material prepared through the granular epoxy resin composition is lowered due to the relative decrease in the content of the filler.
  • the granular epoxy resin composition of the present invention includes a curing agent.
  • the curing agent contains reactive hydrogen, which reacts with the epoxide groups of the epoxy resin to promote curing of the composition.
  • the curing agent a curing agent known in the art as having a curing reaction with an epoxy resin may be used.
  • the curing agent may be a phenolic compound having two or more phenolic hydroxyl groups in one molecule.
  • usable curing agents include phenol novolak resins, cresol novolac resins, phenol aralkyl resins, multifunctional phenol compounds, and the like, and may include one or more of these.
  • the curing agent one having a softening point of 50 to 85 °C, for example, 60 to 79 °C, and another example of 64 to 75 °C may be used.
  • a hydroxyl equivalent of 150 to 300 g/eq, for example, 190 to 230 g/eq, and a viscosity (based on 150 °C) of 0.01 to 10 poise, for example, 0.01 to 2 poise may be used.
  • the content of the curing agent may be 2 to 20% by weight, for example 2 to 15% by weight.
  • the content of the curing agent is less than the above range, curability and moldability may be deteriorated, and when it exceeds the above range, reliability of the semiconductor may be poor and strength may be reduced due to an increase in moisture absorption.
  • the granular epoxy resin composition of the present invention includes a filler.
  • the filler serves to improve the mechanical properties (eg, strength) of the epoxy resin composition and lower the amount of moisture absorption.
  • inorganic fillers commonly used in the field of electronic materials may be used without particular limitation.
  • inorganic fillers such as metal oxides, metal nitrides, silica, silica nitride, alumina, aluminum nitride, and boron nitride may be used, and these may be used alone or in combination of two or more.
  • the shape of the filler is not particularly limited, and angular, spherical, and amorphous shapes may all be used.
  • Non-limiting examples of the filler that can be used in the present invention include natural silica, synthetic silica, fused silica, and the like, and for example, spherical silica particles may be used.
  • the filler may include two or more types of fillers having different particle sizes. In this case, moldability and workability of the granular epoxy resin composition can be further improved.
  • the filler may be used by mixing two types of fillers having different average particle diameters (D50), for example, a first filler having an average particle diameter (D50) of 3.0 to 20 ⁇ m, for example, 3.0 to 15 ⁇ m and an average
  • a second filler having a particle diameter (D50) of 0.1 to 3 ⁇ m, for example, 0.1 to 2 ⁇ m may be mixed and used in an appropriate ratio.
  • the content of the filler may be 50 to 95% by weight, for example 70 to 90% by weight. If the content of the filler is less than the above range, the moisture absorption amount of the cured product may increase, thereby degrading the reliability of the semiconductor device, and if it exceeds the above range, fluidity may decrease and moldability may deteriorate.
  • the granular epoxy resin composition of the present invention may include an anionic polymer.
  • the anionic polymer provides workability suitable for compression molding by imparting excellent flowability, filling properties, and swelling/leakage prevention properties during compression molding of the granular epoxy resin composition, thereby providing excellent moldability as a semiconductor device encapsulant. and reliability can be improved.
  • the anionic polymer is a polymer having a functional group or moiety exhibiting a negative charge, and the functional group or moiety may be present in the main backbone or at the end or middle of a side chain.
  • the functional group may be one or more of a carboxyl group (-COO-), a sulfonic acid group (-SO 3 -), or an acetoxy group (-CH 2 COO-).
  • the functional group may include a carboxyl group.
  • the anionic polymer may be linear or branched in which a plurality of side chains are bonded to a linear main backbone.
  • a carboxyl group included in the anionic polymer and exhibiting a negative charge may participate in cross-linking with the epoxy resin, and the non-polar hydrocarbon of the main skeleton in the anionic polymer may increase compatibility with the epoxy/phenol resin.
  • the carboxyl group showing a negative charge of the anionic polymer due to the carboxyl group showing a negative charge of the anionic polymer, the dispersibility of the filler in the epoxy resin composition is improved, and sedimentation is prevented, resulting in excellent storage stability, which leads to moldability and storage stability (pot life) of the epoxy resin composition. ), bleed resistance can be improved.
  • the granular epoxy resin composition of the present invention can exhibit flowability, excellent filling properties, and swelling/leakage prevention properties suitable for a compression molding process during semiconductor chip molding.
  • the anionic polymer exhibits excellent fine gap-filling characteristics, for example, excellent filling characteristics even at a gap pitch of 30 microns or less. Due to this, a relatively thin sealing layer may be formed, and the fillability may be remarkably improved.
  • the anionic polymer uniformly disperses fillers having a size of 10 microns or less to stabilize them in a resin matrix, thereby significantly improving workability during compression molding and moldability of the granular epoxy resin composition.
  • the anionic polymer may include a carboxylic acid group and an ether group in a main backbone.
  • the anionic polymer may be represented by Formula 1 below.
  • R 1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms
  • R 2 is hydrogen, a carboxylic acid, a hydroxy group, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;
  • p 1 to 20;
  • the acid value of the anionic polymer may be 10 to 350 mgKOH/g, for example 25 to 320 mgKOH/g. If the acid value is out of the above range, storage stability may be poor.
  • the weight average molecular weight of the anionic polymer may be 500 to 10,000 g/mol, for example 4,000 to 6,000 g/mol.
  • swelling and spreading properties may not be controlled, and when it exceeds the above range, the curing properties of the epoxy molding material using the granular epoxy resin cured product It can be a factor that lowers the long-term reliability of molded products.
  • the content of the anionic polymer may be 0.3 to 1.2% by weight, for example 0.4 to 0.8% by weight.
  • the content of the anionic polymer is less than the above range, swelling properties and spreading control may be insufficient, and when it exceeds the above range, storage stability and workability may be poor.
  • the granular epoxy resin composition of the present invention may additionally include additives commonly used in the composition.
  • additives commonly used in the composition.
  • usable additives include curing catalysts, coupling agents, colorants, release agents, and the like.
  • the curing catalyst is to accelerate the curing reaction, and an imidazole-based compound, a naphthalene-based latent catalyst, an amine-based compound, an organometallic compound, an organophosphorus compound, a boron compound, or the like may be used.
  • a coupling agent is added for stable dispersion of organic and inorganic materials, and epoxy silane, amino silane, mercapto silane, acrylic silane, vinyl silane, etc. may be used as the coupling agent.
  • a colorant is added to impart color to the resin composition, and carbon black, bengala, etc. may be used as the colorant.
  • a release agent is added to ensure releasability between the EMC and the mold, and paraffin wax, carnauba wax, polyethylene wax, ester wax, etc. may be used as the release agent.
  • paraffin wax, carnauba wax, polyethylene wax, ester wax, etc. may be used as the release agent.
  • an anion scavenger, an antifoaming agent, and the like may be further included.
  • the additives may be added within an amount known in the art, and for example, may be included in an amount of 0.01 to 5% by weight based on the total weight of the granular epoxy resin composition, but is not limited thereto.
  • the present invention provides a semiconductor device encapsulated using the granular epoxy resin composition described above.
  • the semiconductor device may be a transistor, a diode, a microprocessor, a semiconductor memory, or a power semiconductor.
  • the granular epoxy resin composition according to the present invention can be applied to package stacking type POP (Package On Package) and semiconductor chip stacking type COC (Chip On Chip).
  • a method of encapsulating a semiconductor device using the granular epoxy resin composition of the present invention is a conventional method in the art, such as transfer molding, compression molding, injection molding, and the like. It can be done according to the method.
  • melt-mixed mixture was passed through a granulator at a temperature of 70 to 130 ° C using a melt kneader to prepare a granular epoxy resin composition of each experimental example. did
  • Epoxy resin aralkyl type epoxy resin (softening point 57 ° C, EEW 280 g / eq, viscosity (150 ° C) 0.9 Pa s)
  • Curing agent aralkyl type phenolic resin (softening point 66 ° C, hydroxyl equivalent 205 g / eq, viscosity (150 ° C) 0.8 Pa s)
  • Ionic polymer 1 Anionic polymers containing carboxyl groups (Hydroxystearic acid oligomers, Mw 5,500 g/mol, acid value 32 mgKOH/g)
  • Ionic polymer 2 Anionic polymers containing carboxyl groups (Hydroxystearic acid oligomers, Mw 2,200 g/mol, acid value 73 mgKOH/g)
  • Ionic polymer 3 anionic polymer containing a carboxyl group (Octadecenyl succinic acid, Mw 600 g/mol, acid value 300 mgKOH/g)
  • Ionic polymer 4 anionic polymer containing no carboxyl group (Phosphate ester, Mw 1,200 g/mol, acid value 85 mgKOH/g)
  • Ionic polymer 5 anionic polymer containing no carboxyl group (Fatty acid ethylene ester, acid value 17 mgKOH/g)
  • Ionic polymer 6 cationic polymer (Alkylamide polyol, Mw 53,000 g/mol)
  • Ionic Polymer 7 Cationic Polymer (Polyoxyalkylene amine derivative, Mw 2,600 g/mol)
  • the discharge amount of the epoxy resin composition was 24.2 g, which was calculated from the specific gravity (1.85) of the epoxy resin composition, cured thickness, and substrate size.
  • the granular epoxy resin composition of the present invention has a swelling change rate of less than 15% under vacuum and molding temperature, and it is used to prevent swelling in the compression molding process performed under high temperature and pressure during semiconductor chip molding, thereby preventing swelling. It is possible to improve the fillability and moldability of the manufactured semiconductor molding material while minimizing equipment failure caused by leakage of the molten epoxy resin composition to the outside of the substrate or mold.
  • the rheological properties that is, the swelling change rate, measured from the granular epoxy resin composition specimens to less than 15%, whether it corresponds to the granular epoxy resin composition having excellent moldability and filling properties as a molding material is preliminarily determined. can be screened on.
  • the granular epoxy resin composition of the present invention can provide high reliability when applied to thin-film semiconductor devices and integrated semiconductor devices by improving fine gap filling characteristics.

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Abstract

The present invention relates to a granular epoxy resin composition and a semiconductor device encapsulated using same.

Description

과립형 에폭시 수지 조성물Granular Epoxy Resin Composition
본 발명은 과립형 에폭시 수지 조성물 및 이를 이용하여 봉지된 반도체 소자에 관한 것이다. The present invention relates to a granular epoxy resin composition and a semiconductor device sealed using the same.
다양한 형태의 반도체 소자, 일 예로 집적회로(IC), 대용량 집적회로(LSI), 트랜지스터, 다이오드 등을 보호하기 위해 밀봉하여 반도체 장치의 특성 및 신뢰성을 향상시키는 물질로 에폭시 수지 조성물(EMC, epoxy molding compound)이 사용되고 있다. Epoxy resin composition (EMC, epoxy mold compound) is being used.
최근 전자 기기의 소형화, 경량화, 고성능화 추세에 따라 반도체의 고집적화가 가속화되면서, 반도체 소자의 밀봉에 사용되는 재료의 성능 개선을 위한 연구가 다방면으로 지속되고 있다. 특히, 반도체 소자 내 웨이퍼 칩(wafer chip)의 크기가 커지고, 반도체 소자의 두께가 얇아지면서, 반도체 소자 상의 봉지재의 두께 및 단위 소자당 봉지재의 사용량도 점차 줄어들고 있다. 반도체 소자 상의 봉지재의 두께는 반도체 소자의 리드 프레임 또는 회로 기판 탑재면의 반대측 표면을 밀봉하는 봉지재의 두께를 의미하며, 1 이상의 반도체 소자가 리드 프레임 또는 회로 기판 상에 적층하여 탑재되는 경우 리드 프레임 또는 회로 기판 탑재면의 반대측 최상면의 반도체 소자의 표면을 밀봉하는 봉지재의 두께를 의미한다. As the high integration of semiconductors accelerates according to the recent trend of miniaturization, light weight, and high performance of electronic devices, research to improve the performance of materials used for sealing semiconductor devices continues in various fields. In particular, as the size of a wafer chip in a semiconductor device increases and the thickness of the semiconductor device becomes thinner, the thickness of the encapsulant on the semiconductor device and the amount of the encapsulant per unit device are gradually reduced. The thickness of the encapsulant on the semiconductor device means the thickness of the encapsulant sealing the opposite surface of the lead frame or circuit board mounting surface of the semiconductor device, and when one or more semiconductor devices are stacked and mounted on the lead frame or circuit board, the lead frame or It means the thickness of the sealing material that seals the surface of the semiconductor element on the uppermost surface on the opposite side of the circuit board mounting surface.
반도체 소자의 봉지 방식은 고형의 에폭시 수지 조성물을 원통형으로 타정한 타블렛을 이용한 이송 성형(transfer molding) 방식이 주를 이루었으나, 최근 반도체의 미세화, 집적화 등의 기술발전 및 원가 절감에 대한 시장의 요구가 증가에 따라 압축 성형(compression mold) 방식이 널리 적용되고 있다.The encapsulation method of semiconductor devices has been mainly a transfer molding method using a tablet in which a solid epoxy resin composition is compressed into a cylindrical shape. As , the compression mold method is widely applied.
그러나, 종래의 에폭시 수지 조성물은 압축 성형에 적합한 흐름성, 미세 갭-필링(gap filling) 특성, 부풀음(swelling)/누설(leakage) 방지 특성을 확보하기 어려운 문제가 있다. 이에, 압축 성형에 적합한 작업성 및 성형성을 갖는 과립 형태의 반도체 소자 봉지용 수지 조성물에 대한 개발이 요구된다. However, the conventional epoxy resin composition has a problem in that it is difficult to secure flowability suitable for compression molding, fine gap-filling characteristics, and swelling/leakage prevention characteristics. Accordingly, there is a need to develop a resin composition for encapsulating a semiconductor device in a granular form having workability and moldability suitable for compression molding.
또한, 실제 반도체 소자를 제조하여 에폭시 수지 조성물이 만족스러운 물성을 나타내는지를 평가하는 방식을 채택할 경우, 제품 개발에 많은 비용과 시간이 소요된다. 이에, 실제 제품으로 가공하기 전에 우수한 성형성을 갖는 과립형 에폭시 수지 조성물을 미리 스크리닝할 수 있는 방법에 대한 연구가 필요하다. In addition, when a method of manufacturing an actual semiconductor device and evaluating whether an epoxy resin composition exhibits satisfactory physical properties is adopted, a lot of cost and time are required for product development. Therefore, it is necessary to study a method for pre-screening a granular epoxy resin composition having excellent moldability before processing into an actual product.
본 발명은 반도체 소자 밀봉 시, 흐름성 및 충진성이 우수하여 EMC의 성형성이 우수하고, 성형 시 부풀음(swelling) 방지 특성이 향상된 과립형 에폭시 수지 조성물을 제공한다. 특히, 본 발명은 과립형 에폭시 수지 조성물의 부풀음 변화율을 제어함으로써, 이를 사용하여 반도체 칩의 밀봉 시, 용융된 에폭시 수지 조성물이 금형 외부로 누출되는 현상이 현저히 줄어들어 몰딩재의 성형성이 우수하고, 신뢰성이 우수한 반도체 패키지를 제조할 수 있는 과립형 에폭시 수지 조성물을 제공한다.The present invention provides a granular epoxy resin composition having excellent flowability and filling properties when sealing a semiconductor device, excellent moldability of EMC, and improved anti-swelling property during molding. In particular, the present invention controls the swelling change rate of the granular epoxy resin composition, so that when sealing a semiconductor chip using the same, the leakage of the molten epoxy resin composition to the outside of the mold is significantly reduced, resulting in excellent moldability and reliability of the molding material. A granular epoxy resin composition capable of producing this excellent semiconductor package is provided.
또한, 본 발명은 상기 과립형 에폭시 수지 조성물로 봉지된 반도체 소자를 제공한다.In addition, the present invention provides a semiconductor device sealed with the granular epoxy resin composition.
본 발명은 에폭시 수지, 경화제 및 충전재를 포함하고, 진공 및 몰딩 온도 하에서 부풀음 변화율이 15 % 미만인 과립형 에폭시 수지 조성물을 제공한다.The present invention provides a granular epoxy resin composition comprising an epoxy resin, a curing agent and a filler, and having a swelling change rate of less than 15% under vacuum and molding temperature.
본 발명의 과립형 에폭시 수지 조성물은 진공 및 몰딩 온도 하에서 부풀음 변화율이 15 % 미만인 것으로, 이를 사용하여 반도체 칩 몰딩 시 고온, 압력 하 수행되는 압축 성형과정에서 부풀음 현상(swelling)을 방지하고, 이로 인해 용융된 에폭시 수지 조성물이 기판 또는 금형 외부로 새어 나옴으로써 초래되는 설비 오류 발생을 최소화하면서, 제조된 반도체 몰딩재의 충진성, 성형성을 향상시킬 수 있다. 또한, 본 발명에 따르면, 과립형 에폭시 수지 조성물 시편으로부터 측정된 유변 물성, 즉 부풀음 변화율을 15 % 미만으로 제어함으로써, 몰딩재로서 우수한 성형성 및 충진성을 갖는 과립형 에폭시 수지 조성물에 해당하는지를 사전에 스크리닝할 수 있다. The granular epoxy resin composition of the present invention has a swelling change rate of less than 15% under vacuum and molding temperature, and it is used to prevent swelling in the compression molding process performed under high temperature and pressure during semiconductor chip molding, thereby preventing swelling. It is possible to improve the fillability and moldability of the manufactured semiconductor molding material while minimizing equipment failure caused by leakage of the molten epoxy resin composition to the outside of the substrate or mold. In addition, according to the present invention, by controlling the rheological properties, that is, the swelling change rate, measured from the granular epoxy resin composition specimens to less than 15%, whether it corresponds to the granular epoxy resin composition having excellent moldability and filling properties as a molding material is preliminarily determined. can be screened on.
또한, 본 발명의 과립형 에폭시 수지 조성물은 미세 갭 필링 특성을 향상시켜 박막형 반도체 소자, 집적화된 반도체 소자 등에 적용 시 높은 신뢰성을 제공할 수 있다.In addition, the granular epoxy resin composition of the present invention can provide high reliability when applied to thin-film semiconductor devices and integrated semiconductor devices by improving fine gap filling characteristics.
이하, 본 발명에 대하여 상세히 설명한다. 그러나, 하기 내용에 의해서만 한정되는 것은 아니며, 필요에 따라 각 구성요소가 다양하게 변형되거나 선택적으로 혼용될 수 있다. 따라서, 본 발명의 사상 및 기술범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Hereinafter, the present invention will be described in detail. However, it is not limited only by the following contents, and each component may be variously modified or selectively mixed as needed. Therefore, it should be understood to include all modifications, equivalents or substitutes included in the spirit and scope of the present invention.
<과립형 에폭시 수지 조성물><Granular epoxy resin composition>
반도체 소자 제조 공정 중 에폭시 수지 조성물을 사용하여 압축 성형 시, 고온에서 경화되어 형성되는 에폭시 몰딩재(EMC, epoxy molding compound)의 부풀음 현상이 발생하면, 용융된 에폭시 수지 조성물이 기판 및 금형 외부로 새어 나와 공정 설비의 오염을 발생시키고, 나아가 압축 성형기의 고장을 초래할 수 있다. 뿐만 아니라 누출된 에폭시 조성물을 제거하는 과정이 필요하여 생산성이 저하될 수 있다. During compression molding using an epoxy resin composition during the manufacturing process of a semiconductor device, if swelling occurs in the epoxy molding compound (EMC) formed by curing at high temperatures, the molten epoxy resin composition leaks out of the substrate and mold. It can cause contamination of the process equipment and furthermore, the failure of the compression molding machine. In addition, a process of removing the leaked epoxy composition may be required, which may decrease productivity.
그러나, 본 발명은 진공 및 몰딩 온도 하에서 과립형 에폭시 수지 조성물의 부풀음 변화율을 15 % 미만으로 제어함으로서, 상기 과립형 에폭시 수지 조성물을 사용하여 반도체 칩 몰딩 시, 제조된 에폭시 몰딩재의 보이드(void) 발생을 억제함과 동시에 흐름성, 성형성 및 충진성을 향상시킬 수 있다. 이로 인하여, 공정 상 용융된 에폭시 수지 조성물이 금형 외부로 누출되는 것이 방지되어 신뢰성이 향상될 뿐만 아니라 공정 설비의 오류 발생을 줄이고, 공정 설비의 오염 발생을 최소화시켜 금형 교체 주기, 설비 청소 주기를 늘려 생산성을 향상시킬 수 있다. However, the present invention controls the swelling change rate of the granular epoxy resin composition to less than 15% under vacuum and molding temperature, so that voids occur in the manufactured epoxy molding material when molding a semiconductor chip using the granular epoxy resin composition. It is possible to improve flowability, formability and filling property at the same time as suppressing the As a result, the leakage of the molten epoxy resin composition during the process is prevented from leaking out of the mold, thereby improving reliability, reducing the occurrence of errors in process equipment, and minimizing contamination of process equipment, thereby increasing the mold replacement cycle and equipment cleaning cycle. productivity can be improved.
본 발명에 따른 과립형 에폭시 수지 조성물은 진공 및 몰딩 온도 하에서 부풀음 변화율이 15 % 미만, 예를 들어 10 % 미만, 다른 예로 3 % 미만이다. 부풀음 변화율은 하기 식으로 판정하였다. The granular epoxy resin composition according to the present invention has a swelling change rate under vacuum and molding temperature of less than 15%, for example less than 10%, in another example less than 3%. The swelling change rate was determined by the following formula.
부풀음 변화율(%) = (H/H0 - 1) x 100Bulge change rate (%) = (H/H 0 - 1) x 100
(H0: 초기 높이, H: 부풀음 높이)(H 0 : initial height, H: swelling height)
과립형 에폭시 수지 조성물의 부풀어 오른 높이가 전술한 범위를 초과하는 경우, 압축 성형 시 금형 사이로 에폭시 수지 조성물이 누출되어 장비를 오염시키고, 성형물의 불량을 초래할 수 있다. When the swollen height of the granular epoxy resin composition exceeds the above range, the epoxy resin composition leaks between molds during compression molding, contaminating equipment, and causing defects in molded products.
상기 측정 시 온도는 압축 성형 시의 몰딩 온도이고, 예를 들어 145 내지 165 ℃, 일례로 145 내지 155 ℃일 수 있다. 상기 몰딩 온도로 과립형 에폭시 수지 조성물이 더 이상 부풀어 오르지 않을 때까지, 예를 들어 3 내지 10분간 가열할 수 있다. 진공 및 몰딩 온도 조건을 충족시킬 수 있는 한, 특정한 측정 장치를 사용하는 것으로 제한되지 않으며, 예를 들어, 진공 상태로 만들 수 있는 밀폐 장치 내에 핫 플레이트(Hot Plate)를 포함하는 장치를 사용하여 측정할 수 있다. 일 예로, 640 torr 미만의 진공 하, 150 ℃의 핫 플레이트 위에서 5분간 가열한 후 평가할 수 있다.The temperature during the measurement is a molding temperature during compression molding, and may be, for example, 145 to 165 °C, for example 145 to 155 °C. It may be heated to the molding temperature until the granular epoxy resin composition no longer swells, for example, for 3 to 10 minutes. It is not limited to using a specific measuring device as long as the vacuum and molding temperature conditions can be met, for example, measuring using a device including a hot plate in a sealing device that can be made into a vacuum state. can do. For example, it may be evaluated after heating for 5 minutes on a hot plate at 150 ° C. under a vacuum of less than 640 torr.
본 발명의 과립형 에폭시 수지 조성물은 압축 성형기를 이용하여 반도체 칩을 몰딩할 때, 에폭시 몰딩재로 형성되지 않고 기판 바깥으로 빠져 나온 경화물의 양이 압축 성형을 위해 기판 위에 토출된 과립형 에폭시 수지 조성물의 양 대비 3 % 미만일 수 있다. 상기 몰딩 조건은 몰딩 온도 145 내지 165 ℃, 압축 압력 10 내지 50 ton, 진공도 10 내지 800 torr이다. 일 예로, 몰딩 온도 155 ℃, 압축 압력 30 ton, 진공도 70 torr 하에서 몰딩한 후 평가할 수 있다.The granular epoxy resin composition of the present invention is a granular epoxy resin composition in which, when a semiconductor chip is molded using a compression molding machine, the amount of cured material that is not formed as an epoxy molding material and escapes out of the substrate is discharged onto the substrate for compression molding. may be less than 3% relative to the amount of The molding conditions are a molding temperature of 145 to 165 °C, a compression pressure of 10 to 50 ton, and a vacuum degree of 10 to 800 torr. For example, it may be evaluated after molding under a molding temperature of 155 ° C., a compression pressure of 30 ton, and a vacuum degree of 70 torr.
본 발명에 따른 과립형 에폭시 수지 조성물은 에폭시 수지, 경화제 및 충전재를 포함하고, 필요에 따라 본 발명의 물성을 저해하지 않는 범위 내에서 음이온성 고분자, 경화 촉매, 커플링제, 착색제, 이형제, 개질제, 난연제, 저응력화제, 소포제 등의 해당 기술분야에서 통상적으로 사용되는 1종 이상의 첨가제를 더 포함할 수 있다.The granular epoxy resin composition according to the present invention includes an epoxy resin, a curing agent and a filler, and, if necessary, an anionic polymer, a curing catalyst, a coupling agent, a colorant, a release agent, a modifier, One or more additives commonly used in the art, such as a flame retardant, a stress reducing agent, and an antifoaming agent, may be further included.
에폭시 수지epoxy resin
본 발명의 과립형 에폭시 수지 조성물은 주 수지로서 에폭시 수지를 포함할 수 있다. 상기 에폭시 수지는 경화제와 반응하여 경화된 후 삼차원 망상 구조를 형성함으로써 피착체에 강하고 견고하게 접착하는 성질과 내열성을 부여할 수 있다.The granular epoxy resin composition of the present invention may contain an epoxy resin as a main resin. The epoxy resin reacts with a curing agent to form a three-dimensional network structure after being cured, thereby imparting strong and robust adhesion and heat resistance to an adherend.
상기 에폭시 수지로는 해당 기술분야에서 통상적으로 사용되는 에폭시 수지라면 특별한 제한없이 사용할 수 있다. 사용 가능한 에폭시 수지의 비제한적인 예로는, 비스페놀 A형 에폭시 수지, 지환형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 비스페놀 F형 에폭시 수지, 비스페놀 S형 에폭시 수지, 나프탈렌형 에폭시 수지, 안트라센 에폭시 수지, 테트라메틸 비페닐형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 비스페놀 A 노볼락형 에폭시 수지, 비스페놀 S 노볼락형 에폭시 수지, 비페닐 노볼락형 에폭시 수지, 나프톨 노볼락형 에폭시 수지, 나프톨 페놀 공축 노볼락형 에폭시 수지, 나프톨 크레졸 공축 노볼락형 에폭시 수지, 방향족 탄화수소 포름알데히드 수지 변형 페놀 수지형 에폭시 수지, 트리페닐 메탄형 에폭시 수지, 테트라페닐 에탄형 에폭시 수지, 디사이클로펜타디엔형 에폭시 수지, 디사이클로펜타디엔 페놀 부가반응형 에폭시 수지, 비페닐형 에폭시 수지, 페놀 아랄킬형 에폭시 수지, 다관능성 페놀 수지, 나프톨 아랄킬형 에폭시 수지 등이 있고, 이들 중 1종 이상을 포함할 수 있다. As the epoxy resin, any epoxy resin commonly used in the art may be used without particular limitation. Non-limiting examples of usable epoxy resins include bisphenol A type epoxy resins, alicyclic epoxy resins, cresol novolac type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, Tetramethyl Biphenyl 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 Furnace Rockfish type epoxy resin, naphthol cresol coaxial novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenyl methane type epoxy resin, tetraphenyl ethane type epoxy resin, dicyclopentadiene type epoxy resin, dicyclo There are pentadiene phenol addition reaction type epoxy resins, biphenyl type epoxy resins, phenol aralkyl type epoxy resins, multifunctional phenol resins, naphthol aralkyl type epoxy resins, and the like, and one or more of these may be included.
또한, 에폭시 수지로 연화점(Soft Point)이 40 내지 75 ℃, 예를 들어 50 내지 65 ℃인 것을 사용할 수 있다. 뿐만 아니라, 상기 에폭시 수지로는 에폭시 당량(EEW)이 100 내지 400 g/eq, 예를 들어 180 내지 350 g/eq, 다른 예로 250 내지 300 g/eq이고, 점도(150 ℃ 기준)가 0.01 내지 50 poise, 예를 들어 0.01 내지 10 poise, 다른 예로 0.01 내지 2 poise인 것을 사용할 수 있다. 전술한 에폭시 수지 조성물은 고함량의 충전재가 포함되더라도 흐름성, 유동성을 확보할 수 있으며, 혼련이 용이하여 분산성이 향상되고, 이로 인해 우수한 성형성을 가질 수 있다.In addition, an epoxy resin having a softening point of 40 to 75 °C, for example, 50 to 65 °C may be used. In addition, the epoxy resin has an epoxy equivalent weight (EEW) of 100 to 400 g/eq, for example, 180 to 350 g/eq, and another example of 250 to 300 g/eq, and a viscosity (based on 150 °C) of 0.01 to 300 g/eq. 50 poise, for example 0.01 to 10 poise, another example 0.01 to 2 poise may be used. The above-described epoxy resin composition can secure flowability and fluidity even when a high content of filler is included, and can be easily kneaded to improve dispersibility, thereby having excellent moldability.
본 발명의 과립형 에폭시 수지 조성물의 총 중량을 기준으로, 상기 에폭시 수지의 함량은 2 내지 20 중량%, 예를 들어 5 내지 15 중량%일 수 있다. 에폭시 수지의 함량이 전술한 범위 미만인 경우 조성물의 점도가 높아져 흐름성 및 성형성이 저하되고, 이로 인해 반도체 소자 내 에폭시 수지 조성물의 미충진 문제가 발생할 수 있으며, 작업성이 저하될 수 있다. 한편, 에폭시 수지의 함량이 전술한 범위를 초과하는 경우 흡습량 증가로 인해 반도체의 신뢰성이 불량해지고, 충전재 함량의 상대적 감소로 인해 상기 과립형 에폭시 수지 조성물을 통해 제조된 에폭시 몰딩재의 강도가 저하될 수 있다.Based on the total weight of the granular epoxy resin composition of the present invention, the content of the epoxy resin may be 2 to 20% by weight, for example 5 to 15% by weight. When the content of the epoxy resin is less than the above-mentioned range, the viscosity of the composition increases and flowability and moldability decrease, which may cause a problem of insufficient filling of the epoxy resin composition in a semiconductor device and degrade workability. On the other hand, when the content of the epoxy resin exceeds the above range, the reliability of the semiconductor becomes poor due to the increase in moisture absorption, and the strength of the epoxy molding material prepared through the granular epoxy resin composition is lowered due to the relative decrease in the content of the filler. can
경화제curing agent
본 발명의 과립형 에폭시 수지 조성물은 경화제를 포함한다. 경화제는 반응성 수소를 포함하며, 이는 상기 에폭시 수지의 에폭사이드기와 반응하여 조성물의 경화를 진행시키는 역할을 한다.The granular epoxy resin composition of the present invention includes a curing agent. The curing agent contains reactive hydrogen, which reacts with the epoxide groups of the epoxy resin to promote curing of the composition.
상기 경화제로는 에폭시 수지와 경화 반응을 하는 것으로 해당 기술분야에 공지된 경화제를 사용할 수 있으며, 일 예로 상기 경화제는 한 분자 내에 2개 이상의 페놀성 수산기를 갖는 페놀계 화합물일 수 있다. 사용 가능한 경화제의 비제한적인 예로는, 페놀 노볼락 수지, 크레졸 노볼락 수지, 페놀 아랄킬 수지, 다관능 페놀 화합물 등이 있고, 이들 중 1종 이상을 포함할 수 있다. As the curing agent, a curing agent known in the art as having a curing reaction with an epoxy resin may be used. For example, 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 resins, cresol novolac resins, phenol aralkyl resins, multifunctional phenol compounds, and the like, and may include one or more of these.
상기 경화제로는 연화점이 50 내지 85 ℃, 예를 들어 60 내지 79 ℃, 다른 예로 64 내지 75 ℃인 것을 사용할 수 있다. 또한, 상기 경화제로는 수산기 당량이 150 내지 300 g/eq, 예를 들어 190 내지 230 g/eq이고, 점도(150 ℃ 기준)가 0.01 내지 10 poise, 예를 들어 0.01 내지 2 poise인 것을 사용할 수 있다. As the curing agent, one having a softening point of 50 to 85 °C, for example, 60 to 79 °C, and another example of 64 to 75 °C may be used. In addition, as the curing agent, a hydroxyl equivalent of 150 to 300 g/eq, for example, 190 to 230 g/eq, and a viscosity (based on 150 °C) of 0.01 to 10 poise, for example, 0.01 to 2 poise may be used. there is.
본 발명의 과립형 에폭시 수지 조성물의 총 중량을 기준으로, 상기 경화제의 함량은 2 내지 20 중량%, 예를 들어 2 내지 15 중량%일 수 있다. 경화제의 함량이 전술한 범위 미만인 경우 경화성 및 성형성이 저하될 수 있으며, 전술한 범위를 초과하는 경우 흡습량 증가로 반도체의 신뢰성이 불량해지고 강도가 저하될 수 있다.Based on the total weight of the granular epoxy resin composition of the present invention, the content of the curing agent may be 2 to 20% by weight, for example 2 to 15% by weight. When the content of the curing agent is less than the above range, curability and moldability may be deteriorated, and when it exceeds the above range, reliability of the semiconductor may be poor and strength may be reduced due to an increase in moisture absorption.
충전재filling
본 발명의 과립형 에폭시 수지 조성물은 충전재를 포함한다. 충전재는 에폭시 수지 조성물의 기계적 물성(예컨대, 강도)을 향상시키고, 흡습량을 낮추는 역할을 한다.The granular epoxy resin composition of the present invention includes a filler. The filler serves to improve the mechanical properties (eg, strength) of the epoxy resin composition and lower the amount of moisture absorption.
상기 충전재로는 통상적으로 전자소재 분야에서 사용되는 무기 충전재를 특별한 제한없이 사용할 수 있다. 예를 들어, 금속 산화물, 금속 질화물, 실리카, 실리카 나이트라이드, 알루미나, 알루미늄 나이트라이드, 보론 나이트라이드 등의 무기 충전재를 사용할 수 있고, 이들을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. 상기 충전재의 형태는 특별히 제한되지 않으며, 각상, 구상, 비정질 형태를 모두 사용할 수 있다. 본 발명에서 사용할 수 있는 충전재의 비제한적인 예로는 천연 실리카, 합성 실리카, 용융 실리카 등이 있으며, 예를 들어 구상 실리카 입자를 사용할 수 있다. As the filler, inorganic fillers commonly used in the field of electronic materials may be used without particular limitation. For example, inorganic fillers such as metal oxides, metal nitrides, silica, silica nitride, alumina, aluminum nitride, and boron nitride may be used, and these may be used alone or in combination of two or more. The shape of the filler is not particularly limited, and angular, spherical, and amorphous shapes may all be used. Non-limiting examples of the filler that can be used in the present invention include natural silica, synthetic silica, fused silica, and the like, and for example, spherical silica particles may be used.
상기 충전재는 입경이 상이한 2종 이상의 충전재를 포함할 수 있다. 이 경우, 과립형 에폭시 수지 조성물의 성형성 및 작업성을 더욱 향상시킬 수 있다. 예를 들어, 상기 충전재는 평균 입경(D50)이 상이한 2종의 충전재를 혼합하여 사용할 수 있으며, 일 예로 평균 입경(D50) 3.0 내지 20 ㎛, 예를 들어 3.0 내지 15 ㎛인 제1 충전재 및 평균 입경(D50)이 0.1 내지 3 ㎛, 예를 들어 0.1 내지 2 ㎛인 제2 충전재를 적절한 비율로 혼합하여 사용할 수 있다. The filler may include two or more types of fillers having different particle sizes. In this case, moldability and workability of the granular epoxy resin composition can be further improved. For example, the filler may be used by mixing two types of fillers having different average particle diameters (D50), for example, a first filler having an average particle diameter (D50) of 3.0 to 20 μm, for example, 3.0 to 15 μm and an average A second filler having a particle diameter (D50) of 0.1 to 3 μm, for example, 0.1 to 2 μm may be mixed and used in an appropriate ratio.
본 발명의 과립형 에폭시 수지 조성물의 총 중량을 기준으로, 상기 충전재의 함량은 50 내지 95 중량%, 예를 들어 70 내지 90 중량%일 수 있다. 충전재의 함량이 전술한 범위 미만인 경우 경화물의 흡습량이 증가되어 반도체 장치의 신뢰성을 저하시킬 수 있고, 전술한 범위를 초과하는 경우 유동성이 저하되어 성형성이 불량해질 수 있다.Based on the total weight of the granular epoxy resin composition of the present invention, the content of the filler may be 50 to 95% by weight, for example 70 to 90% by weight. If the content of the filler is less than the above range, the moisture absorption amount of the cured product may increase, thereby degrading the reliability of the semiconductor device, and if it exceeds the above range, fluidity may decrease and moldability may deteriorate.
음이온성 고분자anionic polymer
본 발명의 과립형 에폭시 수지 조성물은 음이온성 고분자를 포함할 수 있다. 상기 음이온성 고분자는 과립형 에폭시 수지 조성물의 압축 성형 시, 우수한 흐름성, 충진성 및 부풀음/누설 방지 특성을 부여함으로써 압축 성형에 적합한 작업성을 부여하고, 이로 인해 반도체 소자 봉지재로서 우수한 성형성 및 신뢰성을 향상시킬 수 있다.The granular epoxy resin composition of the present invention may include an anionic polymer. The anionic polymer provides workability suitable for compression molding by imparting excellent flowability, filling properties, and swelling/leakage prevention properties during compression molding of the granular epoxy resin composition, thereby providing excellent moldability as a semiconductor device encapsulant. and reliability can be improved.
상기 음이온성 고분자는 음의 전하를 나타내는 작용기 또는 모이어티를 갖는 고분자로, 상기 작용기 또는 모이어티는 주 골격 중에 존재하거나 측쇄의 말단 또는 도중에 존재할 수 있다. 상기 작용기는 카르복실기(-COO-), 술폰산기(-SO3-), 또는 아세톡시기(-CH2COO-) 중 하나 이상일 수 있다. 일례로, 상기 작용기는 카르복실기를 포함할 수 있다. The anionic polymer is a polymer having a functional group or moiety exhibiting a negative charge, and the functional group or moiety may be present in the main backbone or at the end or middle of a side chain. The functional group may be one or more of a carboxyl group (-COO-), a sulfonic acid group (-SO 3 -), or an acetoxy group (-CH 2 COO-). For example, the functional group may include a carboxyl group.
상기 음이온성 고분자는 직쇄형이거나, 또는 직쇄형 주 골격에 복수의 측쇄가 결합된 분기형일 수 있다. 일 예로, 상기 음이온성 고분자는 주쇄의 말단 또는 측쇄에 작용기로 카르복실기가 결합된 폴리카르복실산을 주 골격으로 하는 것으로, 탄화수소 사슬 또는 상기 탄화수소 사슬에 산소가 개재한 에테르 결합(-o-)을 가지는 것을 포함할 수 있고, 불포화 C=C 이중 결합을 포함하는 화합물일 수 있다. The anionic polymer may be linear or branched in which a plurality of side chains are bonded to a linear main backbone. For example, the anionic polymer has, as a main skeleton, a polycarboxylic acid having a carboxyl group bonded to a terminal or side chain of a main chain as a functional group, and has a hydrocarbon chain or an ether bond (-o-) in which oxygen is intervened in the hydrocarbon chain. It may include a compound having an unsaturated C=C double bond.
상기 음이온성 고분자 내에 포함되어 음의 전하를 나타내는 카르복실기는 상기 에폭시 수지와의 가교 결합에 참여할 수 있으며, 음이온성 고분자 내 주 골격의 비극성 탄화수소는 에폭시/페놀 수지와의 상용성을 증가시킬 수 있다. 또한, 상기 음이온성 고분자의 음의 전하를 나타내는 카르복실기로 인해 에폭시 수지 조성물 내 충전재의 분산성이 양호해져 침강이 방지됨으로써 저장 안정성이 우수하고, 이로 인해 에폭시 수지 조성물의 성형성, 저장 안정성(포트 라이프), 내블리드성이 향상될 수 있다.A carboxyl group included in the anionic polymer and exhibiting a negative charge may participate in cross-linking with the epoxy resin, and the non-polar hydrocarbon of the main skeleton in the anionic polymer may increase compatibility with the epoxy/phenol resin. In addition, due to the carboxyl group showing a negative charge of the anionic polymer, the dispersibility of the filler in the epoxy resin composition is improved, and sedimentation is prevented, resulting in excellent storage stability, which leads to moldability and storage stability (pot life) of the epoxy resin composition. ), bleed resistance can be improved.
상기 음이온성 고분자가 포함됨으로써, 본 발명의 과립형 에폭시 수지 조성물은 반도체 칩 몰딩시 압축 성형(compression molding) 공정에 적합한 흐름성, 우수한 충진성 및 부풀음(swelling)/누설(leakage) 방지 특성을 발휘할 수 있다. 특히, 상기 음이온성 고분자는 우수한 미세 갭-필링(gap filling) 특성, 예를 들어 갭 피치(gap pitch) 30 마이크론 이하에서도 우수한 충진 특성을 나타낸다. 이로 인해 상대적으로 얇은 두께의 밀봉층을 형성할 수도 있으며, 충진성도 현저히 개선시킬 수 있다.By including the anionic polymer, the granular epoxy resin composition of the present invention can exhibit flowability, excellent filling properties, and swelling/leakage prevention properties suitable for a compression molding process during semiconductor chip molding. can In particular, the anionic polymer exhibits excellent fine gap-filling characteristics, for example, excellent filling characteristics even at a gap pitch of 30 microns or less. Due to this, a relatively thin sealing layer may be formed, and the fillability may be remarkably improved.
또한, 상기 음이온성 고분자는 10 마이크론 이하 크기의 충전재를 균일하게 분산시켜 수지 매트릭스 내에 안정화시켜, 압축 성형 시 작업성 및 과립형 에폭시 수지 조성물의 성형성을 현저히 향상시킨다. In addition, the anionic polymer uniformly disperses fillers having a size of 10 microns or less to stabilize them in a resin matrix, thereby significantly improving workability during compression molding and moldability of the granular epoxy resin composition.
일례로, 상기 음이온성 고분자는 주 골격에 카르복실산기 및 에테르기를 포함하는 것일 수 있다. 또한, 다른 예로 상기 음이온성 고분자는 하기 화학식 1로 표시될 수 있다. For example, the anionic polymer may include a carboxylic acid group and an ether group in a main backbone. In addition, as another example, the anionic polymer may be represented by Formula 1 below.
[화학식 1] [Formula 1]
Figure PCTKR2022017535-appb-img-000001
Figure PCTKR2022017535-appb-img-000001
상기 식에서, In the above formula,
R1은 치환 또는 비치환의 탄소수 1 내지 10의 알킬기이고, R 1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;
R2는 수소, 카르복실산, 하이드록시기, 또는 치환 또는 비치환의 탄소수 1 내지 10의 알킬기이고, R 2 is hydrogen, a carboxylic acid, a hydroxy group, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;
X는 산소, 또는 C=C 이중 결합이고, X is oxygen or a C=C double bond;
p는 1 내지 20이다. p is 1 to 20;
상기 음이온성 고분자의 산가는 10 내지 350 mgKOH/g, 예를 들어 25 내지 320 mgKOH/g일 수 있다. 산가가 전술한 범위를 벗어나는 경우 저장 안정성이 열세해 질 수 있다.The acid value of the anionic polymer may be 10 to 350 mgKOH/g, for example 25 to 320 mgKOH/g. If the acid value is out of the above range, storage stability may be poor.
상기 음이온성 고분자의 중량평균분자량은 500 내지 10,000 g/mol, 예를 들어 4,000 내지 6,000 g/mol일 수 있다. 상기 음이온성 고분자의 중량평균분자량이 전술한 범위 미만인 경우 부풀음 특성 및 퍼짐(spreading) 특성을 제어하지 못할 수 있고, 전술한 범위를 초과할 경우 상기 과립형 에폭시 수지 경화물을 사용한 에폭시 몰딩재의 경화 특성을 저하시켜 성형물의 장기신뢰성을 저하시키는 요인이 될 수 있다. The weight average molecular weight of the anionic polymer may be 500 to 10,000 g/mol, for example 4,000 to 6,000 g/mol. When the weight average molecular weight of the anionic polymer is less than the above range, swelling and spreading properties may not be controlled, and when it exceeds the above range, the curing properties of the epoxy molding material using the granular epoxy resin cured product It can be a factor that lowers the long-term reliability of molded products.
본 발명의 과립형 에폭시 수지 조성물의 총 중량을 기준으로, 상기 음이온성 고분자의 함량은 0.3 내지 1.2 중량%, 예를 들어 0.4 내지 0.8 중량%일 수 있다. 상기 음이온성 고분자의 함량이 전술한 범위 미만인 경우 부풀음 특성 및 퍼짐성(spreading) 제어가 불충분할 수 있고, 전술한 범위를 초과하는 경우 저장 안정성 및 작업성이 열세해 질 수 있다.Based on the total weight of the granular epoxy resin composition of the present invention, the content of the anionic polymer may be 0.3 to 1.2% by weight, for example 0.4 to 0.8% by weight. When the content of the anionic polymer is less than the above range, swelling properties and spreading control may be insufficient, and when it exceeds the above range, storage stability and workability may be poor.
첨가제additive
본 발명의 과립형 에폭시 수지 조성물은 해당 조성물에 일반적으로 사용되는 첨가제들을 추가적으로 포함할 수 있다. 사용 가능한 첨가제의 비제한적인 예로는 경화 촉매, 커플링제, 착색제, 이형제 등이 있다. The granular epoxy resin composition of the present invention may additionally include additives commonly used in the composition. Non-limiting examples of usable additives include curing catalysts, coupling agents, colorants, release agents, and the like.
경화 촉매는 경화 반응을 촉진하는 것으로, 이미다졸계 화합물, 나프탈렌계 잠재성 촉매, 아민계 화합물, 유기금속 화합물, 유기인 화합물, 붕소 화합물 등을 사용할 수 있다. 커플링제는 유기물과 무기물의 안정적인 분산을 위해 첨가되며, 상기 커플링제로는 에폭시 실란, 아미노 실란, 메르캅토 실란, 아크릴 실란, 비닐 실란 등을 사용할 수 있다. 착색제는 수지 조성물에 색상을 부여하기 위해 첨가되며, 상기 착색제로는 카본블랙, 벵갈라 등을 사용할 수 있다. 이형제는 EMC와 금형과의 이형성을 확보하기 위해 첨가되며, 상기 이형제로는 파라핀 왁스, 카르나우바 왁스, 폴리에틸렌 왁스, 에스테르 왁스 등을 사용할 수 있다. 이 외에, 음이온 포착제, 소포제 등을 더 포함할 수 있다.The curing catalyst is to accelerate the curing reaction, and an imidazole-based compound, a naphthalene-based latent catalyst, an amine-based compound, an organometallic compound, an organophosphorus compound, a boron compound, or the like may be used. A coupling agent is added for stable dispersion of organic and inorganic materials, and epoxy silane, amino silane, mercapto silane, acrylic silane, vinyl silane, etc. may be used as the coupling agent. A colorant is added to impart color to the resin composition, and carbon black, bengala, etc. may be used as the colorant. A release agent is added to ensure releasability between the EMC and the mold, and paraffin wax, carnauba wax, polyethylene wax, ester wax, etc. may be used as the release agent. In addition, an anion scavenger, an antifoaming agent, and the like may be further included.
상기 첨가제는 해당 기술분야에 공지된 함량 범위 내에서 첨가될 수 있으며, 일례로 과립형 에폭시 수지 조성물의 전체 중량에 대하여, 각각 0.01 내지 5 중량% 포함될 수 있으나, 이에 한정되는 것은 아니다.The additives may be added within an amount known in the art, and for example, may be included in an amount of 0.01 to 5% by weight based on the total weight of the granular epoxy resin composition, but is not limited thereto.
<반도체 소자><Semiconductor device>
본 발명은 전술한 과립형 에폭시 수지 조성물을 사용하여 봉지된 반도체 소자를 제공한다. 상기 반도체 소자는 트랜지스터, 다이오드, 마이크로프로세서, 반도체 메모리, 전력 반도체 등일 수 있다. 특히, 본 발명에 따른 과립형 에폭시 수지 조성물은 패키지 적층형의 POP(Package On Package) 및 반도체 칩 적층형의 COC (Chip On Chip)에 적용 가능하다. The present invention provides a semiconductor device encapsulated using the granular epoxy resin composition described above. The semiconductor device may be a transistor, a diode, a microprocessor, a semiconductor memory, or a power semiconductor. In particular, the granular epoxy resin composition according to the present invention can be applied to package stacking type POP (Package On Package) and semiconductor chip stacking type COC (Chip On Chip).
본 발명의 과립형 에폭시 수지 조성물을 이용하여 반도체 소자를 봉지하는 방법은 해당 기술 분야에서 통상적인 방법, 예컨대 이송 성형(transfer molding), 압축 성형(compression molding), 사출 성형(injection molding) 등의 성형 방법에 따라 수행될 수 있다.A method of encapsulating a semiconductor device using the granular epoxy resin composition of the present invention is a conventional method in the art, such as transfer molding, compression molding, injection molding, and the like. It can be done according to the method.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다. 그러나, 하기 실시예는 본 발명의 이해를 돕기 위한 것일 뿐 어떠한 의미로든 본 발명의 범위가 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only for facilitating the understanding of the present invention, and the scope of the present invention is not limited to the examples in any sense.
[실험예 1-11][Experimental Example 1-11]
하기 표 1에 기재된 조성에 따라 각 성분을 배합한 후, 용융 혼련기(Kneader)를 이용하여 70 내지 130 ℃의 온도에서 용융 혼합된 혼합물을 granulator에 통과시켜 각 실험예의 과립형 에폭시 수지 조성물을 제조하였다.After blending each component according to the composition shown in Table 1 below, the melt-mixed mixture was passed through a granulator at a temperature of 70 to 130 ° C using a melt kneader to prepare a granular epoxy resin composition of each experimental example. did
각 실험예에 따라 제조된 과립형 에폭시 수지 조성물 2 g을 28 X 61 mm 크기의 20 ml 투명 바이알(vial)에 넣고, 감압 가온(640 torr, 150 ℃, 5분) 상태에서 부풀어 오르는 정도를 측정하였다. 부풀음 변화율은 초기 높이 대비 감압 가온 상태에서의 높이 비율로 하기 식으로 판정하였다. 측정 결과는 하기 표 1에 나타내었고, 변화율이 낮을수록 부풀음 방지 특성이 우수하다.2 g of the granular epoxy resin composition prepared according to each experimental example was placed in a 20 ml transparent vial having a size of 28 X 61 mm, and the degree of swelling was measured under reduced pressure heating (640 torr, 150 ° C., 5 minutes) did The swelling change rate was determined by the following formula as a height ratio in the reduced-pressure heating state compared to the initial height. The measurement results are shown in Table 1 below, and the lower the change rate, the better the anti-swelling property.
부풀음 변화율(%) = (H/H0 - 1) x 100Bulge change rate (%) = (H/H 0 - 1) x 100
(H0: 초기 높이, H: 부풀음 높이)(H 0 : initial height, H: swelling height)
Figure PCTKR2022017535-appb-img-000002
Figure PCTKR2022017535-appb-img-000002
에폭시 수지: 아랄킬형 에폭시 수지 (연화점 57 ℃, EEW 280 g/eq, 점도(150 ℃) 0.9 Pa·s)Epoxy resin: aralkyl type epoxy resin (softening point 57 ° C, EEW 280 g / eq, viscosity (150 ° C) 0.9 Pa s)
경화제: 아랄킬형 페놀 수지 (연화점 66 ℃, 수산기 당량 205 g/eq, 점도(150 ℃) 0.8 Pa·s)Curing agent: aralkyl type phenolic resin (softening point 66 ° C, hydroxyl equivalent 205 g / eq, viscosity (150 ° C) 0.8 Pa s)
충전재 1: 실리카 1 (D50 4.8 μm, D90 9.95 μm)Filler 1: Silica 1 (D50 4.8 μm, D90 9.95 μm)
충전재 2: 실리카 2 (D50 2.0 μm, D90 4.0 μm)Filler 2: Silica 2 (D50 2.0 μm, D90 4.0 μm)
이온성 고분자 1: 카르복실기를 포함한 음이온성 고분자 (Hydroxystearic acid oligomers, Mw 5,500 g/mol, 산가 32 mgKOH/g)Ionic polymer 1: Anionic polymers containing carboxyl groups (Hydroxystearic acid oligomers, Mw 5,500 g/mol, acid value 32 mgKOH/g)
이온성 고분자 2: 카르복실기를 포함한 음이온성 고분자 (Hydroxystearic acid oligomers, Mw 2,200 g/mol, 산가 73 mgKOH/g)Ionic polymer 2: Anionic polymers containing carboxyl groups (Hydroxystearic acid oligomers, Mw 2,200 g/mol, acid value 73 mgKOH/g)
이온성 고분자 3: 카르복실기를 포함한 음이온성 고분자 (Octadecenyl succinic acid, Mw 600 g/mol, 산가 300 mgKOH/g)Ionic polymer 3: anionic polymer containing a carboxyl group (Octadecenyl succinic acid, Mw 600 g/mol, acid value 300 mgKOH/g)
이온성 고분자 4: 카르복실기를 미포함한 음이온성 고분자 (Phosphate ester, Mw 1,200 g/mol, 산가 85 mgKOH/g)Ionic polymer 4: anionic polymer containing no carboxyl group (Phosphate ester, Mw 1,200 g/mol, acid value 85 mgKOH/g)
이온성 고분자 5: 카르복실기를 미포함한 음이온성 고분자 (Fatty acid ethylene ester, 산가 17 mgKOH/g)Ionic polymer 5: anionic polymer containing no carboxyl group (Fatty acid ethylene ester, acid value 17 mgKOH/g)
이온성 고분자 6: 양이온성 고분자 (Alkylamide polyol, Mw 53,000 g/mol)Ionic polymer 6: cationic polymer (Alkylamide polyol, Mw 53,000 g/mol)
이온성 고분자 7: 양이온성 고분자 (Polyoxyalkylene amine derivative, Mw 2,600 g/mol)Ionic Polymer 7: Cationic Polymer (Polyoxyalkylene amine derivative, Mw 2,600 g/mol)
[물성 평가] [Evaluation of physical properties]
각 실험예에서 제조된 에폭시 수지 조성물의 물성을 하기와 같이 측정하였으며, 이의 결과를 하기 표 2에 나타내었다.The physical properties of the epoxy resin composition prepared in each experimental example were measured as follows, and the results are shown in Table 2 below.
스파이럴 플로우(spiral flow)spiral flow
각 실험예에 따라 제조된 에폭시 수지 조성물을 스파이럴 플로우 몰드를 이용하여 가열이송성형기(압력 70 kg/㎠, 온도 155 ℃, 경화 시간 200초)에서 몰딩한 후 제조물의 흐름성을 측정하였다. After molding the epoxy resin composition prepared according to each experimental example in a heat transfer molding machine (pressure 70 kg/cm 2 , temperature 155 ° C., curing time 200 seconds) using a spiral flow mold, the flowability of the product was measured.
겔 타임(gelation time)gelation time
각 실험예에 따라 제조된 에폭시 수지 조성물 소량을 겔 타이머에 넓고 고르게 편 후, 조성물의 겔화 소요시간을 측정하였다.After spreading a small amount of the epoxy resin composition prepared according to each experimental example widely and evenly on a gel timer, the gelation time of the composition was measured.
경도(155 ℃ x 200 sec, Shore D)Hardness (155 ℃ x 200 sec, Shore D)
각 실험예에 따라 제조된 에폭시 수지 조성물을 가열이송성형기(압력 70 kg/㎠, 온도 155 ℃, 경화 시간 200초)에서 몰딩한 후 제조물의 경도를 측정하였다.After molding the epoxy resin composition prepared according to each experimental example in a heat transfer molding machine (pressure 70 kg/cm 2 , temperature 155° C., curing time 200 seconds), the hardness of the product was measured.
Leakage (%)Leakage (%)
각 실험예에 따라 제조된 에폭시 수지 조성물을 압축 성형기(압력 30 ton, 온도 155 ℃, 진공도 70 torr, 경화 시간 200초, 기판 크기 240 x 78 mm, 에폭시 수지 조성물 경화 두께 700 μm)에서 몰딩한 후, 기판 바깥으로 빠져 나온 에폭시 수지 조성물의 무게를 측정하였다. 하기 식으로 Leakage(%)를 계산하였고, 그 결과는 하기 표 2에 나타내었다. Leakage 비율이 낮을수록 Leakage 방지 특성이 우수하다.After molding the epoxy resin composition prepared according to each experimental example in a compression molding machine (pressure 30 ton, temperature 155 ° C, vacuum degree 70 torr, curing time 200 seconds, substrate size 240 x 78 mm, curing thickness of the epoxy resin composition 700 μm) , the weight of the epoxy resin composition coming out of the substrate was measured. Leakage (%) was calculated by the following formula, and the results are shown in Table 2 below. The lower the leakage ratio, the better the anti-leakage property.
Leakage(%) = W/W0 x 100Leakage(%) = W/W 0 x 100
(W0: 에폭시 수지 조성물 토출량 (g), (W 0 : discharge amount of epoxy resin composition (g),
W: 기판 바깥으로 빠져 나온 경화물 양 (g))W: amount of cured material protruding out of the substrate (g))
상기 식에서, 에폭시 수지 조성물의 토출량은 24.2g으로, 에폭시 수지 조성물의 비중(1.85), 경화 두께 및 기판 크기로부터 계산하였다. In the above formula, the discharge amount of the epoxy resin composition was 24.2 g, which was calculated from the specific gravity (1.85) of the epoxy resin composition, cured thickness, and substrate size.
Figure PCTKR2022017535-appb-img-000003
Figure PCTKR2022017535-appb-img-000003
상기 표 2의 결과로부터 확인되는 바와 같이, 본 발명에 따른 부풀음 변화율을 갖는 실험예 1-6의 에폭시 수지 조성물은 측정 항목 모두에서 전반적으로 우수한 물성을 나타내었다. 반면, 본 발명에 따른 범위를 벗어나는 부풀음 변화율을 갖는 실험예 7-11의 에폭시 수지 조성물의 경우 전반적으로 열세한 물성을 나타내었다.As confirmed from the results of Table 2, the epoxy resin compositions of Experimental Examples 1-6 having a swelling change rate according to the present invention exhibited generally excellent physical properties in all measurement items. On the other hand, in the case of the epoxy resin composition of Experimental Examples 7-11 having a swelling change rate outside the range according to the present invention, overall poor physical properties were exhibited.
본 발명의 과립형 에폭시 수지 조성물은 진공 및 몰딩 온도 하에서 부풀음 변화율이 15 % 미만인 것으로, 이를 사용하여 반도체 칩 몰딩 시 고온, 압력 하 수행되는 압축 성형과정에서 부풀음 현상(swelling)을 방지하고, 이로 인해 용융된 에폭시 수지 조성물이 기판 또는 금형 외부로 새어 나옴으로써 초래되는 설비 오류 발생을 최소화하면서, 제조된 반도체 몰딩재의 충진성, 성형성을 향상시킬 수 있다. 또한, 본 발명에 따르면, 과립형 에폭시 수지 조성물 시편으로부터 측정된 유변 물성, 즉 부풀음 변화율을 15 % 미만으로 제어함으로써, 몰딩재로서 우수한 성형성 및 충진성을 갖는 과립형 에폭시 수지 조성물에 해당하는지를 사전에 스크리닝할 수 있다. 또한, 본 발명의 과립형 에폭시 수지 조성물은 미세 갭 필링 특성을 향상시켜 박막형 반도체 소자, 집적화된 반도체 소자 등에 적용 시 높은 신뢰성을 제공할 수 있다.The granular epoxy resin composition of the present invention has a swelling change rate of less than 15% under vacuum and molding temperature, and it is used to prevent swelling in the compression molding process performed under high temperature and pressure during semiconductor chip molding, thereby preventing swelling. It is possible to improve the fillability and moldability of the manufactured semiconductor molding material while minimizing equipment failure caused by leakage of the molten epoxy resin composition to the outside of the substrate or mold. In addition, according to the present invention, by controlling the rheological properties, that is, the swelling change rate, measured from the granular epoxy resin composition specimens to less than 15%, whether it corresponds to the granular epoxy resin composition having excellent moldability and filling properties as a molding material is preliminarily determined. can be screened on. In addition, the granular epoxy resin composition of the present invention can provide high reliability when applied to thin-film semiconductor devices and integrated semiconductor devices by improving fine gap filling characteristics.

Claims (5)

  1. 에폭시 수지, 경화제 및 충전재를 포함하고, 진공 및 몰딩 온도(145 내지 165 ℃) 하에서 하기 식으로 표시되는 부풀음 변화율이 15 % 미만인 과립형 에폭시 수지 조성물:A granular epoxy resin composition comprising an epoxy resin, a curing agent and a filler and having a swelling change rate of less than 15% under vacuum and molding temperature (145 to 165 ° C.) expressed by the following formula:
    부풀음 변화율(%) = (H/H0 - 1) x 100Bulge change rate (%) = (H/H 0 - 1) x 100
    상기 식에서,In the above formula,
    H0는 초기 높이이고, H 0 is the initial height,
    H는 부풀음 높이임.H is the swelling height.
  2. 제1항에 있어서, According to claim 1,
    압축 성형기를 이용한 몰딩 시, 기판 바깥으로 빠져 나온 경화물의 양이 압축 성형을 위해 기판 위에 토출된 에폭시 수지 조성물의 양 대비 3 % 미만인 과립형 에폭시 수지 조성물.A granular epoxy resin composition in which the amount of cured material protruding out of the substrate during molding using a compression molding machine is less than 3% of the amount of the epoxy resin composition discharged onto the substrate for compression molding.
  3. 제1항에 있어서, According to claim 1,
    상기 과립형 에폭시 수지 조성물은 카르복실산기를 포함하는 음이온성 고분자를 더 포함하고, The granular epoxy resin composition further comprises an anionic polymer containing a carboxylic acid group,
    상기 음이온성 고분자가 하기 화학식 1로 표시되는 것인 과립형 에폭시 수지 조성물:A granular epoxy resin composition in which the anionic polymer is represented by Formula 1 below:
    [화학식 1] [Formula 1]
    Figure PCTKR2022017535-appb-img-000004
    Figure PCTKR2022017535-appb-img-000004
    상기 식에서, In the above formula,
    R1은 치환 또는 비치환의 탄소수 1 내지 10의 알킬기이고, R 1 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;
    R2는 수소, 카르복실산, 하이드록시기, 또는 치환 또는 비치환의 탄소수 1 내지 10의 알킬기이고, R 2 is hydrogen, a carboxylic acid, a hydroxy group, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;
    X는 산소, 또는 C=C 이중 결합이고, X is oxygen or a C=C double bond;
    p는 1 내지 20임.p is 1 to 20;
  4. 제3항에 있어서, According to claim 3,
    상기 음이온성 고분자의 산가가 10 내지 350 mgKOH/g이고, 중량평균분자량이 500 내지 10,000 g/mol인 과립형 에폭시 수지 조성물.The acid value of the anionic polymer is 10 to 350 mgKOH / g, and the weight average molecular weight is 500 to 10,000 g / mol granular epoxy resin composition.
  5. 제1항 내지 제4항 중 어느 한 항에 따른 과립형 에폭시 수지 조성물을 이용하여 봉지된 반도체 소자. A semiconductor device sealed using the granular epoxy resin composition according to any one of claims 1 to 4.
PCT/KR2022/017535 2021-12-30 2022-11-09 Granular epoxy resin composition WO2023128247A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03167251A (en) * 1989-11-27 1991-07-19 Matsushita Electric Works Ltd Epoxy resin composition for semiconductor sealing
JP2006274184A (en) * 2005-03-30 2006-10-12 Sumitomo Bakelite Co Ltd Epoxy resin composition and semiconductor device
KR20130055514A (en) * 2011-11-18 2013-05-28 닛토덴코 가부시키가이샤 Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same
WO2016204183A1 (en) * 2015-06-16 2016-12-22 日立化成株式会社 Resin composition for film formation, sealing film using same, sealing film provided with support and semiconductor device
KR20200085784A (en) * 2017-11-27 2020-07-15 나믹스 가부시끼가이샤 Film-like semiconductor encapsulant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03167251A (en) * 1989-11-27 1991-07-19 Matsushita Electric Works Ltd Epoxy resin composition for semiconductor sealing
JP2006274184A (en) * 2005-03-30 2006-10-12 Sumitomo Bakelite Co Ltd Epoxy resin composition and semiconductor device
KR20130055514A (en) * 2011-11-18 2013-05-28 닛토덴코 가부시키가이샤 Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same
WO2016204183A1 (en) * 2015-06-16 2016-12-22 日立化成株式会社 Resin composition for film formation, sealing film using same, sealing film provided with support and semiconductor device
KR20200085784A (en) * 2017-11-27 2020-07-15 나믹스 가부시끼가이샤 Film-like semiconductor encapsulant

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