KR101980949B1 - Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same - Google Patents

Abstract

상기 화학식 1에서, A는 방향족 고리기; X는 O 또는 N원자; R은 수소, 탄소수 1 내지 10의 알킬기, 탄소수 6 내지 30의 아릴기, 알릴기, 에폭시기, 글리시딜기 또는 아크릴기; m1 및 m2는 각각 독립적으로 1 내지 5인 정수; n은 0 내지 20인 정수이다.The present invention relates to an epoxy resin composition for encapsulating a semiconductor device comprising an epoxy resin, a curing agent and an inorganic filler containing a compound represented by the following general formula (1), and a semiconductor device sealed using the epoxy resin composition.
[Chemical Formula 1]

In Formula 1, A represents an aromatic ring group; X is O or N atom; R is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an allyl group, an epoxy group, a glycidyl group or an acrylic group; m1 and m2 are each independently an integer of 1 to 5; n is an integer of 0 to 20;

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] EPOXY RESIN COMPOSITION FOR ENCAPSULATING SEMICONDUCTOR DEVICE AND SEMICONDUCTOR DEVICE ENCAPSULATED USING THE SAME [

TECHNICAL FIELD The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device sealed with the composition. More particularly, the present invention relates to an epoxy resin composition for semiconductor encapsulation having a low elasticity and a low shrinkage physical property while minimizing the deterioration of the physical properties of the epoxy resin composition, and a semiconductor device sealed using the epoxy resin composition.

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 of its low cost and suitable for mass production.

Conventionally, due to the characteristics of the semiconductor packaging process, aliphatic or aromatic epoxy resins having a softening point of 50 to 150 占 폚 have been mainly used. 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, as the semiconductor device is made thinner, the package tends to be warped due to thermal expansion or heat shrinkage between the substrate and the sealing layer, and the sealing layer has high elasticity properties, causing problems such as damage or breakage of the chip by the sealing layer .

In order to solve the above problems, a method of suppressing the curing shrinkage of the resin composition by increasing the glass transition temperature of the epoxy resin composition using an epoxy resin and / or a phenol resin having a high glass transition temperature, To decrease the linear expansion coefficient of the epoxy resin composition.

However, when an epoxy resin composition having a high glass transition temperature is used, there is a problem that the modulus of elasticity is greatly increased and is vulnerable to external stress due to heat or external impact. When the content of the inorganic filler is increased, A problem arises.

Therefore, development of an epoxy resin composition for sealing a semiconductor device which can realize a low shrinkage rate and a low elastic modulus while minimizing deterioration of physical properties such as fluidity and moldability is required.

An object of the present invention is to provide an epoxy resin composition having low shrinkage and low elasticity properties while minimizing deterioration of physical properties of the epoxy resin composition.

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

The above and other objects of the present invention can be achieved by the present invention described below.

In one aspect, the present invention provides an epoxy resin composition for encapsulating semiconductor devices, which comprises an epoxy resin comprising a compound represented by the following formula (1), a curing agent, and an inorganic filler.

[Chemical Formula 1]

In Formula 1, A represents an aromatic ring group; X is O or N atom; R is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an allyl group, an epoxy group, a glycidyl group or an acrylic group; m1 and m2 are each independently an integer of 1 to 5; n is an integer of 0 to 20;

In an embodiment, A may be a phenylene group or a naphthylene group, X is an O atom, and R may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an epoxy group or a glycidyl group, And n may be an integer of 0 to 10.

In an embodiment, the compound represented by the formula (1) may be selected from compounds represented by the following formulas (1a) to (1d).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In the above formulas (1a) to (1d), X represents O or N atom; R is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an allyl group, an epoxy group, a glycidyl group or an acrylic group.

In an embodiment, the epoxy resin containing the compound of Formula 1 may have a softening point of 150 ° C or less.

In an embodiment, the epoxy resin composition for semiconductor device encapsulation may comprise 0.5 to 20% by weight of an epoxy resin containing the compound represented by the formula (1), 0.1 to 13% by weight of a curing agent, and 70 to 95% by weight of an inorganic filler have.

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 according to the present invention has a high glass transition temperature, low elasticity, and low shrinkage characteristics upon curing by using an epoxy compound having a specific structure having an aromatic polycyclic skeleton bonded with two naphthalenes.

In addition, the epoxy compound used in the epoxy resin composition of the present invention has a softening point of as low as 150 캜 or less, which is excellent in fluidity and moldability.

Use of the epoxy resin composition of the present invention having the above characteristics can effectively suppress the occurrence of package warpage and can be particularly useful for a semiconductor package having a one-side sealing structure.

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 " aryl group " 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 multi- And may include, for example, a phenyl group, a biphenyl group, a naphthyl group, a naphthol group, an anthracenyl group, and the like, but is not limited thereto.

First, the epoxy resin composition for semiconductor encapsulation according to the present invention will be described.

The epoxy resin composition of the present invention comprises (A) an epoxy resin, (B) a curing agent and (C) an inorganic filler.

(A) an epoxy resin

The epoxy resin includes the epoxy compound of the present invention represented by the above formula (1).

[Chemical Formula 1]

In Formula 1, A represents an aromatic ring group; X is an O (oxygen) or N (nitrogen) atom; R is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an allyl group, an epoxy group, a glycidyl group or an acrylic group; m1 and m2 are each independently an integer of 1 to 5; n is an integer of 0 to 20; Preferably, A may be a phenylene group or a naphthylene group, X is an O atom, and R may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an epoxy group or a glycidyl group, And n may be an integer of 0 to 10.

Specifically, the compound represented by Formula 1 may be selected from compounds represented by Chemical Formulas 1a to 1d.

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In the above formulas (1a) to (1d), X represents O or N atom; R is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an allyl group, an epoxy group, a glycidyl group or an acrylic group.

The epoxy compound represented by Formula 1 is prepared by reacting dihydroxynaphthalene with benzylaldehyde to form a phenol compound having two naphthalene rings bonded thereto and then reacting with epichlorohydrin to introduce an epoxy group .

The epoxy resin containing the epoxy compound represented by the formula (1) has aromatic polycyclic rings in the skeleton and has a high aromaticity, so that the shrinkage and elastic modulus after curing are lower than those of the conventional epoxy compounds. In addition, since the epoxy resin containing the compound represented by Formula 1 has a softening point of 150 ° C or lower, preferably 100 ° C to 150 ° C, and more preferably 100 ° C to 130 ° C or so, Is excellent.

On the other hand, the epoxy resin may be used in combination with an epoxy compound other than the epoxy compound represented by the formula (1), if necessary, in order to control physical properties.

As the other epoxy compounds, epoxy compounds generally used in the art can be used and are not particularly limited. Examples of the other epoxy compounds 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, Novolak 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 epoxy resins, dicyclopentadiene series Epoxy resins, and specific examples thereof include cresol novolak type epoxy resins, multifunctional epoxy resins, phenol aralkyl type epoxy resins, biphenyl type epoxy resins, and mixtures thereof.

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 .

(B) Curing agent

As the curing agent, curing agents generally used for sealing semiconductor devices may be used without limitation, and preferably, 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.

The phenol novolak type phenolic resin may be, for example, a phenol novolak type phenolic resin represented by the following formula (2).

(2)

The average value of d in the formula (2) is 1 to 7.

The phenol novolak type phenol resin represented by the above formula (2) has a short crosslinking point interval, and when it reacts with the epoxy resin, the crosslinking density becomes high and the glass transition temperature of the cured product can be increased, The warping of the package can be suppressed more effectively.

The phenol aralkyl type phenol resin may be, for example, a phenol aralkyl type phenolic resin having a novolak structure including a biphenyl derivative in a molecule represented by the following formula (3).

(3)

In Formula 3, the average value of e is 1 to 7.

The phenolic aralkyl type phenol resin represented by the above-mentioned formula (3) reacts with an epoxy resin to form a carbon layer (char) to block the transfer of heat and oxygen around, thereby achieving flame retardancy.

The xylo-type phenol resin may be, for example, a xylok-type phenol resin represented by the following general formula (4).

[Chemical Formula 4]

In the formula (4), the average value of f is 0 to 7.

The xylyl phenol resin represented by the above formula (4) is preferable in terms of enhancing the fluidity and reliability of the resin composition.

The multifunctional phenol resin may be, for example, a multifunctional phenol resin containing a repeating unit represented by the following formula (5).

[Chemical Formula 5]

The average value of g in the formula (5) is 1 to 7.

The multifunctional phenol resin containing the repeating unit represented by the formula (5) is preferable in terms of reinforcing the high temperature bending property of the epoxy resin composition.

These curing agents may be used alone or in combination. Further, it is also possible to use an additional compound prepared by subjecting the above-mentioned curing agent to a linear reaction with other components such as an epoxy resin, a curing accelerator, a releasing agent, a coupling agent, and a stress relieving agent in the same manner as the melt master batch.

The curing agent may be contained in an amount of 0.1 to 13% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 8% by weight in the epoxy resin composition for sealing a semiconductor device.

The mixing ratio of the epoxy resin and the curing agent can be adjusted in accordance with 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 is in the above range, excellent strength can be realized after curing the epoxy resin composition.

(C) 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 silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, . These may be used alone or in combination.

Preferably, fused silica having a low linear expansion coefficient is 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, the fused silica containing 50 to 99% by weight of spherical fused silica having an average particle diameter of 5 to 30 탆 and the spherical fused silica having an average particle diameter of 0.001 to 1 탆 in an amount of 1 to 50% It is preferable that the mixture is contained in an amount of 40 to 100% by weight based on 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%.

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

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. Specific examples of the tertiary amine 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. 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. The curing accelerator may be an adduct formed 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.

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, aminosilane, ureido silane, mercaptosilane, and the like. 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%, preferably about 0.05 wt% to 3 wt%, and more preferably about 0.1 wt% to 2 wt%, based on the total weight of the epoxy resin composition . The strength of the epoxy resin composition cured product is improved in the above range.

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.

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, preferably about 0.05% by weight to 3% by weight, and more preferably 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.

Since the epoxy resin composition for semiconductor encapsulation according to the present invention has a low shrinkage ratio and modulus of elasticity after curing, package bending due to shrinkage and expansion due to heat after semiconductor sealing and chip breakage due to external impact can be minimized.

More specifically, the epoxy resin composition for semiconductor encapsulation according to the present invention has a low shrinkage characteristic as measured by the following formula (1) to have a curing shrinkage of 0.30% or less, preferably 0.25% or less, more preferably 0.20% or less .

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

In the formula (1), L ₀ is the length of the molded specimen obtained by molding the epoxy resin composition at 175 ° C and 70 kgf / cm ² using a transfer molding press, and L ₁ is the length of the molded specimen at 175 ° C This is the length of the specimen measured after post molding curing in the oven for 4 hours and cooling.

In addition, the epoxy resin composition for semiconductor encapsulation according to the present invention is molded using a transfer molding machine, and after post curing, the elastic modulus measured on the specimen is 900 MPa or less, preferably 600 MPa or less, .

The transfer molding was performed under conditions of a mold temperature of 170 to 180 ° C, an injection pressure of 800 to 1200 psi, and a curing time of 120 seconds. The size of the molded specimen was 20 × 13 × 1.6 mm. The post curing was performed in a hot air drier at 170 to 180 ° C for 2 hours. The modulus of elasticity was measured using a Dynamic Mechanical Analyzer (TA, Q8000 DMA) at a temperature raising rate of 5 ° C / Lt; 0 > C to 300 < 0 > C.

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 usefully applied to semiconductor devices, particularly thin film type semiconductor devices requiring low shrinkage and low elasticity characteristics. 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.

Example

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.

The specifications of each component used in the following examples and comparative examples are as follows.

(A) an epoxy resin

(a1) An epoxy resin (a1) prepared according to the following synthesis method was used.

320 g (2.0 mol) of 2,7-dihydroxynaphthalene and 135 g (1.0 mol) of m-anisaldehyde were dissolved in 800 g of methyl isobutyl ketone and dissolved therein. Then, 50 g of sulfuric acid was added. Thereafter, the mixture was heated to 100 DEG C while paying attention to heat generation, and water produced using a fractionation tube was taken out and reacted for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and washed with water until the washing water exhibited neutrality. The solvent was removed from the organic layer under reduced pressure to obtain 364 g of the reaction product (1)

160 g of the reaction product (1), 300 g of epichlorohydrin and 1.5 g of tetraethylbenzylammonium chloride were placed in a flask, and the temperature of the flask was raised to 65 DEG C. After confirming that the reaction product (1) was dissolved, 50 g of a 49% aqueous sodium hydroxide solution Lt; / RTI > Thereafter, stirring was continued for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain an epoxy compound (A-1) represented by the following formula.

(A-1)

 245 g of methyl isobutyl ketone and 55 g of n-butanol were added to and dissolved in the obtained epoxy compound (A-1), and 50 g of a 10% sodium hydroxide aqueous solution was added to this solution. After reacting at 80 DEG C for 2 hours, And the washing with water was repeated three times with 150 g of water. Then, the solvent was evaporated off under reduced pressure to obtain 154 g of an epoxy resin (a1). The softening point of the epoxy resin (a1) was measured and found to be about 120 ° C.

(a2) An epoxy resin (a2) prepared according to the following synthesis method was used.

 320 g (2.0 mol) of 2,7-dihydroxynaphthalene and 122 g (1.0 mol) of 4-hydroxybenzaldehyde were dissolved in 800 g of methyl isobutyl ketone and dissolved therein. Then, 50 g of sulfuric acid was added. Thereafter, the mixture was heated to 100 DEG C while paying attention to heat generation, and water produced by using a fractionation tube was extracted and allowed to react for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and washed with water until the washing water showed neutrality. From the organic layer, the solvent was removed under reduced pressure to obtain 370 g of the reaction product (2).

160 g of the reaction product (2), 420 g of epichlorohydrin and 1.5 g of tetraethylbenzylammonium chloride were placed in a flask, and the temperature of the flask was raised to 65 ° C. After confirming that the reaction product (2) was dissolved, 75 g of a 49% aqueous sodium hydroxide solution Lt; / RTI > Thereafter, stirring was continued for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain a compound (A-2) represented by the following formula.

(A-2)

 To the resulting epoxy compound (A-2), 245 g of methyl isobutyl ketone and 55 g of n-butanol were added and dissolved. To this solution, 50 g of a 10% sodium hydroxide aqueous solution was added and reacted at 80 DEG C for 2 hours. Then, the solvent was evaporated under reduced pressure to obtain 171 g of an epoxy resin (a2). The softening point of the epoxy resin (a2) was measured and found to be about 130 캜.

(a3) An epoxy resin (a3) prepared according to the following synthesis method was used.

 320 g (2.0 mol) of 2,7-dihydroxynaphthalene and 167 g (1.0 mol) of 3,4-dimethoxybenzaldehyde were dissolved in 800 g of methyl isobutyl ketone and dissolved. After dissolving, 50 g of sulfuric acid Was added. Thereafter, the mixture was heated to 100 DEG C while paying attention to heat generation, and water produced by the fractionation tube was taken out and reacted for 8 hours. After the completion of the reaction, when the reaction mixture was cooled to room temperature, the reaction mixture was washed with water until the wash water showed neutrality, and then the solvent was removed from the organic layer under reduced pressure to obtain 404 g of reaction product (3).

160 g of the reaction product (3), 420 g of epichlorohydrin, and 1.5 g of tetraethylbenzylammonium chloride were placed in a flask, and the temperature of the flask was raised to 65 DEG C. After confirming that the reaction product (2) was dissolved, 75 g of a 49% aqueous sodium hydroxide solution Lt; / RTI > Thereafter, stirring was continued for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain a compound (A-3) represented by the following formula.

(A-3)

To the resulting epoxy compound (A-3), 245 g of methyl isobutyl ketone and 55 g of n-butanol were added and dissolved. To this solution, 50 g of a 10% sodium hydroxide aqueous solution was added and the mixture was reacted at 80 DEG C for 2 hours. The water was evaporated off under reduced pressure to obtain 171 g of an epoxy resin (a3). The softening point of the epoxy resin (a3) was measured to be about 130 캜.

(a4) An epoxy resin (a4) prepared according to the following synthesis method was used.

 320 g (2.0 mol) of 2,7-dihydroxynaphthalene and 198 g (1.0 mol) of 4-phenoxybenzaldehyde were dissolved in 800 g of methyl isobutyl ketone and dissolved therein. Then, 50 g of sulfuric acid was added. Thereafter, the mixture was heated to 100 DEG C while paying attention to heat generation, and water produced using a fractionation tube was taken out and reacted for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, washed with water until the washing water exhibited neutrality, and then the solvent was removed from the organic layer under reduced pressure to obtain 412 g of the reaction product (4).

160 g of the reaction product (4), 420 g of epichlorohydrin and 1.5 g of tetraethylbenzylammonium chloride were placed in a flask and the temperature was raised to 65 캜. After confirming that the reaction product (4) was dissolved, 75 g of a 49% Lt; / RTI > Thereafter, stirring was continued for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain a compound (A-4) represented by the following formula.

(A-4)

245 g of methyl isobutyl ketone and 55 g of n-butanol were added to the obtained epoxy compound (A-4) and dissolved. To this solution, 50 g of a 10% sodium hydroxide aqueous solution was added and reacted at 80 DEG C for 2 hours. The water was evaporated off under reduced pressure to obtain 161 g of an epoxy resin (a4). The softening point of the epoxy resin (a4) was measured and found to be about 110 캜.

(a5) HP-4770 (DIC corporation) was used.

(a6) An epoxy resin (a6) prepared according to the following synthesis method was used.

320 g (2.0 mol) of 2,7-dihydroxynaphthalene and 120 g (1.0 mol) of 4-methylbenzaldehyde were dissolved in 800 g of methyl isobutyl ketone and dissolved therein. Then, 50 g of sulfuric acid was added. Thereafter, the mixture was heated to 100 DEG C while paying attention to heat generation, and water produced using a fractionation tube was taken out and reacted for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, washed with water until the washing water exhibited neutrality, and then the solvent was removed from the organic layer under reduced pressure to obtain 374 g of reaction product (6).

160 g of the reaction product (6), 420 g of epichlorohydrin and 1.5 g of tetraethylbenzylammonium chloride were placed in a flask, and the temperature of the flask was raised to 65 ° C. After confirming that the reaction product (4) was dissolved, 75 g of a 49% aqueous solution of sodium hydroxide Lt; / RTI > Thereafter, stirring was continued for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain a compound (A-6). To the resulting epoxy compound (A-6), 245 g of methyl isobutyl ketone and 55 g of n-butanol were added and dissolved. To this solution, 50 g of a 10% sodium hydroxide aqueous solution was added and the mixture was reacted at 80 DEG C for 2 hours. Lt; / RTI > and washed three times with 150 g of water until < RTI ID = 0.0 > Then, the solvent was evaporated off under reduced pressure to obtain 147 g of an epoxy resin (a6). The softening point of the epoxy resin (a6) was measured to be about 160 캜.

(a6)

(a7) An epoxy resin (a7) prepared according to the following synthesis method was used.

320 g (2.0 mol) of 2,7-dihydroxynaphthalene and 180 g (1.0 mol) of 4-phenylbenzaldehyde were dissolved in 800 g of methyl isobutyl ketone and dissolved therein. Then, 50 g of sulfuric acid was added. Thereafter, the mixture was heated to 100 DEG C while paying attention to heat generation, and water produced using a fractionation tube was taken out and reacted for 8 hours. After the completion of the reaction, when the reaction mixture was cooled to room temperature, the reaction mixture was washed with water until the washing water exhibited neutrality, and then the solvent was removed from the organic layer under reduced pressure to obtain 410 g of reaction product (7).

160 g of the reaction product (7), 420 g of epichlorohydrin, and 1.5 g of tetraethylbenzylammonium chloride were placed in a flask, and the temperature of the flask was raised to 65 DEG C. After confirming that the reaction product (7) was dissolved, 75 g of a 49% aqueous solution of sodium hydroxide Lt; / RTI > Thereafter, stirring was continued for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain a compound (A-7). To the resulting epoxy compound (A-7), 245 g of methyl isobutyl ketone and 55 g of n-butanol were added and dissolved. To this solution was added 50 g of a 10% sodium hydroxide aqueous solution and the mixture was reacted at 80 DEG C for 2 hours. Lt; / RTI > and washed three times with 150 g of water until < RTI ID = 0.0 > Then, the solvent was evaporated under reduced pressure to obtain 151 g of an epoxy resin (a7). The softening point of the epoxy resin (a7) was measured and found to be about 180 ° C.

(a7)

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

(C) Curing accelerator: triphenylphosphine was used.

(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.

(E) Coupling agent: (e1) A mixture of KBP-803 (Shinetsu), which is a mercaptopropyltrimethoxysilane, and SZ-6070 (Dow Corning chemical), which is an e2) methyltrimethoxysilane, was used.

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

Examples 1 to 4 and Comparative Examples 1 to 3

Each of the above components was weighed according to the composition shown in the following 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 Example Comparative Example One 2 3 4 One 2 3 (A) (a1) 8.5 - - - - - - (a2) - 8.5 - - - - - (a3) - - 8.5 - - - - (a4) - - - 8.5 - - - (a5) - - - - 8.5 - - (a6) - - - - - 8.5 - (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) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 (e2) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (F) (f1) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (f2) 0.3 0.3 0.3 0.3 0.3 0.3 0.3

The physical properties of the epoxy resin compositions for semiconductor encapsulation of Examples 1 to 4 and Comparative Examples 1 to 3 were measured by the following measurement methods. The measurement results are shown in Table 2 below.

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 specimen (125 mm × 12.6 mm × 6.4 mm) was molded using an ASTM mold 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 calipers. The hardening shrinkage was calculated from the following equation (1).

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

In the formula (1), L ₀ is the length of the molded specimen obtained by molding the epoxy resin composition at 175 ° C and 70 kgf / cm ² using a transfer molding press, and L ₁ is the length of the molded specimen at 175 ° C Length of the specimen after post molding curing in the oven for 4 hours and after cooling.

(3) Modulus of elasticity (MPa): A test specimen of 20 mm x 13 mm x 1.6 mm was molded using a transfer molding machine under conditions of a mold temperature of 170 to 180 DEG C, an injection pressure of 800 to 1200 psi, and a curing time of 120 seconds. The test specimens were post-cured for 2 hours in a hot-air drier at 170-180 캜, and the Elastic Modulus of the specimens was measured using a Q8000 DMA (Dynamic Mechanical Analyzer) manufactured by TA Corporation. At this time, the temperature increase was measured in a temperature range of 5 ° C / min and -10 ° C to 300 ° C.

(4) Glass transition temperature: Measured using a thermomechanical analyzer (TMA). At this time, the TMA was set to a condition of measuring up to 300 DEG C by raising the temperature by 10 DEG C per minute at 25 DEG C. [

(5) Moisture absorption rate (%): The resin compositions prepared in the above Examples and Comparative Examples were extruded at a mold temperature of 170 to 180, a clamp pressure of 70 kgf / cm ² , a feed pressure of 1000 psi, a feed rate of 0.5 to 1 cm / To obtain a disk-shaped cured specimen having a diameter of 50 mm and a thickness of 1.0 mm. The obtained specimens were placed in an oven at 170 to 180 ° C., post-cured for 4 hours, left for 168 hours at 85 ° C. and 85 RH% relative humidity, and the weight change due to moisture absorption was measured, (2), the moisture absorption rate was calculated.

(2): moisture absorption rate = (weight of sample after moisture absorption-weight of sample before moisture absorption) / (weight of sample before moisture absorption) × 100

(6) Shore-D: Using an MPS (Multi Plunger System) molding machine equipped with a mold for eTQFP (exposed Thin Quad Flat Package) package having a width of 24 mm, a length of 24 mm and a thickness of 1 mm including a copper metal element After hardening the epoxy resin composition to be evaluated at 175 ° C for 50, 60, 70, 80 and 90 seconds, the hardness of the cured product was measured by a Shore-D type hardness meter directly on the package on the mold. The higher the value, the better the degree of cure.

(7) Adhesive force (kgf): A copper metal element was prepared in accordance with the mold for measurement of adhesion, and the resin composition prepared in the above-mentioned Examples and Comparative Examples was pressed at a mold temperature of 170 to 180 占 폚 and a clamp pressure of 70 kgf / cm ² , a feed pressure of 1000 psi, a feed rate of 0.5 to 1 cm / s, and a curing time of 120 seconds to obtain a cured specimen. The obtained specimen was post-cured (PMC) in an oven at 170 to 180 ° C for 4 hours. In this case, the area of the epoxy resin composition contacting the specimen was 40 ± 1 mm ² , and the adhesion was measured by using a universal testing machine (UTM) for 12 specimens per each measuring step, and then the average value was calculated.

(8) Storage stability: The flow length was measured at the intervals of 24 hours in the same manner as in the fluidity measurement in the above (1) while the prepared epoxy resin composition was stored in a thermostatic hygrostat set at 25 ° C / 50RH% for 1 week, Percentage (%) of flow length was obtained. The larger this percentage value, the better the storage stability.

(9) Softening point

The sample was filled in 4 rings according to KS M 3823 (softening point test method of epoxy resin), 3/8 steel ball was placed on the ring, and indirect heating was performed to evaluate the dropping temperature of the steel ball when the sample softened.

Evaluation items Example Comparative Example One 2 3 4 One 2 3 basic
Properties Flowability (inch) 62 63 60 60 60 15 - Cure shrinkage (%) 0.18 0.14 0.17 0.22 0.35 0.31 - Modulus of elasticity (MPa) 500 900 450 400 910 300 - Glass transition temperature (캜) 180 182 179 183 140 185 - Moisture absorption rate (%) 0.20 0.21 0.22 0.20 0.22 0.31 - Adhesion (kgf) 81 75 78 80 69 78 - package
evaluation Hardness (Shore-D) 50 seconds 67 72 70 69 62 65 - 60 seconds 72 73 72 73 68 70 - 70 seconds 74 77 75 76 71 74 - 80 seconds 76 78 77 76 74 76 - 90 seconds 77 79 78 76 75 77 - Save
stability 24hr 98% 97% 98% 98% 98% 98% - 48hr 95% 94% 94% 95% 95% 95% - 72hr 92% 91% 91% 92% 91% 92% -

From Table 2, it can be seen that Examples 1 to 4 have higher glass transition temperature and lower elastic modulus and cure shrinkage characteristics than Comparative Example 1. [ In the case of storage stability, it can be seen that there is almost no difference in fluidity even after 72 hours. In the case of the degree of hardening, the properties slightly higher than those of the comparative example are exhibited, and it is confirmed that the properties of fluidity and adhesion are equal to or higher than those of the comparative example.

In the case of Comparative Example 2, the softening point showed a low fluidity at 160 ° C. or higher, and it was found that the inner voids and sufficient hardening density were not formed during molding, and the moisture absorption rate and shrinkage ratio were increased. In the case of Comparative Example 3, the curing was progressed at the time of heating to melt-knead the cured product at a softening point of 180 ° C or higher, and therefore evaluation could not proceed.

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 (8)

An epoxy resin comprising a compound represented by the following formula (1); Curing agent; And an inorganic filler.
[Chemical Formula 1]

In Formula 1, A represents a phenylene group or a naphthylene group; X is an O atom; R is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an epoxy group or a glycidyl group; m1 and m2 are each independently an integer of 1 to 5; n is an integer of 0 to 10;
delete delete delete The method according to claim 1,
Wherein the compound represented by the formula (1) is selected from compounds represented by the following formulas (1a) to (1d).
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

In the above general formulas (1a) to (1d), X represents an O atom; R is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an epoxy group or a glycidyl group.
The method according to claim 1,
Wherein the epoxy resin comprising the compound represented by Formula 1 has a softening point of 150 占 폚 or less.
The method according to claim 1,
0.5 to 20% by weight of an epoxy resin containing a compound represented by the formula (1), 0.1 to 13% by weight of a curing agent, and 70 to 95% by weight of an inorganic filler.
A semiconductor device encapsulated with the epoxy resin composition for semiconductor device encapsulation according to any one of claims 1 to 7.