KR20180069632A - Epoxy resin composition for encapsulating semicomductor device and semiconductor device encapsulated using the same - Google Patents

Abstract

The present invention relates to an epoxy resin composition for encapsulating a semiconductor device which includes an epoxy resin modified with alkoxysilane having an amine group or a mercapto group, a hardener, and an inorganic filler; and to a semiconductor device encapsulated using the same. The epoxy resin composition for encapsulating a semiconductor device according to the present invention uses the epoxy resin modified with alkoxysilane having an amine group or a mercapto group, thereby realizing high elasticity modulus and high shrinkage rate.

Description

TECHNICAL FIELD [0001] The present invention relates to an epoxy resin composition for encapsulating semiconductor devices, and a semiconductor device encapsulated with the epoxy resin composition. [0002]

TECHNICAL FIELD The present invention relates to an epoxy resin composition for sealing a semiconductor device and a semiconductor device sealed with the epoxy resin composition. More particularly, the present invention relates to an epoxy resin composition for encapsulating a semiconductor device, which comprises an epoxy resin modified with an alkoxysilane having an amine group or a mercapto group and capable of realizing high shrinkage and high elasticity properties, and a semiconductor device .

BACKGROUND ART As a method of packaging a semiconductor device such as IC and LSI and obtaining a semiconductor device, transfer molding using an epoxy resin composition is widely used because it is suitable for a low cost and mass production. The epoxy resin composition for semiconductor encapsulation generally generally comprises an epoxy resin, a curing agent, an inorganic filler, and the like.

However, due to the miniaturization, light weight, and high performance of electronic products, semiconductor chips have become thinner, higher integration and / or surface mounting have increased, which can not be solved by conventional epoxy resin compositions. Particularly, there is a problem in that warpage and defects of the package are likely to occur due to thermal expansion and heat shrinkage between the substrate and the sealing layer as the semiconductor device is made thinner.

Depending on the type of the semiconductor package, the elastic modulus and the shrinkage ratio of the sealing layer may need to be increased in order to improve package bending and reliability. However, since the elastic modulus and the shrinkage ratio generally have a trade-off relationship, it is difficult to increase both the elastic modulus and the shrinkage ratio. The elastic modulus can be increased by increasing the content of the inorganic filler in the epoxy resin composition. In this case, however, there is a problem in that the flowability and moldability of the epoxy resin composition are deteriorated and the shrinkage rate decreases in proportion to the increase in the modulus of elasticity. In order to increase the shrinkage ratio, a method of increasing the content of the epoxy resin having a low glass transition temperature may be considered. In this case, there is a problem that the elastic modulus generally decreases.

Therefore, development of an epoxy resin composition capable of simultaneously realizing a high modulus of elasticity and a high shrinkage ratio has been demanded.

An object of the present invention is to provide an epoxy resin composition for sealing semiconductor devices having high elasticity and high shrinkage characteristics.

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

In one aspect, the present invention relates to an epoxy resin modified with an alkoxysilane having an amine group or a mercapto group; Curing agent; And an inorganic filler. The present invention also provides an epoxy resin composition for sealing a semiconductor device.

Specifically, the epoxy resin may include a functional group represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from the group consisting of hydrogen, hydroxyl, halogen, substituted or unsubstituted C 1 -C 30 alkyl, substituted or unsubstituted C 3 -C 30 cycloalkyl An alkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted C2 to 30 A substituted or unsubstituted aryl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, At least one of R ₁ to R ₃ is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A is a single bond, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, Represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted C2 to C20 hetero A substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms, or a combination thereof, and B is N or S. However, when B is S, R ₄ does not exist.

Specifically, each of R ₁ , R ₂ and R ₃ is independently hydrogen or a substituted or unsubstituted C 1 -C 30 alkoxy group, and A is a single bond or a substituted or unsubstituted alkyl of 1 to 30 carbon atoms It can be a ring.

Meanwhile, the alkoxy silane-modified epoxy resin having an amine group or a mercapto group may have an epoxy equivalent of 160 to 360, and the Si content of the epoxy resin may be 0.5 to 5% by weight.

The epoxy resin composition according to the present invention may comprise 0.5 to 20% by weight of an epoxy resin modified with an alkoxysilane having an amine group or a mercapto group, 0.1 to 13% by weight of a curing agent and 70 to 97% by weight of an inorganic filler.

In one embodiment, the epoxy resin may be a phenol novolak epoxy resin modified with an alkoxysilane having an amine group or a mercapto group, wherein the epoxy resin composition has a curing shrinkage ratio measured by the following formula (1) May be 0.15 to 0.35%.

(1): Cure shrinkage percentage (%) = {(L ₀ -L ₁ ) / L ₀ } × 100

(In the formula (1), L ₀ is the major axis length of from 175 ℃ of the mold cavity at which the molded test specimens molded, L ₁ is cured after the molded molded test specimens for putting four hours in an oven at 170 ~ 180 ℃ And then the length of the specimen after cooling)

Further, the epoxy resin composition comprising the phenol novolac epoxy resin modified with an alkoxysilane having an amine group or a mercapto group was molded using a transfer molding machine and then post-cured, May have a modulus of elasticity of 2,000 to 4,000 MPa.

In another embodiment, the epoxy resin may be a cresol novolak epoxy resin modified with an alkoxysilane having an amine group or a mercapto group, wherein the epoxy resin composition has a curing shrinkage ratio measured by the following formula (1) Can be 0.2 to 0.5%.

(1): Cure shrinkage percentage (%) = {(L ₀ -L ₁ ) / L ₀ } × 100

(In the formula (1), L ₀ is the major axis length of from 175 ℃ of the mold cavity at which the molded test specimens molded, L ₁ is cured after the molded molded test specimens for putting four hours in an oven at 170 ~ 180 ℃ And then the length of the specimen after cooling)

Further, the epoxy resin composition comprising the cresol novolak epoxy resin modified with an alkoxy silane having an amine group or a mercapto group was molded using a transfer molding machine and then post-cured, May have a modulus of elasticity of 1,500 to 3,000 MPa.

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

The epoxy resin composition for sealing a semiconductor device according to the present invention can realize a high elastic modulus and a high shrinkage ratio by using an epoxy resin modified with an alkoxysilane having an amine group or a mercapto group.

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

In the following description of the present invention, detailed description of known related arts will be omitted when it is determined that the gist of the present invention may be unnecessarily obscured by the present invention.

In the case where the word 'includes', 'having', 'done', etc. are used in this specification, other parts can be added unless '~ only' is used. Unless the context clearly dictates otherwise, including the plural unless the context clearly dictates otherwise.

Also, in interpreting the constituent elements, even if there is no separate description, it is interpreted as including the error range.

In the present specification, " X to Y " representing the range means " X or more and Y or less ".

As used herein, the term "substituted or unsubstituted" means that at least one hydrogen atom of the functional group is a hydroxyl group, a halogen atom, an amino group, a nitro group, a cyano group, a C 1 to C 20 alkyl group, a C 1 to C 20 haloalkyl group, C30 aryl group, C3-C30 heteroaryl group, C3-C10 cycloalkyl group, C3-C10 heterocycloalkyl group, C7-C30 arylalkyl group, C1-C30 heteroalkyl group, The term " halo " means fluorine, chlorine, iodine or bromine.

"Aryl" means a substituent group in which all the elements of a cyclic substituent have p-orbital and p-orbital forms a conjugate, and a single ring structure or a fused multiple ring of two or more rings And includes, for example, phenyl, biphenyl, naphthyl, naphthol, anthracene, and the like, but is not limited thereto.

As used herein, "heteroaryl" means that from 1 to 3 atoms selected from the group consisting of nitrogen, oxygen, sulfur and phosphorus are contained in the aryl group of C6 to C30 and the remainder is carbon. Examples thereof include pyridinyl, Pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, acridinyl, quinazolinyl, cinnolinyl, phthalazinyl, thiazolyl, benzothiazolyl, inter Benzothiophenyl, furanyl, benzofuranyl, isobenzofuranyl, benzothiazolyl, benzothiazolyl, benzothiazolyl, benzothiazolyl, benzisoxazolyl, oxazolyl, benzoxazolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, , But is not limited thereto.

In this specification, 'hetero' in the context of 'heterocycloalkyl', 'heteroaryl', 'heterocycloalkylene' and 'heteroarylene' means nitrogen, oxygen, sulfur or phosphorus atom.

The inventors of the present invention have conducted intensive studies to develop an epoxy resin for sealing a semiconductor device capable of simultaneously realizing a high shrinkage ratio and a high elastic modulus. As a result, by using an epoxy resin modified with an alkoxysilane having an amine group or a mercapto group, It is possible to achieve the same object, and the present invention has been completed.

Specifically, the epoxy resin composition of the present invention comprises (A) an epoxy resin modified with an alkoxysilane having an amine group or a mercapto group, (B) a curing agent and (C) an inorganic filler.

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

Epoxy resin

In the present invention, the epoxy resin includes an epoxy resin modified with an alkoxysilane having an amine group or a mercapto group.

Specifically, the epoxy resin may include a functional group represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 3 to 30 carbon atoms A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted C2- A substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, the carbon number of 1 to 30 and an alkoxy group or a combination of at least one of the R ₁ to R ₃ is a substituted or unsubstituted alkoxyl group having 1 to 30 carbon atoms, and a is a single bond, a substituted Represents a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted C2 to C20 hetero A substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms, or a combination thereof, and B is N or S. However, when B is S, R ₄ does not exist.

Specifically, in formula (1), R ₁ , R ₂ and R ₃ are each independently hydrogen or a substituted or unsubstituted C1 to C30 alkoxy group, and A is a single bond or a substituted or unsubstituted C1- Lt; / RTI >

On the other hand, the epoxy resin modified with an alkoxysilane having an amine group or a mercapto group has an epoxy equivalent of 160 to 360, specifically 160 to 315, or 160 to 300, more specifically 160 to 250, Lt; / RTI > Within the above range, the modulus of elasticity and the increase in the shrinkage rate can be suitably realized, and the curing degree and the moisture absorption rate can be excellent.

The Si content of the alkoxy silane-modified epoxy resin having an amine group or a mercapto group may be 0.5 to 5% by weight, specifically 0.5 to 2% by weight.

The silicon content in the epoxy resin was measured by extracting 0.5 g of the sample with 5 mL of concentrated nitric acid or hydrochloric acid at 200 ° C. for 15 minutes, injecting 1 mL of hydrogen peroxide at room temperature, and then measuring the silicon content with ICP-OES (OPTIMA 7300DV) Can be measured.

On the other hand, the epoxy resin may be any one modified with an alkoxysilane having an amine group or a mercapto group, and the kind thereof is not particularly limited. Examples of the epoxy resin include epoxy resins obtained by epoxidation of condensates of phenol or alkyl phenols with hydroxybenzaldehyde, phenol novolak type epoxy resins, cresol novolak type epoxy resins, multifunctional epoxy resins, naphthol Novolak type epoxy resins, novolak type epoxy resins such as bisphenol A / bisphenol F / bisphenol AD, glycidyl ethers of bisphenol A / bisphenol F / bisphenol AD, bishydroxybiphenyl type epoxy resins, dicyclopentadiene epoxy Resins and the like. More specifically, the epoxy resin may be a cresol novolak type epoxy resin, a multifunctional epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, or a mixture thereof. The polyfunctional epoxy resin composition may be, for example, a triphenolalkane type epoxy resin such as triphenolmethane type epoxy resin, triphenolpropane type epoxy resin and the like, but is not limited thereto.

On the other hand, the epoxy resin (A) is used in an amount of about 0.5 to 20% by weight, specifically about 3 to 15% by weight, more specifically about 3 to 12% by weight .

Hardener

As the curing agent, curing agents generally used for sealing semiconductor devices may be used without limitation, and specifically, a curing agent having two or more reactors may be used.

Specific examples of the curing agent include phenol aralkyl type phenol resin, phenol novolak type phenol resin, xylok type phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, terpene type phenol resin, Phenolic resin, dicyclopentadiene-based phenol resin, novolak-type phenol resin synthesized from bisphenol A and resole, polyhydric phenol compound including tris (hydroxyphenyl) methane, dihydroxybiphenyl, maleic anhydride and phthalic anhydride, , Aromatic amines such as methanophenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone, but are not limited thereto.

For example, the curing agent may include at least one of a phenol novolak type phenol resin, a xylock type phenol resin, a phenol aralkyl type phenol resin, and a multifunctional phenol resin.

These curing agents may be used alone or in combination. In addition, the curing agent may be used in the form of an additional compound prepared by linearly reacting the curing agent with other components such as an epoxy resin, a curing accelerator, a release agent, a coupling agent, a stress relieving agent, and the like.

The curing agent may be contained in an amount of 0.1 to 13% by weight, specifically 0.1 to 10% by weight, more specifically 0.1 to 8% by weight in the epoxy resin composition for encapsulating semiconductor devices.

The compounding ratio of the epoxy resin and the curing agent can 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 equivalent ratio between the epoxy resin and the curing agent is within the above range, excellent strength can be realized after curing the epoxy resin composition.

Inorganic filler

The inorganic filler is intended to improve the mechanical properties and low stress of the epoxy resin composition. As the inorganic filler, general inorganic fillers used for the semiconductor sealing material can be used without limitation, and are not particularly limited. Examples of the inorganic filler include fused silica, crystalline silicate, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, glass fiber and the like . These may be used alone or in combination.

Specifically, fused silica having a low linear expansion coefficient can be used for low stress. The fused silica refers to amorphous silica having a true specific gravity of 2.3 or less and includes amorphous silica obtained by melting crystalline silica or synthesized from various raw materials. Although the shape and the particle diameter of the fused silica are not particularly limited, a fused silica mixture containing 50 to 99 wt% of spherical fused silica having an average particle diameter of 5 to 30 탆 and 1 to 50 wt% of spherical fused silica having an average particle diameter of 0.001 to 1 탆 To 40% by weight to 100% by weight with respect to the total filler. Further, the maximum particle diameter can be adjusted to any one of 45 탆, 55 탆 and 75 탆 according to the application. In the spherical fused silica, conductive carbon may be included as a foreign substance on the surface of silica, but it is also important to select a substance having a small amount of polar foreign substances.

The amount of the inorganic filler to be used varies depending on required properties such as moldability, low stress, and high temperature strength. In an embodiment, the inorganic filler may be included in the epoxy resin composition in an amount of 70 wt% to 97 wt%, for example, 80 wt% to 90 wt% or 83 wt% to 97 wt%.

Other ingredients

In addition to the above components, the epoxy resin composition according to the present invention may further include at least one of a curing accelerator, a coupling agent, a release agent, and a colorant.

Hardening accelerator

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

Specific examples of the organometallic compound include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, and the like. Organic phosphorus compounds include tris-4-methoxyphosphine, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, phenylphosphine, diphenylphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine Pin-1,4-benzoquinone adducts and the like. Imidazoles include, but are not limited to, 2-phenyl-4 methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, -Methylimidazole, 2-heptadecylimidazole, and the like, but the present invention is not limited thereto. Specific examples of the boron compound include tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoro Triethylamine, tetrafluoroborane amine, 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. Diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolac resin salt. However, the present invention is not limited thereto.

More specifically, organic phosphorus compounds, boron compounds, amine-based or imidazole-based curing accelerators may be used alone or in combination as the curing accelerator. As the curing accelerator, it is also possible to use an adduct made by reacting with an epoxy resin or a curing agent.

In the present invention, the amount of the curing accelerator to be used 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 1.5% by weight, more specifically about 0.05 to 1% by weight . In the above range, the curing of the epoxy resin composition is promoted and the curing degree is also good.

Coupling agent

The coupling agent is for improving the interface strength by reacting between the epoxy resin and the inorganic filler, and may be, for example, a silane coupling agent. The silane coupling agent is not particularly limited as long as it reacts between the epoxy resin and the inorganic filler to improve the interface strength between the epoxy resin and the inorganic filler. Specific examples of the silane coupling agent include epoxy silane, amino silane, ureido silane, mercaptosilane, and alkyl silane. The coupling agent may be used alone or in combination.

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

Release agent

As the release agent, at least one 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 can be used.

The releasing agent may be contained in an amount of 0.1 to 1% by weight in the epoxy resin composition.

coloring agent

The coloring agent is for laser marking of a semiconductor element sealing material, and colorants well-known in the art can be used and are not particularly limited. For example, the colorant may comprise at least one of carbon black, titanium black, titanium nitride, dicopper hydroxide phosphate, iron oxide, mica.

The colorant may be contained in an amount of about 0.01% by weight to 5% by weight, specifically about 0.05% by weight to 3% by weight, and more specifically about 0.1% by weight to 2% by weight based on the total weight of the epoxy resin composition.

In addition, the epoxy resin composition of the present invention may contain a stress-relieving agent such as a modified silicone oil, a silicone powder, and a silicone resin to the extent that the object of the present invention is not impaired; Antioxidants such as Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane; And the like may be further contained as needed.

The epoxy resin composition of the present invention using an epoxy resin modified by an alkoxysilane having an amine group or a mercapto group as described above exhibits a higher elastic modulus and a shrinkage rate than an epoxy resin composition using the unmodified epoxy resin. For example, the epoxy resin composition according to the present invention has an elastic modulus and / or a curing shrinkage ratio which is increased by 30 to 40% or more as compared with a composition using an unmodified epoxy resin.

Specifically, when the epoxy resin is a phenol novolac epoxy resin modified with an alkoxysilane having an amine group or a mercapto group, the epoxy resin composition preferably has a viscosity of from 2,000 to 4,000 MPa, more preferably from 2,500 to 3,500 MPa And has a curing shrinkage ratio of 0.15 to 0.35%, specifically 0.2 to 0.3%.

When the epoxy resin is modified with an alkoxysilane having an amine group or a mercapto group, the epoxy resin composition preferably has an elastic modulus of 1,500 to 3,000 MPa, , And has a curing shrinkage ratio of 0.2 to 0.5%, specifically 0.25 to 0.4%.

Here, the curing shrinkage percentage means a value measured by the following formula (1).

(1): Cure shrinkage percentage (%) = {(L ₀ - L ₁ ) / L ₀ } × 100

(In the formula (1), L ₀ is the major axis length of from 175 ℃ of the mold cavity at which the molded test specimens molded, L ₁ is cured after the molded molded test specimens for putting four hours in an oven at 170 ~ 180 ℃ And then the length of the specimen after cooling)

Specifically, the moldability was measured using a transfer molding machine at a mold temperature of 170 to 180 DEG C, an injection pressure of 800 to 1200 psi, a curing time of 120 The epoxy resin composition was molded to prepare a specimen for measurement of 20 x 13 x 1.6 mm and the resulting specimen was cured in a hot-air dryer at 170-180 ° C for 2 hours, Was measured at a temperature of 260 占 폚 while raising the temperature from -10 占 폚 to 300 占 폚 at a rate of 5 占 폚 / min using DMA (Dynamic Mechanical Analyzer).

The epoxy resin composition may be prepared by uniformly mixing the above components uniformly at a predetermined mixing ratio using a Hensel mixer or a Lodige mixer and then kneading the mixture in a roll mill or a kneader kneader, and then cooled and pulverized to obtain a final powder product.

The epoxy resin composition of the present invention as described above can be applied to semiconductor devices, particularly semiconductor devices requiring high shrinkage and high elasticity properties. 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, it is also possible to perform molding by an injection molding method or a casting method.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example

Specific specifications of the components used in the following examples and comparative examples are as follows.

(A) an epoxy resin

(a1) An epoxy resin (a1) synthesized by the following method was used.

400 g of EPPN-501HY (Nippon Kayaku) was mixed with 40 g of a silicone coupling agent Y-9669 (Momentive) having an amine-reactive group, and the temperature was raised to 100 캜 and melted, followed by stirring for 30 minutes. Thereafter, it was cooled at room temperature and then pulverized to obtain an epoxy resin (a1). The epoxy equivalent of the epoxy resin synthesized as described above was 187 and the silicone content was 1%.

(a2) An epoxy resin (a2) synthesized by the following method was used.

400 g of EPPN-501HY (Nippon Kayaku) was mixed with 80 g of a silicone coupling agent Y-9669 (Momentive) having an amine-reactive group, and the temperature was raised to 100 캜, and the mixture was reacted by stirring for 30 minutes. Thereafter, it was cooled at room temperature and then pulverized to obtain an epoxy resin (a2). The epoxy equivalent of the epoxy resin synthesized as described above was 230, and the silicone content was 1.9%.

(a3) An epoxy resin (a3) synthesized by the following method was used.

400 g of EPPN-501HY (Nippon Kayaku) was mixed with 120 g of a silicone coupling agent Y-9669 (Momentive) having an amine-reactive group, and then the temperature was raised to 100 캜, and the mixture was reacted by stirring for 30 minutes. The mixture was cooled at room temperature and then pulverized to obtain an epoxy resin (a3). The epoxy equivalent of the epoxy resin synthesized as described above was 311, and the silicon content was 2.6%.

(a4) An epoxy resin (a4) synthesized by the following method was used.

400 g of EPPN-501HY (Nippon Kayaku) was mixed with 160 g of a silicone coupling agent Y-9669 (Momentive) having an amine-reactive group and then heated to 100 캜 for melting, followed by stirring for 30 minutes. The mixture was cooled at room temperature and then pulverized to obtain an epoxy resin (a4). The epoxy equivalent of the epoxy resin synthesized as described above was 357 and the silicone content was 3.2%.

(a5) An epoxy resin (a5) synthesized by the following method was used.

400 g of YDCN-500-4P (Kukdo Kagaku) were mixed with 40 g of a silicone coupling agent Y-9669 (Momentive) having an amine-reactive group, and then the temperature was raised to 100 ° C and the mixture was reacted by stirring for 30 minutes. The mixture was cooled at room temperature and then pulverized to obtain an epoxy resin (a5). The epoxy equivalent of the epoxy resin synthesized as described above was 227 and the silicone content was 0.7%.

(a6) Unmodified EPPN-501HY (Nippon Kayaku) was used. The epoxy equivalent of the epoxy resin was 153.

(a7) unmodified YDCN-500-4P (Kukdo Chemical) was used. The epoxy equivalent of the epoxy resin was 206.

(B) Curing agent

Multifunctional phenol resin MEH-7500-3S (Meiwa) was used.

(C) Curing accelerator

The curing accelerator synthesized by the following method was used.

42.6 g of salicylamide and 21.6 g of 25% sodium methoxide solution were added to 50 g of methanol and reacted at room temperature for 30 minutes to completely dissolve. Then, 50 g of 4- (hydroxyphenyl) triphenylphosphonium bromide (4-hydroxyphenyl) triphenyl phosphonium bromide) was slowly added thereto, and the mixture was further reacted for 1 hour. Water was added thereto to form a precipitate, which was then filtered to obtain a white solid compound. (Yield: 85%).

(D) Inorganic filler: A 9: 1 (weight ratio) mixture of spherical fused silica having an average particle diameter of 18 μm and spherical fused silica having an average particle diameter of 0.5 μm was used.

(E1) Coupling agent : (e1) KBM-303 (Shinetsu), which is an epoxy group-containing trimethoxysilane, and SZ-6070 (Dow Corning chemical), which is e2) methyltrimethoxysilane, were used.

(F) Additive: Carbon black MA-600 (Matsusita Chemical) was used as the (f1) carnauba wax and (f2) colorant.

Examples 1 to 5 and Comparative Examples 1 to 2

Each of the above components was weighed according to the composition shown in Table 1, and then uniformly mixed using a Henschel mixer to prepare a powdery primary composition. Thereafter, the mixture was melt-kneaded at 120 DEG C using a continuous kneader, followed by cooling and pulverization to prepare an epoxy resin composition for sealing semiconductor devices.

division
(weight%) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 (A) (a1) 8.5 - - - - - - (A) (a2) - 8.5 - - - - - (A) (a3) - - 8.5 - - - - (A) (a4) - - - 8.5 - - - (A) (a5) - - - - 8.5 - - (A) (a6) - - - - - 8.5 - (A) (a7) - - - - - - 8.5 (B) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (C) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 (D) 85 85 85 85 85 85 85 (E) (e1) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (E) (e2) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (F) (f1) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (F) (f2) 0.3 0.3 0.3 0.3 0.3 0.3 0.3

The physical properties of the epoxy resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 thus prepared were measured according to the following properties evaluation methods. The measurement results are shown in Table 2.

Property evaluation method

(1) Fluidity (inch): The 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 Shrinkage (%): Flexural Strength A molded specimen (125 × 12.6 × 6.4 mm) was obtained using an ASTM mold for specimen preparation at 175 ° C. and 70 kgf / cm ² using a transfer molding press . The obtained specimens were post-cured (PMC) in an oven at 170 to 180 ° C for 4 hours, cooled, and then the length of the specimens was measured with a caliper. The hardening shrinkage was calculated from the following equation (1).

(1): Cure shrinkage percentage (%) = {(L ₀ - L ₁ ) / L ₀ } × 100

L ₀ is the long axis length at 175 of the mold cavity in which the molding test piece is molded, L ₁ is the post-hardening time of the molding test piece in the oven of 170 to 180 for 4 hours, The length of the specimen after cooling)

(3) Modulus of elasticity (MPa): A test specimen of 20 x 13 x 1.6 mm was molded using a transfer molding machine under conditions of a mold temperature of 175 占 폚, injection pressure of 1000 占 psi, and a curing time of 120 seconds. The specimens for measurement were cured in a hot air drier at 175 ± 5 ° C for 2 hours, and then the elastomeric modulus of the specimens was measured using a Q8000 DMA (Dynamic Mechanical Analyzer) manufactured by TA Corporation. The temperature was raised at a rate of 5 ° C / min, and the temperature was increased from -10 ° C to 300 ° C and the temperature was measured at 260 ° C.

Evaluation items Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Flowability (inch) 61 60 60 55 46 62 45 Cure shrinkage (%) 0.23 0.25 0.26 0.27 0.28 0.16 0.21 Modulus of elasticity (MPa) 3153 3219 3408 3546 2175 2352 1639

As can be seen from Tables 1 and 2, Examples 1 to 5 of the present invention comprising an epoxy resin modified with an alkoxysilane having an amine group or a mercapto group, a curing agent and an inorganic filler exhibited excellent flowability, hardening shrinkage and elasticity Were all excellent at the same time.

In particular, in Examples 1 to 4, in which the same epoxy resin was modified while varying the content of the silicone coupling agent including the amine reactor, the same epoxy resin was used, but in the case of Comparative Example 1 which was not modified with the silicone coupling agent, Curing shrinkage and elastic modulus.

In Example 5, in which another kind of epoxy resin was modified with a silicone coupling agent including an amine reactor, the same epoxy resin as in Example 5 was used, but in the case of Comparative Example 2 which was not modified with a silicone coupling agent Excellent fluidity, hardening shrinkage and elastic modulus.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (9)

An epoxy resin modified with an alkoxysilane having an amine group or a mercapto group;
Curing agent; And
An epoxy resin composition for sealing semiconductor devices comprising an inorganic filler.
The method according to claim 1,
Wherein the epoxy resin comprises a functional group represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
Each of R ₁ , R ₂ , R ₃ and R ₄ is independently hydrogen, a hydroxyl group, a halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, A substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms , A substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted C1- Or a combination thereof,
At least one of R ₁ to R ₃ is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms,
Wherein A is a single bond, a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, A substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms, or a combination thereof,
And B is N or S (provided that when B is S, R < ₄ > does not exist).
3. The method of claim 2,
Each of R ₁ , R ₂ and R ₃ is independently hydrogen or a substituted or unsubstituted C 1 -C 30 alkoxy group,
Wherein A is a single bond or a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms.
The method according to claim 1,
Wherein the alkoxy silane-modified epoxy resin having an amine group or a mercapto group has an epoxy equivalent of 160 to 360.
The method according to claim 1,
Wherein the Si content in the alkoxy silane-modified epoxy resin having an amine group or a mercapto group is 0.5 to 5 wt%.
The method according to claim 1,
0.5 to 20% by weight of an epoxy resin modified with an alkoxysilane having an amine group or a mercapto group,
0.1 to 13% by weight of a curing agent and
And 70 to 97% by weight of an inorganic filler.
The method according to claim 1,
The epoxy resin is obtained by modifying a phenol novolac epoxy resin with an alkoxysilane having an amine group or a mercapto group,
Wherein the epoxy resin composition measured by the following formula (1) has a curing shrinkage of 0.15 to 0.35%
(1): Cure shrinkage percentage (%) = {(L ₀ - L ₁ ) / L ₀ } × 100
(In the formula (1), L ₀ is the major axis length of from 175 ℃ of the mold cavity at which the molded test specimens molded, L ₁ is cured after the molded molded test specimens for putting four hours in an oven at 170 ~ 180 ℃ And then the length of the specimen after cooling)
Wherein the epoxy resin composition is molded using a transfer molding machine and then post-cured to have a modulus of elasticity of 2,000 to 4,000 MPa as measured at 260 占 폚.
The method according to claim 1,
The epoxy resin is obtained by modifying a cresol novolak epoxy resin with an alkoxysilane having an amine group or a mercapto group,
Wherein the epoxy resin composition has a curing shrinkage of 0.2 to 0.5% as measured by the following formula (1)
(1): Cure shrinkage percentage (%) = {(L ₀ - L ₁ ) / L ₀ } × 100
(In the formula (1), L ₀ is the major axis length of from 175 ℃ of the mold cavity at which the molded test specimens molded, L ₁ is cured after the molded molded test specimens for putting four hours in an oven at 170 ~ 180 ℃ And then the length of the specimen after cooling)
Wherein the epoxy resin composition is molded using a transfer molding machine and then post-cured. The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the epoxy resin composition has a modulus of elasticity of 1,500 to 3,000 MPa.
A semiconductor device sealed with the epoxy resin composition for sealing a semiconductor device according to any one of claims 1 to 8.