WO2017142251A1 - Epoxy resin composition for sealing semiconductor device, and semiconductor device sealed by using same - Google Patents

Abstract

The present invention relates to an epoxy resin composition for sealing a semiconductor device, the epoxy resin composition comprising: an epoxy resin; a curing agent; an inorganic filler; and an aromatic monomer containing two or more amine groups, wherein the aromatic monomer containing two or more amine groups is contained in an amount of approximately 0.1 to 1.0 wt% in the epoxy resin composition.

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, the present invention relates to an epoxy resin composition for sealing a semiconductor device having excellent adhesion to a silicon nitride film and a semiconductor device sealed using the same.

In order to protect a semiconductor device such as an integrated circuit (IC), a large scale integration (LSI), and the like from an external environment such as moisture, a technique of sealing a semiconductor device using an epoxy resin composition is widely used. The epoxy resin composition for sealing a semiconductor device generally includes an epoxy resin, a curing agent, a curing catalyst, and the like. Conventionally, techniques for improving the characteristics and reliability of semiconductor devices have been mainly developed by improving epoxy resins or phenol resins. .

Meanwhile, as electronic products become thinner, smaller, and higher in recent years, the use of highly integrated semiconductor packages by stacking a plurality of semiconductor chips is increasing. Here, the term "stack" refers to a technique of vertically stacking at least two semiconductor chips or packages. By using the stack technique, the memory capacity of the semiconductor may be increased and the efficiency of using the mounting area may be improved.

The through silicon via chip stack package includes a through silicon via formed on each chip, and the through silicon vias are electrically connected to each other. In the case of through-silicon via chip stack packages, the required mounting area is smaller and the chip operating speed can be improved compared to the case of connecting chips through wire bonding.

On the other hand, in the case of the through-silicon via chip stack package as described above, the silicon nitride film (Si3N4) and the sealing epoxy resin composition are in direct contact with each other at the interface between the chips. , The adhesive force with the silicon nitride film is low, there is a problem that the interface peeling occurs. Therefore, development of the epoxy resin composition for semiconductor element sealing excellent in the adhesive force with a silicon nitride film is calculated | required.

As a related prior art, there is Japanese Patent Laid-Open No. 2007-262238.

An object of the present invention is to provide an epoxy resin composition for semiconductor element sealing that is excellent in adhesion to a silicon nitride film.

Another object of the present invention is to provide an epoxy resin composition for sealing semiconductor elements excellent in flame retardancy.

Still another object of the present invention is to provide an epoxy resin composition for sealing semiconductor devices having excellent strength while minimizing toughness and flow balance deterioration.

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

In one aspect, the invention is an epoxy resin composition comprising an epoxy resin, a curing agent, an inorganic filler and an aromatic monomer comprising at least two amine groups, wherein the aromatic monomer comprising at least two amine groups is about 0.1 in the epoxy resin composition. To provide an epoxy resin composition for sealing a semiconductor device comprises from about 1% by weight.

In this case, the aromatic monomer including two or more amine groups may be m-phenylenediamine, 2,3-diaminonaphthalene, 3,3'-diaminobenzidine, tolidine, 3,3'-dihydroxybenzidine or these It can include a combination of.

On the other hand, the epoxy resin composition may further comprise a reactive rubber, wherein the reactive rubber is a hydroxyl group, carboxyl group, amine group, epoxy group as a reactive group Or combinations thereof. The reactive rubber is, for example, carboxyl terminated butadiene acrylonitrile, amine-terminated butadiene, amine-terminated butadiene-acrylonitrile, epoxy-terminated butadiene, epoxy-terminated butadiene -Acrylonitrile or combinations thereof.

The epoxy resin composition may be formed such that T represented by the following Formula (1) satisfies about 1.2 to about 2.0.

Equation (1): T = Ta / (Tb + Tc + Td)

In said Formula (1), Ta, Tb, Tc, and Td are the values represented by following formula (2), formula (3), formula (4), and formula (5), respectively.

Equation (2):

In the formula (2), [A _h ] is the weight percent of the h-th epoxy resin included in the composition, Eq (A _h ) is the equivalent of the h-th epoxy resin, and l is an integer of 1 to 3.

Equation (3):

In the formula (3), [Bi] is the weight% of the i-th curing agent included in the composition, Eq (Bi) is the equivalent of the i-th curing agent, m is an integer of 1 to 3.

Equation (4):

In the formula (4), [Cj] is the weight% of the aromatic monomer containing two or more j-th amine groups included in the composition, Eq (Cj) is the equivalent of the j-th aromatic monomer, n is 1 to 3 Is an integer.

Equation (5):

In the formula (5), [Dk] is the weight percent of the k-th reactive rubber included in the composition, Eq (Dk) is the equivalent of the k-th reactive rubber, and o is an integer of 1 to 3.

Specifically, the epoxy resin composition includes about 0.1% to about 15% by weight of epoxy resin, about 0.1% to about 13% by weight of curing agent, about 70% to about 95% by weight of inorganic filler, and two or more amine groups. About 0.1 to about 1.0 weight percent aromatic monomer and about 0.1 to about 1.0 weight percent reactive rubber.

In another aspect, the present invention provides a semiconductor device sealed by the epoxy resin composition as described above.

The epoxy resin composition according to the present invention has excellent adhesion with the silicon nitride film, and when applied to a stacked semiconductor device, interfacial peeling is effectively suppressed.

In addition, the epoxy resin composition according to the present invention includes a plurality of aromatic rings and exhibits excellent flame retardancy.

In addition, the epoxy resin composition according to the present invention can realize excellent strength while minimizing toughness and flow balance degradation.

1 is a view for explaining a specimen for measuring the flow balance.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated more concretely.

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.

In the case where 'comprises', 'haves', 'consists of' and the like mentioned in the present specification are used, 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 interpreting a component, it is interpreted to include an error range even if there is no separate description.

The first, second, etc. are used to describe various components, but these components are not limited by these terms. These terms are only used to distinguish one component from another. Therefore, the first component mentioned below may be a second component within the technical spirit of the present invention.

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

Hereinafter, the epoxy resin composition according to the present invention will be described in detail.

The epoxy resin composition for semiconductor element sealing of this invention contains the aromatic monomer containing 2 or more of (A) epoxy resin, (B) hardening | curing agent, (C) inorganic filler, and (D) amine group. Moreover, the epoxy resin composition for semiconductor element sealing of this invention can further contain (E) reactive rubber as needed.

(A) epoxy resin

As the epoxy resin used in the present invention, epoxy resins generally used for sealing semiconductor devices may be used, and are not particularly limited. Specifically, an epoxy compound containing two or more epoxy groups in the molecule can be used. 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 Chemical Formula 1.

[Formula 1]

In Formula 1, 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. Specifically, 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 polyfunctional epoxy resin of the above [Formula 1] 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 Chemical Formula 2.

[Formula 2]

In [Formula 2], the average value of b is 1 to 7.

The phenol aralkyl type epoxy resin of [Formula 2] forms a structure having a biphenyl in the middle based on a phenol skeleton, and thus has excellent hygroscopicity, toughness, oxidative resistance and crack resistance, and has a low crosslinking density to burn at high temperatures. 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 Formula 3 below.

[Formula 3]

In [Formula 3], 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 [Formula 3] has the effect of fluidity and reliability 유동 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, the epoxy resin may be a low chlorine ion (ion), sodium ions (sodium ion), 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.

(B) curing agent

As the curing agent, curing agents generally used for sealing semiconductor devices may be used without limitation. Specifically, as the curing agent, a phenol aralkyl type phenol resin, a phenol phenol novolak phenol resin, a xylox phenol resin, a cresol novolak phenol resin, a naphthol phenol resin, a terpene phenol resin, a polyfunctional phenol resin, Phenolic resins such as dicyclopentadiene-based phenol resins, novolak-type phenol resins synthesized from bisphenol A and resol and the like can be used.

Specifically, 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 4], and the phenol aralkyl type phenol resin is, for example, represented by the following [Formula 5] It may be a phenol aralkyl type phenol resin having a novolak structure containing a biphenyl derivative in a molecule thereof. In addition, the xylol-type phenolic resin may be, for example, a xylok-type phenolic resin represented by the following [Formula 6], and the polyfunctional phenolic resin is, for example, represented by the following [Formula 7] It may be a polyfunctional phenol resin containing the repeating unit represented.

[Formula 4]

In [Formula 4] d is 1 to 7.

[Formula 5]

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

 [Formula 6]

In [Formula 6], the average value of f is 0 to 7.

 [Formula 7]

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

The phenol novolak type phenolic resin represented by Chemical Formula 4 has a short crosslinking point spacing, and when reacted with an epoxy resin, the crosslinking density becomes high, thereby increasing the glass transition temperature of the cured product. The curvature of a package can be suppressed. The phenol aralkyl type phenol resin represented by Chemical Formula 5 forms a carbon layer (char) by reacting with an epoxy resin to achieve flame retardancy by blocking transfer of heat and oxygen around. The xylol-type phenolic resin represented by Chemical Formula 6 has an effect of enhancing the fluidity and reliability of the resin composition. The polyfunctional phenolic resin including the repeating unit represented by Chemical Formula 7 has an effect of enhancing the high temperature bending property of the epoxy resin composition. .

These curing agents may be used alone or in combination, and may also be used as an addition compound made by performing a linear reaction such as a melt master batch with other components such as an epoxy resin, a curing accelerator, a releasing agent, a coupling agent, and a stress relaxation agent.

The curing agent may be included in about 0.1 to about 13% by weight, specifically about 0.1 to about 10% by weight, more specifically 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.

The blending 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.

(C) inorganic filler

As the inorganic filler, general inorganic fillers used in semiconductor sealing materials may be used without limitation, and are 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.

For example, molten silica having a low coefficient of linear expansion may be used to reduce stress. Fused silica refers to amorphous silica having a specific gravity of 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 about 1 to about spherical molten silica having a spherical molten silica having an average particle diameter of about 5 to about 30 µm and an average particle diameter of about 0.001 to about 1 µm. Preferably, the molten silica mixture, including about 50% by weight, comprises from about 40% to about 100% by weight of 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.

(D) an aromatic monomer containing two or more amine groups

The epoxy resin composition of this invention contains the aromatic monomer containing two or more amine groups. When an aromatic monomer containing two or more amine groups is added, crosslinking is induced by the reaction between the amine and the epoxy of the epoxy resin, thereby improving adhesion to the silicon nitride film and improving strength after molding. Effect occurs. In addition, the addition of an aromatic monomer has an effect of increasing the content of the aromatic ring in the epoxy resin to improve flame retardancy.

As an aromatic monomer containing two or more said amine groups, it is m-phenylenediamine, 2, 3- diamino naphthalene, 3,3'- diaminobenzidine, tolidine, 3,3'- dihydride, for example. Hydroxybenzidine or a combination thereof, but is not limited thereto.

On the other hand, the aromatic monomer containing two or more amine groups may be included in about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0% by weight of the epoxy resin composition. In addition, the aromatic monomer including two or more amine groups may be included in the range of about one or more of the above numerical values and about one or less of the above numerical values in the epoxy resin composition. For example, the aromatic monomer including two or more amine groups may be included in about 0.1 to about 1% by weight, specifically about 0.2 to about 0.3% or about 0.5 to about 1.0% by weight of the epoxy resin composition. Can be. In the above range, there is an effect of improving adhesion and strength.

(E) reactive rubber

The epoxy resin composition of this invention can contain a reactive rubber further as needed. The reactive rubber is for adjusting the toughness and flow balance of the epoxy resin composition.

The reactive rubber may include a hydroxyl group, a carboxyl group, an amine group, an epoxy group, or a combination thereof, but is not limited thereto.

The reactive rubber may be included in about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0 weight percent of the epoxy resin composition. In addition, the aromatic monomer including two or more amine groups may be included in the range of about one or more of the above numerical values and about one or less of the above numerical values in the epoxy resin composition. For example, the reactive rubber may be included in about 0.1 to about 0.7% by weight, specifically about 0.1 to 0.5% by weight of the epoxy resin composition. Toughness and flow balance can be appropriately adjusted in the above range.

Specifically, the reactive rubber is carboxyl terminated butadiene acrylonitrile, amine-terminated butadiene, amine-terminated butadiene-acrylonitrile, epoxy-terminated butadiene, epoxy-terminated butadiene -Acrylonitrile or combinations thereof, but is not limited thereto.

On the other hand, the epoxy resin composition of the present invention is one or two or more components in each of the epoxy resin (A), the curing agent (B), the aromatic monomer (D) and / or the reactive rubber (E) containing two or more amine groups. It may include. At this time, the content of the epoxy resin (A), the curing agent (B), the aromatic monomer (D) containing two or more amine groups and the reactive rubber (E) to satisfy the specific conditions, the strength and toughness of the epoxy resin composition Toughness and flow balance can be properly adjusted. Specifically, when the epoxy resin composition is prepared such that T represented by the following formula (1) is about 1.2 to about 2.0, an epoxy resin composition excellent in all of strength, toughness and flow balance may be used. You can get it. For example, T represented by Formula (1) may be about 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0. In addition, T represented by the formula (1) may be in the range of at least one of the above numerical values and at most one of the above numerical values.

Equation (1): T = Ta / (Tb + Tc + Td)

In said Formula (1), Ta, Tb, Tc, and Td are the values represented by following formula (2), formula (3), formula (4), and formula (5), respectively.

Equation (2):

In the formula (2), [A _h ] is the weight percent of the h-th epoxy resin included in the composition, Eq (A _h ) is the equivalent of the h-th epoxy resin, and l is an integer of 1 to 3.

Equation (3):

In the formula (3), [Bi] is the weight% of the i-th curing agent included in the composition, Eq (Bi) is the equivalent of the i-th curing agent, m is an integer of 1 to 3.

Equation (4):

In the formula (4), [Cj] is the weight% of the aromatic monomer containing two or more j-th amine groups included in the composition, Eq (Cj) is the equivalent of the j-th aromatic monomer, n is 1 to 3 Is an integer.

Equation (5):

In the formula (5), [Dk] is the weight percent of the k-th reactive rubber included in the composition, Eq (Dk) is the equivalent of the k-th reactive rubber, and o is an integer of 1 to 3.

(F) other ingredients

In addition to the above components, the epoxy resin composition may further include one or more of a curing accelerator, a coupling agent, and a colorant, as necessary.

A hardening accelerator is a substance which accelerates reaction of an epoxy resin and a hardening | 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 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 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.

The coupling agent may be a silane coupling agent. The said silane coupling agent may react between an epoxy resin and an inorganic filler, and what is necessary is just to improve the interface strength of an epoxy resin and an inorganic filler, The kind is not specifically limited. Specific examples of the silane coupling agent include epoxysilane, aminosilane, ureidosilane, mercaptosilane, and the like. The coupling agents may be used alone or in combination.

The coupling agent may be included in an amount of about 0.01 to about 5 wt%, specifically about 0.05 to about 3 wt%, and more specifically about 0.1 to about 2 wt%, based on the total weight of the epoxy resin composition. In the above range, the strength of the cured epoxy resin composition is improved.

The colorant is for laser marking of the semiconductor device encapsulant, and may include, for example, carbon black, titanium nitride, titanium black, or a mixture thereof.

The colorant may be included in about 0.05 to about 4.0% by weight of 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.

In addition, the epoxy resin composition is higher fatty acid in the range that does not impair the object of the present invention; Higher fatty acid metal salts; And release agents such as ester waxes and carnauba waxes; Stress relieving agents such as modified silicone oil, silicone powder, and silicone resin; Tetrakis [methylene-3- (3,5-di-tertbutyl-4-hydroxyphenyl) propionate Tetrakis [methylene-3- (3,5-di-tertbutylbutyl-4-hydroxyphenyl) propionate] methane antioxidants such as methane); And the like may be further added as necessary.

On the other hand, the epoxy resin composition is uniformly sufficiently mixed with the above components at a predetermined mixing ratio using a Henschel mixer or Lodige mixer, and then roll-mill or kneader ( kneader), and then cooled and milled to obtain a final powder product.

The epoxy resin composition of the present invention as described above is excellent in adhesive force with the silicon nitride film can be applied to a stacked semiconductor device can implement excellent durability. Specifically, the epoxy resin composition of the present invention may have an adhesive strength of about 40 kgf to about 60 kgf, specifically about 44 kgf to about 50 kgf.

Further, the epoxy resin composition of the present invention has a toughness at room temperature (about 25 ° C.) of 50 kgf · mm or more, specifically, about 50 kgf · mm to about 65 kgf · mm, and a toughness at about 260 ° C. of about 26 kgf · mm or more, more specifically, about 30 kgf · mm to about 45 kgf · mm.

In addition, the epoxy resin composition of the present invention is high in the content of the aromatic group in the composition due to the addition of the aromatic amine is excellent in flame retardancy.

The epoxy resin composition of the present invention as described above can be usefully applied to semiconductor devices, in particular, stacked semiconductor devices. 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, molding can also be performed by injection molding or casting.

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

Hereinafter, the present invention will be described in detail through specific examples.

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

(A) epoxy resin:

(A1) HP-4770 (equivalent amount = 204) of DIC Corporation was used.

(A2) YX-8800 (equivalent weight: 181) of Japan epoxy resin was used.

(B) curing agent:

(B1) MEH-7500-3S (equivalent value = 103) manufactured by Meiwa Corporation was used.

(B2) MEH-7851S (equivalent = 203) from Meiwa Corporation was used.

(C) inorganic filler:

Fused Silica (Admatech) having an average particle diameter of 20 µm and Synthetic Silica (Admatech) having an average particle diameter of 0.5 µm were mixed and used in a 9: 1 weight ratio.

(D) Aromatic monomer: m-phenylenediamine (Sigma Aldrich) (equivalent weight = 54) was used.

(E) Reactive rubber: A carboxyl terminated butadiene-acrylonitrile (Sigma aldrich) (equivalent weight = 105) was used.

(F) Curing accelerator: TPP (triphenylphosphine, Hokko Chemical) was used.

(G) Coupling agent: Y-9669 from GE Silicones was used.

(H) Colorant: MA-100R manufactured by Mitsubishi Corporation was used.

Example  And Comparative example

The components were weighed according to the composition (unit: parts by weight) of Table 1 below, and then uniformly mixed using a Henschel mixer to prepare a primary composition in powder form. After the melt kneading at 95 ℃ using a continuous kneader after cooling and pulverizing to prepare an epoxy resin composition for sealing a semiconductor device.

division		Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4
(A)	(A1)	2.7	2.67	2.64	2.79	3.3	2.4	2.8
	(A2)	6.3	6.23	6.16	6.51	7.7	5.6	6.4
(B)	(B1)	2.85	1.22	1.19	1.26	-	0.9	1.34
	(B2)	1.25	2.78	2.71	2.94	-	2.1	2.94
(C)		85	85	85	85	85	85	85
(D)		0.2	0.3	0.5	-	2.2	1.3	0.01
(E)		0.2	0.3	0.3	-	0.3	1.2	0.01
(F)		0.5	0.5	0.5	0.5	0.5	0.5	0.5
(G)		0.7	0.7	0.7	0.7	0.7	0.7	0.7
(H)		0.3	0.3	0.3	0.3	0.3	0.3	0.3

According to the following physical property measurement method, the adhesion, strength, toughness, flow balance and flame retardance with the silicon nitride film were measured. The measurement results are shown in the following [Table 2].

Property measurement method

(1) Adhesion force with the silicon nitride film (kgf): The silicon wafer on which silicon nitride was deposited was cut to a predetermined size (30 mm x 30 mm) and fixed inside the mold, and then the epoxy resin composition of Table 1 was prepared on the prepared metal test piece. ~ 180 ℃, conveying pressure 1000psi, conveying speed 0.5 ~ 1cm / sec, curing time of 120 seconds to obtain a hardened specimen, and then put the specimen in an oven of 170 ~ 180 ℃ 4 hours post-cure (PMC; post mold Immediately after cure, and left for 120 hours at 60 ° C. and 60% relative humidity conditions, and then under precondition conditions, three times of one pass of IR reflow for 30 seconds at 260 ° C., respectively. Measured. At this time, the area of the epoxy resin composition in contact with the metal specimen was 40 ± 1mm ² , the adhesion was measured by measuring the average value after measuring by using a universal testing machine (UTM) for 12 specimens for each measurement process.

(2) Strength (kgf · m / m ² ): After making standard specimen (125 × 12.6 × 6.4 mm) according to ASTM D-790 and curing it at 175 ℃ for 4 hours, using UTM (Universal Testing Machine) It measured at 35 degreeC and 260 degreeC.

(3) Toughness (kgf · mm): After making the standard specimen (125 × 12.6 × 6.4 mm) according to ASTM D-790 and curing it at 175 ℃ for 4 hours, use the universal testing machine (UTM) at 35 ℃, It measured at 260 degreeC.

(4) Flow balance: The package as shown in Figure 1 by molding 50 ~ 70% Tablet of the reference weight by transfer molding at 175 ℃ for 80 seconds using the MPS (Multi Plunger System) molding machine with the epoxy resin composition of Table 1 Was produced. Then, the ratio of the length of a, b observed with the package surface visually was measured.

(5) Flame retardancy: measured on a 1/8 inch thick specimen in accordance with the UL94 vertical combustion test method.

division	Adhesive force (kgf)	Strength (kgfm / m 2 )	Toughness (kgfmm)		flow balance	Flame retardant
			Room temperature	260 ℃
Example 1	44	15.5	51	36	0.78	V-0
Example 2	45	15.8	51	38	0.82	V-0
Example 3	49	16.2	51	42	0.91	V-0
Comparative Example 1	38	15.1	45	21	0.80	V-1
Comparative Example 2	33	15.2	45	19	0.65	V-0
Comparative Example 3	36	14.9	45	21	0.73	V-1
Comparative Example 4	37	15.4	45	24	0.96	V-0

As shown in Table 2, in Examples 1 to 4 containing 0.1 to 1.0% by weight of an aromatic monomer containing two or more amine groups, all of adhesion, strength, toughness, flow balance and flame retardancy were excellent. It can be seen that. On the other hand, when the aromatic monomer containing two or more amine groups is not included (Comparative Example 1), or the content of the aromatic monomer containing two or more amine groups is outside the scope of the present invention (Comparative Examples 2 to 4), It can be seen that the physical properties of at least one of the strength, toughness and flame retardancy are reduced.

Claims (8)

1. It is an epoxy resin composition containing an epoxy resin, a hardening | curing agent, an inorganic filler, and the aromatic monomer containing two or more amine groups,

   The aromatic monomer containing two or more amine groups is contained in the epoxy resin composition in about 0.1 to about 1.0% by weight epoxy resin composition for sealing semiconductor elements.
2. The method of claim 1,

   The aromatic monomer including two or more amine groups may be m-phenylenediamine, 2,3-diaminonaphthalene, 3,3'-diaminobenzidine, tolidine, 3,3'-dihydroxybenzidine or a combination thereof. Epoxy resin composition for sealing a semiconductor device comprising a.
3. The method of claim 1,

   The epoxy resin composition further comprises a reactive rubber.
4. The method of claim 3,

   The reactive rubber is an epoxy resin composition comprising a hydroxyl group, a carboxyl group, an amine group, an epoxy group or a combination thereof.
5. The method of claim 3,

   The reactive rubber is carboxyl terminated butadiene acrylonitrile, amine-terminated butadiene, amine-terminated butadiene-acrylonitrile, epoxy-terminated butadiene, epoxy-terminated butadiene-acrylonitrile or Epoxy resin composition containing these combinations.
6. The method of claim 3,

   The epoxy resin composition has an epoxy resin composition having T of about 1.2 to about 2.0 represented by the following formula (1).

   Equation (1): T = Ta / (Tb + Tc + Td)

   In the formula (1), Ta, Tb, Tc and Td are values represented by the following formula (2), formula (3), formula (4) and formula (5), respectively.

   Equation (2):

   

   In the formula (2), [A _h ] is the weight percent of the h-th epoxy resin included in the composition, Eq (A _h ) is the equivalent of the h-th epoxy resin, l is an integer of 1 to 3.

   Equation (3):

   

   In the formula (3), [Bi] is the weight percent of the i-th curing agent included in the composition, Eq (Bi) is the equivalent of the i-th curing agent, m is an integer of 1 to 3.

   Equation (4):

   

   In the formula (4), [Cj] is the weight% of the aromatic monomer containing two or more j-th amine groups included in the composition, Eq (Cj) is the equivalent of the j-th aromatic monomer, n is 1 to 3 Integer of.

   Equation (5):

   

   In the formula (5), [Dk] is the weight percent of the k-th reactive rubber included in the composition, Eq (Dk) is the equivalent of the k-th reactive rubber, o is an integer of 1 to 3.
7. The method of claim 3,

   The epoxy resin composition is about 0.1% to about 15% by weight epoxy resin, about 0.1% to about 13% by weight curing agent, about 70% to about 95% by weight inorganic filler, aromatic monomer containing two or more amine groups 0.1 to about 1.0 weight percent and about 0.1 to about 1.0 weight percent reactive rubber.
8. The semiconductor element sealed by the epoxy resin composition of any one of Claims 1-7.

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