WO2017090890A1 - Epoxy resin composition for sealing semiconductor device and semiconductor device sealed using same - Google Patents

Abstract

The present invention relates to an epoxy resin composition for sealing a semiconductor device, the composition containing an epoxy resin, a curing agent, an inorganic filler, and a flame retardant represented by chemical formula 1, and to a semiconductor device sealed by the same. In chemical formula 1, R is hydrogen or a C1-C20 hydrocarbon group.

Description

Epoxy resin composition for semiconductor device sealing and semiconductor device sealed using the same

The present invention relates to an epoxy resin composition for semiconductor device sealing and a semiconductor device sealed using the same. More specifically, it is possible to minimize the reduction in shrinkage, curing strength and continuous workability of the epoxy resin composition according to the addition of the flame-retardant material including a phosphorus-based flame retardant of a specific structure, epoxy resin for sealing a semiconductor device exhibiting excellent flame retardancy and the same It relates to a semiconductor element sealed using.

In the case of the epoxy resin composition used for sealing of semiconductor elements, etc., flame retardancy is generally required, and in the case of semiconductor companies, flame retardancy of UL94 V-0 level is required. In order to secure such flame retardancy, the halogen-type flame retardant was conventionally added and used for the epoxy resin composition. However, in the case of halogen-based flame retardants, toxic carcinogens such as dioxane and difuran are generated during incineration or fire, and acid gases such as hydrogen bromide and hydrogen chloride are generated during combustion, and are toxic to the human body. There is a problem of corrosion of parts such as lead frames.

In order to solve the above problems, studies have been attempted to develop non-halogen organic flame retardants and inorganic flame retardants. As organic flame retardants, phosphorus-based flame retardants such as phosphazene and phosphate esters or resins containing nitrogen have been studied. However, in the case of nitrogen-containing resin, the flame retardancy is not sufficient, and in the case of phosphorus-based flame retardant, even if only a small amount is used, there is a problem that the shrinkage ratio of the epoxy resin composition is increased, and the glass transition temperature after curing of the resin composition is lowered.

In recent years, as digital devices with small and thin designs are becoming more common, semiconductor packages mounted therein are also thin and short. Therefore, when the shrinkage ratio of the epoxy resin as a sealing material increases, warpage of the semiconductor package may occur. do. If warpage occurs in the semiconductor package, soldering defects occur at the time of soldering, thereby causing electrical defects. For this reason, the use of phosphorus-based flame retardants that increase the shrinkage of the epoxy resin composition is limited.

On the other hand, as inorganic flame retardant materials such as magnesium hydroxide or zinc borate have been studied, in the case of the inorganic flame retardant materials, in order to ensure sufficient flame retardancy, should be used in excess, in this case, the curability or continuous of the sealing epoxy resin composition There exists a problem that moldability etc. fall.

Therefore, it is possible to minimize the reduction in shrinkage, curing strength and continuous workability of the epoxy resin composition, and it is necessary to develop an epoxy resin composition for sealing semiconductor devices that exhibits excellent flame resistance.

Related prior art is disclosed in Korean Patent Laid-Open No. 2012-0110267.

An object of the present invention is to provide an epoxy resin composition for sealing a semiconductor device that can implement excellent flame retardancy while minimizing the physical properties such as shrinkage, curing strength and workability due to the addition of flame retardant.

Another object of the present invention is to provide a semiconductor device sealed by the epoxy resin composition as described above.

In one aspect, the present invention provides an epoxy resin composition for sealing a semiconductor device comprising an epoxy resin, a curing agent, an inorganic filler and a flame retardant represented by the following formula (1).

[Formula 1]

In Formula 1, R is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms. Preferably, R may be hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and more preferably, R is It may be a phenyl group, a biphenyl group or a naphthalene group.

In embodiments, the flame retardant may be represented by the following formula (2) or formula (3).

[Formula 2]

[Formula 3]

The flame retardant may be included in about 0.01% to about 3% by weight of the epoxy resin composition.

In addition, the epoxy resin composition is about 0.1% to about 15% by weight of the epoxy resin, about 0.1% to about 13% by weight of the curing agent, about 70% to about 95% by weight of the inorganic filler and flame retardant represented by Formula 1 0.01 wt% to about 3 wt%.

In another aspect, the present invention provides a semiconductor device sealed by the epoxy resin composition according to the present invention.

The epoxy resin composition according to the present invention exhibits excellent flame retardancy while minimizing deterioration in shrinkage, curing strength and continuous workability of the epoxy resin composition due to the addition of the flame retardant by using a phosphorus-based flame retardant.

Hereinafter, the present invention will be described in more detail.

In describing the present invention, when it is determined that the detailed description of the related known technology may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

When "include", "have", "consist", or the like mentioned in the present specification, other parts may be added unless "only" is used. In the case where the component is expressed in the singular, the plural includes the plural unless specifically stated otherwise.

In addition, in interpreting a component, even if there is no separate description, it is interpreted as including an error range.

In addition, in this specification, "X-Y" which shows a range means "X or more and Y or less."

Epoxy resin composition

First, the epoxy resin composition which concerns on this invention is demonstrated.

The epoxy resin composition for semiconductor element sealing of this invention contains an epoxy resin, a hardening | curing agent, an inorganic filler, and a flame retardant.

At this time, the flame retardant may be represented by the following formula (1).

[Formula 1]

In Formula 1, R is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms, preferably, hydrogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms or 6 to 6 carbon atoms 20 may be an aryl group. More preferably, R may be a phenyl group, a biphenyl group or a naphthalene group.

The present inventors conducted a study to develop a technology that can realize a sufficient flame retardancy without lowering the existing physical properties of the epoxy resin composition, when using the flame retardant represented by the formula (1), curing shrinkage rate, strength after curing, work It was found that excellent flame retardancy can be realized without deteriorating physical properties such as properties, and completed the present invention.

Specifically, the flame retardant represented by Chemical Formula 1 may be represented by the following Chemical Formula 2 or Chemical Formula 3.

[Formula 2]

[Formula 3]

Meanwhile, in the present invention, the flame retardant represented by Chemical Formula 1 may be included in about 0.01% to about 3% by weight, preferably about 0.05% to about 1% by weight of the epoxy resin composition. When the content of the flame retardant is within the above range, it is possible to implement excellent flame retardant properties without deteriorating the physical properties of the resin composition.

On the other hand, the epoxy resin may be used epoxy resins generally used for semiconductor device sealing, it is not particularly limited. For example, an epoxy compound containing two or more epoxy groups in a molecule may be used as the epoxy resin. Such epoxy resins include epoxy resins obtained by epoxidizing condensates of phenol or alkyl phenols with hydroxybenzaldehyde, phenol novolak type epoxy resins, cresol novolak type epoxy resins, polyfunctional type epoxy resins, naphthol novolak type epoxys, etc. Resins, novolac epoxy resins of bisphenol A / bisphenol F / bisphenol AD, glycidyl ethers of bisphenol A / bisphenol F / bisphenol AD, bishydroxybiphenyl epoxy resins, dicyclopentadiene epoxy resins, and the like. Can be. More specifically, the epoxy resin may include at least one of a cresol novolac epoxy resin, a polyfunctional epoxy resin, a phenol aralkyl type epoxy resin and a biphenyl type epoxy resin.

The multifunctional epoxy resin may be, for example, an epoxy resin represented by the following Formula (4).

[Formula 4]

In Formula [4], R1, R2, R3, R4, and R5 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R6 and R7 are each independently a hydrogen atom, a methyl group, or an ethyl group, and a is 0 to 6 Is an integer. Preferably, R1, R2, R3, R4 and R5 are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group or hexyl group R6 and R7 may be hydrogen, but are not necessarily limited thereto.

The multifunctional epoxy resin of [Formula 4] can reduce the deformation of the package, and has excellent advantages in fast curing, latentness and preservation, as well as excellent cured strength and adhesiveness.

More specifically, the multifunctional epoxy resin composition may be a triphenol alkane type epoxy resin such as a triphenol methane type epoxy resin, a triphenol propane type epoxy resin, or the like.

The phenol aralkyl type epoxy resin may be, for example, a phenol aralkyl type epoxy resin having a novolak structure including a biphenyl derivative represented by the following Formula 5.

[Formula 5]

In [Formula 5], the average value of b is 1 to 7.

The phenol aralkyl type epoxy resin of [Formula 5] forms a structure having a biphenyl in the middle based on a phenol skeleton, and thus has excellent hygroscopicity, toughness, oxidation resistance, and crack resistance. While forming a carbon layer (char) has the advantage that it can secure a certain level of flame resistance in itself.

The biphenyl type epoxy resin may be, for example, a biphenyl type epoxy resin represented by the following formula (6).

[Formula 6]

In [Formula 6], R8, R9, R10, R11, R12, R13, R14 and R15 are each independently an alkyl group having 1 to 4 carbon atoms, the average value of c is 0 to 7.

The biphenyl type epoxy resin of the above [Formula 6] is preferable from the viewpoint of fluidity and reliability strengthening of the resin composition.

These epoxy resins may be used alone or in combination, and are additive compounds made by preliminary reactions such as melt master batches with other components such as hardeners, curing accelerators, mold release agents, coupling agents, and stress relieving agents. It can also be used in the form. On the other hand, in order to improve the moisture resistance reliability, it is preferable to use the epoxy resin that is low in chlorine ions, sodium ions, and other ionic impurities contained in the epoxy resin.

The epoxy resin is about 0.1% to about 15% by weight of the epoxy resin composition for sealing semiconductor devices, specifically about 0.1% to about 12% by weight, more specifically about 3% to about 12% by weight It may be included in the content of. When the content of the epoxy resin satisfies the above range, it is possible to better implement the adhesive strength and strength of the epoxy resin composition after curing.

Next, as the curing agent, curing agents generally used for sealing semiconductor devices may be used without limitation, and preferably, curing agents having two or more reactors may be used.

Specifically, as the curing agent, a phenol aralkyl type phenol resin, a phenol phenol novolak type phenol resin, a xylok type phenol resin, a cresol novolak type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, a polyfunctional type Phenol resins, dicyclopentadiene phenol resins, polyhydric phenol compounds including novolac-type phenol resins synthesized from bisphenol A and resol, tris (hydroxyphenyl) methane, dihydroxybiphenyl, maleic anhydride and phthalic anhydride Aromatic amines such as acid anhydride, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like may be used, but are not limited thereto.

For example, the curing agent may include one or more of phenol novolak-type phenol resin, xylox phenol resin, phenol aralkyl type phenol resin, and polyfunctional phenol resin. The phenol novolak type phenol resin may be, for example, a phenol novolak type phenol resin represented by the following [Formula 7], and the phenol aralkyl type phenol resin is represented by, for example, [Formula 8] below It may be a phenol aralkyl type phenol resin having a novolak structure containing a biphenyl derivative in a molecule thereof. In addition, the xylloxyl phenolic resin may be, for example, a xyloxyl phenolic resin represented by the following [Formula 9], and the polyfunctional phenolic resin is, for example, represented by the following [Formula 10] It may be a polyfunctional phenol resin containing the repeating unit represented.

[Formula 7]

In Formula 7, d is 1 to 7.

[Formula 8]

In [Formula 8], the average value of e is 1 to 7.

[Formula 9]

In [Formula 9], the average value of f is 0 to 7.

[Formula 10]

The average value of g in [Formula 10] is 1 to 7.

These curing agents may be used alone or in combination, and may also be used as additive compounds made by preliminary reactions such as melt master batches with other components such as epoxy resins, curing accelerators, release agents, coupling agents, and stress relaxation agents.

The curing agent may be included in about 0.1% to about 13% by weight, preferably about 0.1% to about 10% by weight, more preferably about 0.1% to about 8% by weight of the epoxy resin composition. When the content of the curing agent satisfies the above range, the curing degree of the epoxy resin composition and the strength of the cured product are excellent.

On the other hand, the compounding ratio of the epoxy resin and the curing agent may be adjusted according to the requirements of mechanical properties and moisture resistance reliability in the package. For example, the chemical equivalent ratio of the epoxy resin to the curing agent may be about 0.95 to about 3, specifically about 1 to about 2, more specifically about 1 to about 1.75. When the compounding ratio of the epoxy resin and the curing agent satisfies the above range, it is possible to implement excellent strength after curing the epoxy resin composition.

Next, the inorganic fillers may be used without limitation, general inorganic fillers used in the semiconductor sealing material, it is not particularly limited. For example, as the inorganic filler, fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, glass fiber, etc. may be used. Can be. These may be used alone or in combination.

Preferably, molten silica having a low coefficient of linear expansion is used to reduce stress. Fused silica refers to amorphous silica having a specific gravity of about 2.3 or less, and also includes amorphous silica made by melting crystalline silica or synthesized from various raw materials. The shape and particle diameter of the molten silica are not particularly limited, but the spherical molten silica having a spherical molten silica having an average particle diameter of about 5 μm to about 30 μm and a spherical molten silica having an average particle diameter of about 0.001 μm to about 1 μm Preferably comprises from about 40% to about 100% by weight of the molten silica mixture comprising about 1% to about 50% by weight relative to the total filler. Moreover, according to a use, the maximum particle diameter can be adjusted to any one of about 45 micrometers, about 55 micrometers, and about 75 micrometers, and can be used. In the spherical molten silica, conductive carbon may be included as a foreign material on the silica surface, but it is also important to select a material containing less polar foreign matter.

The amount of the inorganic filler used depends on the required physical properties such as formability, low stress, and high temperature strength. In embodiments, the inorganic filler may be included in about 70% to about 95% by weight, for example about 80% to about 90% or about 83% to about 97% by weight of the epoxy resin composition. Within this range, flame retardancy, fluidity and reliability of the epoxy resin composition can be ensured.

On the other hand, the epoxy resin composition which concerns on this invention can further contain a hardening accelerator as needed.

The curing accelerator is a substance that promotes the reaction of the epoxy resin and the curing agent. As said hardening accelerator, a tertiary amine, an organometallic compound, an organophosphorus compound, an imidazole, a boron compound, etc. can be used, for example. Tertiary amines include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl ) Phenol and tri-2-ethylhexyl acid salt.

Specific examples of the organometallic compound include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, and the like. Organophosphorus compounds include tris-4-methoxyphosphine, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, phenylphosphine, diphenylphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphate And pin-1,4-benzoquinones adducts. The imidazoles include 2-phenyl-4methylimidazole, 2-methylimidazole, # 2-phenylimidazole, # 2-aminoimidazole, 2-methyl-1-vinylimidazole, and 2-ethyl-4. -Methylimidazole, 2-heptadecylimidazole, and the like, but are not limited thereto. Specific examples of the boron compound include tetraphenylphosphonium-tetraphenylborate, triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoro Roboranetriethylamine, tetrafluoroboraneamine, and the like. In addition, 1, 5- diazabicyclo [4.3.0] non-5-ene (1, 5- diazabicyclo [4.3.0] non-5-ene: DBN), 1, 8- diazabicyclo [5.4. 0] undec-7-ene (1,8-diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolak resin salts, and the like.

More specifically, an organophosphorus compound, a boron compound, an amine type, or an imidazole series hardening accelerator can be used individually or in mixture as said hardening accelerator. The curing accelerator may also use an epoxy resin or an adduct made by preliminary reaction with a curing agent.

The amount of the curing accelerator used in the present invention may be about 0.01% to about 2% by weight based on the total weight of the epoxy resin composition, specifically about 0.02% to about 1.5% by weight, more specifically about 0.05% to about It may be about 1% by weight. In the above range, there is an advantage that the curing of the epoxy resin composition is promoted and the degree of curing is also good.

In addition, the epoxy resin composition of the present invention may further include a conventional additive contained in the composition. In an embodiment, the additive may comprise one or more of a coupling agent, a release agent, a stress relaxer, a crosslinking enhancer, a leveling agent, a colorant.

The coupling agent may use one or more selected from the group consisting of epoxysilane, aminosilane, mercaptosilane, alkylsilane and alkoxysilane, but is not limited thereto. The coupling agent may be included in about 0.1% to about 1% by weight of the epoxy resin composition.

The release agent may use one or more selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt. The release agent may be included in about 0.1% to about 1% by weight of the epoxy resin composition.

The stress relieving agent may use one or more selected from the group consisting of modified silicone oils, silicone elastomers, silicone powders and silicone resins, but is not limited thereto. The stress relieving agent is preferably contained in 0 to about 6.5% by weight, for example from about 0.1% to about 1% by weight in the epoxy resin composition, may optionally be included, both may be contained. At this time, the modified silicone oil is preferably a silicone polymer having excellent heat resistance, and the total epoxy resin composition by mixing one or two or more kinds of a silicone oil having an epoxy functional group, a silicone oil having an amine functional group, and a silicone oil having a carboxyl functional group. About 0.05% to about 1.5% by weight relative to about 20% by weight. However, if the silicone oil exceeds about 1.5% by weight or more, surface contamination is likely to occur and the resin bleed may be long, and when used below about 0.05% by weight, sufficient low modulus of elasticity may not be obtained. There may be. In addition, it is particularly preferable that the silicon powder has a central particle diameter of 15 μm or less because it does not act as a cause of the deterioration of moldability, and is about 0 to about 5 wt%, for example, about 0.1 wt% to about 5 wt% based on the total resin composition. It may be contained in%.

Colorants are for laser marking of semiconductor device sealants, and colorants commonly used in the art, such as carbon black, titanium nitride, titanium black, copper phosphate hydroxide, iron oxides, mica or combinations thereof, may be used. Can be. Colorants may be included from about 0.05% to about 4.0% by weight in the epoxy resin composition. Within this range, incomplete marking of the epoxy resin composition can be prevented from occurring, soot can be prevented from occurring due to sooting during marking, and electrical insulation of the resin composition can be prevented from deteriorating.

The additive may be included in about 0.1% to about 10% by weight, for example about 0.1% to about 3% by weight of the epoxy resin composition.

As a general method for producing an epoxy resin composition using the raw materials described above, a predetermined amount is uniformly mixed sufficiently using a Henschel mixer or Lodige mixer, and then roll-mill After kneading with a kneader or a kneader, cooling and grinding are used to obtain a final powder product.

As a method of sealing a semiconductor element using the epoxy resin composition obtained in the present invention, a low pressure transfer molding method can be generally used. However, the present invention is not limited thereto, and molding may also be performed by an injection molding method or a casting method.

The epoxy resin composition is preplated with a copper lead frame (e.g., silver plated copper lead frame), a nickel alloy lead frame, and a material containing nickel and palladium in the lead frame by the above method. A semiconductor device in which a semiconductor device is sealed may be manufactured by attaching a lead frame, a PCB, or the like plated with one or more of Ag) and gold (Au).

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Example

Specific specifications of the components used in the following Examples and Comparative Examples are as follows.

(A) epoxy resin

(a1) NC-3000 by Nippon Kayaku, a biphenyl aralkyl type epoxy resin, was used.

(a2) EPPN-501HY of Nippon Kayaku, a polyfunctional epoxy resin, was used.

(B) Curing agent: MEH-7500 of Meiwa, a polyfunctional phenol resin, was used.

(C) Curing accelerator: Triphenylphosphine from Hokko, a triphenylphosphine, was used.

(D) Inorganic filler: A spherical molten silica having an average particle diameter of 18 µm and a spherical molten silica having an average particle diameter of 0.5 µm were mixed and used in a weight ratio of 9 to 1.

(E) coupling agent:

KBM-803 (Shinetsu), a mercaptopropyltrimethoxysilane (E1), and SZ-6070 (Dow Corning Chemical, Inc.), a methyltrimethoxysilane, were used in combination.

(F) Additives:

Carnauba wax was used as the release agent (f1) and carbon black MA-600 (Matsusita Chemical Co., Ltd.) was used as the colorant.

(G) flame retardant

(g1) 4-Hydroxyphenyltriphenylphosphonium 3-hydroxy 2-naphthanalide 4-hydroxyphenyl triphenylphosphonium 3-hydroxy-2-naphthanide synthesized by the following method was used.

Into a 1 L round bottom flask, 100 g of triphenylphosphine, 60 g of 4-Bromophenol, and 3.7 g of NiBr ₂ were added thereto, and 130 g of ethylene glycol was added thereto. tetraphenylphosphonium bromide).

[Formula 11]

3-hydroxy-2-naphthanalide in 50g MeOH 27 g was added, 25% sodium methoxide solution was added 21.6 g, and the mixture was completely dissolved while reacting at room temperature for 30 minutes. Then, 43.5 g of a phenol substituted phosphonium bromide salt, which was previously dissolved in 50 g of methanol, was slowly added thereto. After further reacting for 1 hour, the produced white solid compound was filtered to obtain 47 g. NMR data confirmed that the compound of the formula (2).

[Formula 2]

(g2) 4-hydroxyphenyl triphenylphosphonium 3-hydroxy N- (1-naphthyl) 2-naphtamide synthesized by the following method (4-Hydroxyphenyltriphenylphosphonium 3-hydroxy N- (1-naphthyl) 2-naphthamide ) Was used.

32.2 g of 3-hydroxy-N- (1-naphthyl) -2-naphthamide was added to 50 g of MeOH, 21.6 g of 25% sodium methoxide solution was added thereto, followed by reaction at room temperature for 30 minutes, and then completely dissolved in 50 g of methanol. 43.5 g of a phenol-substituted phosphonium bromide salt having the structure shown in Chemical Formula 11 was slowly added thereto, and further reacted for 1 hour, after which the resulting white solid compound of Chemical Formula 3 was filtered to obtain 47 g. NMR data confirmed that the compound of the formula (3).

[Formula 3]

(g3) Sigma-Aldrich's reagent grade Triphenyl phosphate was used.

(g4) Triphenylphosphine oxide of HOKKO CHEMICAL was used.

(g5) ECOMAG Z-10, Magnesium Zinc Hydroxide from TATEHO MAGU, was used.

(g6) Aluminum Hydroxide CL-310 manufactured by SUMITOMO CHEMICAL was used.

Example  1 to 3, Comparative example  1 ~ 2

The components were weighed according to the composition of Table 1 below, and then uniformly mixed using a Henschel mixer (KEUM SUNG MACHINERY CO.LTD (KSM-22)) to prepare a powder-based primary composition. Then, melt kneading at 95 ° C. using a continuous kneader, followed by cooling and pulverization to prepare an epoxy resin composition for sealing a semiconductor device.

The physical properties of the epoxy resin composition for sealing semiconductor elements prepared by Examples 1 to 3 and Comparative Examples 1 to 5, the degree of cure, cure shrinkage rate, glass transition temperature, release force, continuous workability and flame retardancy Measured through. The measurement results are shown in the following [Table 2].

Property Measurement Method

(1) Flowability (inch): Flow length was measured using a transfer molding press at 175 ° C. and 70 kgf / cm ² using an evaluation mold according to EMMI-1-66. The higher the measured value, the better the fluidity.

(2) Curing degree: shore-D: MPS (Multi Plunger System) molding machine equipped with mold for exposed thin quad flat package (eTQFP) package with 24mm width, 24mm length and 1mm thickness including copper metal elements. After curing the epoxy resin composition to be evaluated at 175 ° C. for 40 seconds, 50 seconds, 60 seconds, 70 seconds and 80 seconds, the hardness of the cured product according to the curing time with Shore-D hardness tester directly on the package on the mold. Was measured. The higher the value, the better the degree of curing.

(3) Hardening shrinkage (%): Molded specimens (125 × 12.6 ×) using a transfer molding press at 175 ° C. and 70 kgf / cm ² using ASTM molds for flexural strength specimen preparation for the prepared composition. 6.4 mm). The obtained specimen was placed in an oven at 170 ° C. to 180 ° C. for 4 hours, post-cured (PMC: post molding cure), and then cooled. The length of the specimen was measured by a caliper. The cure shrinkage was calculated from the following equation 1.

<Equation 1>

Hardening shrinkage ratio = (C-D) / C × 100

(In Formula 1, C is the length of the specimen obtained by the transfer molding press of the epoxy resin composition at 175 ℃, 70kgf / cm ² , D is the specimen obtained after curing and cooling the specimen at 170 ~ 180 ℃ 4 hours Length).

(4) Glass transition temperature (° C.): Measured using a thermomechanical analyzer (TMA). At this time, the TMA was set to the conditions to increase the temperature by 10 ℃ per minute at 25 ℃ measured to 300 ℃.

(5) Release force: The mold release force test mold was cleaned three times at 175 ° C. for 300 seconds using melamine resin, and then molded twice at 175 ° C. for 300 seconds using Tablet wax to apply Wax to the test mold. After the epoxy resin composition prepared as described above was molded at 175 ° C. for 120 seconds, a release force with a mold was measured using a release force measuring device. The release force was measured 50 times, and the force was measured using a force pull gauge.

(6) Continuous workability: A 208 LQFP (28 mm x 28 mm x 1.4 mm thickness) was continuously formed at a mold temperature of 175 DEG C, an injection pressure of 9.0 MPa and a curing time of 60 sec using a transfer molding machine. The number of shots before molding defects such as package sticking and curl sticking in the mold was indicated as release defects. The higher the value, the better the continuous workability.

(7) Flame retardant: measured in accordance with UL 94 using a 1/8 inch specimen.

As shown in Table 2, in the epoxy resin compositions of Examples 1 to 3 using the flame retardant of Chemical Formula 1, the degree of curing, curing shrinkage, glass transition temperature, release force, and continuous moldability were all excellent. On the other hand, in the case of Comparative Example 1, which does not use a flame retardant material, the flame retardancy was not secured, and in Comparative Examples 2 and 3 using the organophosphorus-based flame retardant material, it can be seen that the curing shrinkage rate and the glass transition temperature were lowered. In addition, in the case of Comparative Examples 4 and 5 using the inorganic flame retardant material, it can be seen that the continuous moldability is remarkably lowered and the release force is poor, resulting in poor workability.

Claims (7)

1. An epoxy resin composition for sealing semiconductor elements comprising an epoxy resin, a curing agent, an inorganic filler, and a flame retardant represented by the following formula (1).

   [Formula 1]

   

   In Formula 1, R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.
2. The method of claim 1,

   The R is an epoxy resin composition for sealing a semiconductor element which is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
3. The method of claim 1,

   Wherein R is a phenyl group, a biphenyl group or a naphthalene group epoxy resin composition for sealing semiconductor elements.
4. The method of claim 1,

   The flame retardant is an epoxy resin composition for sealing a semiconductor device represented by the following formula (2) or (3).

   [Formula 2]

   

   [Formula 3]

   
5. The method of claim 1,

   The flame retardant is an epoxy resin composition for sealing a semiconductor device containing about 0.01% to about 3% by weight of the epoxy resin composition.
6. The method of claim 1,

   The epoxy resin composition is about 0.1% to about 15% by weight of epoxy resin, about 0.1% to about 13% by weight of the curing agent, about 70% to about 95% by weight of the inorganic filler and about 0.01% by weight of the flame retardant represented by Formula 1 Epoxy resin composition for sealing a semiconductor device comprising from about 3% by weight.
7. The semiconductor element sealed by the epoxy resin composition of any one of Claims 1-6.