KR20180006001A - Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same - Google Patents

Abstract

The present invention relates to an epoxy resin composition for encapsulating a semiconductor, and a semiconductor device encapsulated by using the epoxy resin composition. An objective of the present invention is to provide an epoxy resin composition which is capable of providing properties of low contraction and low elasticity while minimizing deterioration of physical properties such as fluidity, storage stability, adhesive force, moisture absorption rate and the like. The epoxy resin composition of the present invention comprises: an epoxy resin including a compound represented by chemical formula 1, a compound represented by chemical formula 2, or a mixture thereof; a curing agent; and an inorganic filler. In chemical formula 1, l is an integer of 1 to 3. In chemical formula 2, m and n are each independently an integer of 1 to 3.

Description

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

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 low shrinkage and low elasticity, and a semiconductor device sealed with the composition.

Transfer molding using an epoxy resin composition is widely used as a method of packaging semiconductor devices such as IC and LSI and obtaining a semiconductor device because it is suitable for low cost and mass production.

Conventionally, due to the characteristics of the semiconductor packaging process, aliphatic or aromatic epoxy resins having a softening point of 50 to 130 have been mainly used. When the softening point of the epoxy resin is out of the above range, molding is difficult and defects tend to occur.

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 elastic modulus is greatly increased and is vulnerable to external stress due to heat or external impact. When the content of the inorganic filler is increased, .

Therefore, development of an epoxy resin composition for encapsulating a semiconductor device having a low hardening shrinkage ratio and an elastic modulus while minimizing deterioration of other physical properties such as fluidity and storage stability is required.

Related prior art is disclosed in Japanese Patent Application Laid-Open No. 7-53671.

An object of the present invention is to provide an epoxy resin composition capable of realizing low shrinkage and low elasticity properties while minimizing deterioration of physical properties such as fluidity, storage stability, adhesion force, moisture absorption rate and the like.

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

In one aspect, the present invention relates to an epoxy resin comprising a compound represented by the following formula (1), a compound represented by the following formula (2), or a mixture thereof; Curing agent; And an inorganic filler. The present invention also provides an epoxy resin composition for semiconductor encapsulation.

[Chemical Formula 1]

In Formula 1, l is an integer of 1 to 3;

(2)

In Formula 2, m and n are each independently an integer of 1 to 3.

Preferably, the epoxy resin may include a mixture of the compound represented by the formula (1) and the compound represented by the formula (2). For example, the mixture may include a compound represented by the formula (1) In a molar ratio of 1: 9 to 9: 1. Preferably, in the mixture, the number of moles of the compound represented by the formula (1) is not less than the number of moles of the compound represented by the formula (2). For example, the mixture may contain the compound represented by the formula (1): the compound represented by the formula (2) in a molar ratio of 1: 1 to 5: 1, preferably 2: 1 to 4: 1.

According to one embodiment, the compound represented by Formula 1 may include at least one of the compounds represented by Chemical Formulas 1-1 to 1-9.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

According to another embodiment, the compound represented by Formula 2 may include at least one compound represented by Formula 2-1 to Formula 2-3.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

The epoxy resin composition for semiconductor encapsulation may contain 0.5 to 20% by weight of the epoxy resin, 0.1 to 13% by weight of the curing agent, and 70 to 95% by weight of the inorganic filler. If necessary, the curing accelerator, And a coloring agent.

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

The epoxy resin composition of the present invention is excellent in physical properties such as fluidity, storage stability, adhesion, moisture absorption rate and the like, and can achieve low shrinkage and low elasticity properties after curing by using an epoxy compound having a naphthalene skeleton having a specific 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 ".

The inventors of the present invention have conducted studies to develop a material for semiconductor encapsulation having low shrinkage and low elasticity so as to minimize the occurrence of warping of the semiconductor package due to thermal expansion and heat shrinkage and chip breakage caused by external impact, Based naphthalene-based epoxy compound, it is possible to achieve the above object. Thus completing the present invention.

Specifically, the epoxy resin composition of the present invention comprises an epoxy resin, a curing agent, and an inorganic filler including a compound represented by the formula (1), a compound represented by the formula (2), or a mixture thereof. Hereinafter, each component of the epoxy resin composition of the present invention will be described in detail.

Epoxy resin

In the present invention, the epoxy resin includes a compound represented by the following formula (1), a compound represented by the following formula (2), or a mixture thereof.

[Chemical Formula 1]

In Formula 1, l is an integer of 1 to 3.

(2)

In Formula 2, m and n are each independently an integer of 1 to 3.

The compound represented by Formula 1 may be prepared by reacting dihydroxynaphthalene with hydroxybenzyl alcohol to form a reaction product, and then reacting the reaction product with epichlorohydrin or the like to introduce an epoxy group.

The compound represented by Formula 2 may be prepared by reacting dihydroxynaphthalene with hydroxybenzyl alcohol and benzyl alcohol to form a reaction product and reacting the reaction product with epichlorohydrin to introduce an epoxy group .

 The compound of formula (1) or (2) prepared as described above has a bulky structure including naphthalene and benzene rings, and exhibits a low shrinkage ratio and modulus of elasticity after curing. In addition, the compound of formula (1) or (2) contains at least three epoxy functional groups as curing sites in the compound, so that the curing degree increases and a more advantageous effect can be obtained from the viewpoint of the shrinkage ratio.

On the other hand, the epoxy resin may contain the compound of the formula (1) or the compound of the formula (2) alone or a mixture of the compound of the formula (1) and the compound of the formula (2).

Preferably, the epoxy resin includes a mixture of the compound represented by the formula (1) and the compound represented by the formula (2). Specifically, the mixture may contain the compound represented by the formula (1) and the compound represented by the formula (2) in a molar ratio of 1: 9 to 9: 1.

On the other hand, it is more preferable that the number of moles of the compound represented by the formula (1) in the mixture is not less than the number of moles of the compound represented by the formula (2). When the number of moles of the compound represented by the formula (1) is larger than the number of moles of the compound represented by the formula (2), the low shrinkage characteristics are more excellent. Specifically, the mixture may contain the compound represented by the formula (1): the compound represented by the formula (2) in a molar ratio of 1: 1 to 5: 1, preferably 2: 1 to 4: 1.

According to one embodiment, the compound represented by Formula 1 may include at least one of the compounds represented by Chemical Formulas 1-1 to 1-9.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

According to another embodiment, the compound represented by Formula 2 may include at least one compound represented by Formula 2-1 to Formula 2-3.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

On the other hand, the epoxy resin is contained 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 in the epoxy resin composition for encapsulating semiconductor devices .

Hardener

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 phenol resin may be, for example, a phenol novolak type phenol resin represented by the following formula (3).

(3)

In Formula 3, d is 1 to 7.

The phenol novolak type phenolic resin represented by the above-mentioned formula (3) has a short crosslinking point interval, and when it reacts with an epoxy resin, the crosslinking density becomes high so that 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 (4).

[Chemical Formula 4]

In Formula 4, the average value of e is 1 to 7.

The phenol aralkyl type phenol resin represented by the above formula (4) reacts with an epoxy resin to form a carbon layer (char) to block the transfer of heat and oxygen to the surrounding, thereby achieving flame retardancy.

The xylo-type phenol resin may be, for example, a xylok-type phenol resin represented by the following formula (5).

  [Chemical Formula 5]

(In the formula (5), the average value of f is 0 to 7.)

The xylyl phenol resin represented by the above-mentioned formula (5) 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 (6).

[Chemical Formula 6]

(The average value of g in the above formula (6) is 1 to 7.)

The multifunctional phenol resin containing the repeating unit represented by the above formula (6) 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 can be used as an additional compound prepared by subjecting the above curing agent to a linear reaction such as an epoxy resin, a curing accelerator, a releasing agent, a coupling agent, a stress relieving agent and the like and a 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.

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.

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 95 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. 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. 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, 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.

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, 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; (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (methylene- 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 heat shrinkage or thermal expansion after semiconductor sealing and chip breakage due to external impact can be minimized.

Specifically, the epoxy resin composition for semiconductor encapsulation according to the present invention has a low shrinkage specificity of not more than 0.30%, preferably not more than 0.2%, more preferably not more than 0.15%, as measured by the following formula (1) .

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

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

Further, 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 1500 MPa or less, preferably 900 MPa or less, . The transfer molding was performed under the 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 carried out in a hot air drier of 170 to 180 for 2 hours. The modulus of elasticity was measured by using a Dynamic Mechanical Analyzer (TA, Q8000 DMA) at a rate of 5 / 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.

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.

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

(A) an epoxy resin

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

160 g (1.0 mol) of 2,7-dihydroxynaphthalene and 248 g (2.0 mol) of 4-hydroxybenzyl alcohol were added to 500 g of methyl isobutyl ketone and stirred to dissolve and then 25 g of sulfuric acid was added. Thereafter, the mixture was heated to 60 DEG C while paying attention to heat generation, and water produced using a fractionation tube was drawn 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 308 g of the reaction product (1).

Subsequently, 160 g of the above reaction product (1), 740 g (5.0 mol) of epichlorohydrin, and 4.6 g of tetraethylbenzylammonium chloride were placed in a flask, and the temperature of the flask was elevated to 65 ° C. After confirming that the reaction product (1) 164 g of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, the mixture was stirred for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain an epoxy resin

 To the obtained epoxy resin, 550 g of methyl isobutyl ketone and 55 g of n-butanol were added and dissolved. Then, 15 g of a 10% aqueous solution of sodium hydroxide was added to the solution, and the mixture was reacted at 80 DEG C for 2 hours. Thereafter, washing with water was repeated three times with 150 g of water until the pH of the washing solution became neutral. Then, the solvent was evaporated off under reduced pressure to obtain 154 g of the epoxy resin (a1).

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

160 g (1.0 mol) of 1,5-dihydroxynaphthalene and 248 g (2.0 mol) of 4-hydroxybenzylalcohol were dissolved in 500 g of methyl isobutyl ketone and dissolved, followed by addition of 25 g of sulfuric acid. Thereafter, the mixture was heated to 60 DEG C while paying attention to heat generation, and water produced using a fractionation tube was drawn 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 340 g of reaction product (2).

Next, 160 g of the reaction product (2), 740 g (5.0 mol) of epichlorohydrin, and 4.6 g of tetraethylbenzylammonium chloride were placed in a flask, and the temperature was raised to 65. After confirming that the reaction product (2) % Sodium hydroxide aqueous solution was added dropwise over 5 hours. Thereafter, the mixture was stirred for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain an epoxy resin

 To the obtained epoxy resin, 550 g of methyl isobutyl ketone and 55 g of n-butanol were added and dissolved. Then, 15 g of a 10% aqueous solution of sodium hydroxide was added to the solution, and the reaction was carried out at 80 for 2 hours. Thereafter, washing with water was repeated three times with 150 g of water until the pH of the washing solution became neutral. Then, the solvent was evaporated off under reduced pressure to obtain 158 g of an epoxy resin (a2).

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

160 g (1.0 mole) of 2,7-dihydroxynaphthalene, 217 g (1.75 mole) of 4-hydroxybenzylalcohol and 27 g (0.25 mole) of benzyl alcohol were dissolved in 500 g of methyl isobutyl ketone and stirred to dissolve 25 g of sulfuric acid was added. Thereafter, the mixture was heated up to 60 ° C while paying attention to heat generation, and water produced by using a fractionation tube was extracted 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 320 g of reaction product (3).

Subsequently, 160 g of the reaction product (3), 740 g (5.0 mol) of epichlorohydrin, and 4.6 g of tetraethylbenzylammonium chloride were placed in a flask and the temperature was raised to 65. After confirming that the reaction product (3) % Sodium hydroxide aqueous solution was added dropwise over 5 hours. Thereafter, the mixture was stirred for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain an epoxy resin

 To the obtained epoxy resin, 550 g of methyl isobutyl ketone and 55 g of n-butanol were added and dissolved. Then, 15 g of a 10% aqueous solution of sodium hydroxide was added to the solution, and the reaction was carried out at 80 for 2 hours. Thereafter, washing with water was repeated three times with 150 g of water until the pH of the washing solution became neutral. Then, the solvent was evaporated off under reduced pressure to obtain 180 g of an epoxy resin (a3). The resin thus obtained had a molar ratio of about 4: 1 in the formula (1).

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

160 g (1.0 mole) of 1,5-dihydroxynaphthalene, 186 g (1.5 mole) of 4-hydroxybenzylalcohol and 54 g (0.5 mole) of benzyl alcohol were dissolved in 500 g of methyl isobutyl ketone and dissolved by stirring 25 g of sulfuric acid was added. Thereafter, the mixture was heated up to 60 ° C while paying attention to heat generation, and water produced by using a fractionation tube was extracted 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 330 g of reaction product (4).

Next, 160 g of the reaction product (4), 740 g (5.0 mol) of epichlorohydrin, and 4.6 g of tetraethylbenzylammonium chloride were placed in a flask, and the temperature was raised to 65. After confirming that the reaction product (4) % Sodium hydroxide aqueous solution was added dropwise over 5 hours. Thereafter, the mixture was stirred for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain an epoxy resin

 To the obtained epoxy resin, 550 g of methyl isobutyl ketone and 55 g of n-butanol were added and dissolved. Then, 15 g of a 10% aqueous solution of sodium hydroxide was added to the solution, and the reaction was carried out at 80 for 2 hours. Thereafter, washing with water was repeated three times with 150 g of water until the pH of the washing solution became neutral. Then, the solvent was evaporated under reduced pressure to obtain 180 g of an epoxy resin (a4). The resin thus obtained had a molar ratio of about 2: 1 in the formula (1).

(a5) HP-4770 manufactured by DIC was used.

(a6) An epoxy resin synthesized by the following method was used.

144 g (1.0 mol) of 1-naphthol and 248 g (2.0 mol) of 4-hydroxybenzyl alcohol were added to 500 g of methyl isobutyl ketone and stirred to dissolve and then 25 g of sulfuric acid was added. Thereafter, the mixture was heated to 60 DEG C while paying attention to heat generation, and water produced using a fractionation tube was drawn 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 289 g of a reaction product (5).

Next, 144 g of the above reaction product (5), 740 g (5.0 mol) of epichlorohydrin, and 4.6 g of tetraethylbenzylammonium chloride were placed in a flask, and the temperature was raised to 65 ° C. After confirming that the reaction product (5) 164 g of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, the mixture was stirred for 1 hour under the same conditions. Thereafter, unreacted epichlorohydrin was evaporated off by distillation under reduced pressure to obtain an epoxy resin

 To the obtained epoxy resin, 550 g of methyl isobutyl ketone and 55 g of n-butanol were added and dissolved. Then, 15 g of a 10% aqueous solution of sodium hydroxide was added to the solution, and the mixture was reacted at 80 DEG C for 2 hours. Thereafter, washing with water was repeated three times with 150 g of water until the pH of the washing solution became neutral. Then, the solvent was evaporated under reduced pressure to obtain 148 g of an epoxy resin (a6).

(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) was mixed with KBM-803 (Shinetsu), which is a mercaptopropyltrimethoxysilane, and SZ-6070 (Dow Corning chemical), which is e2) methyltrimethoxysilane.

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

Example  1 to 4 and Comparative Example  1-3

Each of the components was weighed according to the composition shown in Table 1, and then uniformly mixed using a Henschel mixer to prepare a powdery first 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 (A) (a1) 8.5 (a2) 8.5 (a3) 8.5 (a4) 8.5 (a5) 8.5 (a6) 8.5 (B) 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 (D) 85 85 85 85 85 85 (E) (e1) 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 (F) (f1) 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

(Unit: wt%)

The physical properties of the epoxy resin compositions for semiconductor encapsulation of Examples 1 to 7 and Comparative Examples 1 to 3 were measured by the following measurement 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 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 a 170-180 oven 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) Elastic modulus (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 specimens were post cured in a hot air drier at 170-180 ° C for 2 hours and then Elastic Modulus of the specimens was measured using a Q8000 DMA (Dynamic Mechanical Analyzer). 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, TMA is 25 10 per minute at By increasing the temperature by ℃, 300 Lt; 0 > C.

(5) Moisture absorption rate (%): The resin compositions prepared in the above Examples and Comparative Examples were heated 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. and post-cured for 4 hours. The samples were allowed to stand at 85 ° C. and 85 RH% relative humidity for 168 hours, 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) Adhesive force (kgf): A copper metal element was prepared in accordance with the mold for measurement of attachment, and the resin composition prepared in the above-mentioned Examples and Comparative Examples was pressed at a mold temperature of 170 to 180 DEG C 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 cured specimens. The obtained specimens were 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.

(7) Hardness (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 curing the epoxy resin composition to be evaluated at 175 ° C for 50 seconds, 60 seconds, 70 seconds, 80 seconds, and 90 seconds, the hardness of the cured product was measured by a Shore-D type hardness meter . The higher the value, the better the degree of cure.

(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 higher this percentage value is, the better the storage stability is.

Evaluation items Example Comparative Example One 2 3 4 One 2 basic
Properties Flowability (inch) 62 63 60 60 60 61 Cure shrinkage (%) 0.19 0.18 0.21 0.22 0.35 0.28 Modulus of elasticity (MPa) 800 850 650 700 900 850 Glass transition temperature (캜) 180 173 179 185 140 164 Moisture absorption rate (%) 0.20 0.21 0.22 0.20 0.22 0.21 Adhesion (kgf) 81 75 74 78 69 75 package
evaluation Cure Time-hardening degree ((Shore-D) 50 seconds 67 71 70 69 62 65 60 seconds 72 72 72 73 68 70 70 seconds 74 73 75 76 71 72 80 seconds 75 73 77 76 74 74 90 seconds 76 74 78 76 75 75 Storage stability 24 hr 98% 97% 98% 98% 98% 97% 48 hr 95% 94% 94% 95% 95% 95% 72 hr 92% 91% 91% 92% 91% 92%

It can be seen from the above Table 2 that, in Examples 1 to 4, low curing shrinkage characteristics are exhibited as compared with Comparative Examples 1 and 2. In Examples 1 to 4, the glass transition temperature was higher than Comparative Examples 1 and 2 without increasing the modulus of elasticity, and the fluidity, adhesion, moisture absorption rate, curing degree, storage stability It can be confirmed that it has stability.

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 comprising a compound represented by the following formula (1), a compound represented by the following formula (2), or a mixture thereof; Curing agent; And an inorganic filler.
[Chemical Formula 1]

In Formula 1, l is an integer of 1 to 3;
(2)

In Formula 2, m and n are each independently an integer of 1 to 3.
The method according to claim 1,
Wherein the epoxy resin comprises a mixture of the compound represented by the formula (1) and the compound represented by the formula (2).
3. The method of claim 2,
Wherein the number of moles of the compound represented by the formula (1) in the mixture is not less than the number of moles of the compound represented by the formula (2).
3. The method of claim 2,
Wherein the mixture contains a compound represented by the formula (1) and a compound represented by the formula (2) in a molar ratio of 1: 9 to 9: 1.
The method according to claim 1,
Wherein the compound represented by the general formula (1) comprises at least one or more compounds represented by the following general formulas (1-1) to (1-9).
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

The method according to claim 1,
Wherein the compound represented by the general formula (2) comprises at least one or more compounds represented by the following general formulas (2-1) to (2-3).
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

The method according to claim 1,
Wherein the epoxy resin composition for semiconductor encapsulation comprises 0.5 to 20% by weight of the epoxy resin, 0.1 to 13% by weight of the curing agent, and 70 to 95% by weight of the inorganic filler.
The method according to claim 1,
Wherein the epoxy resin composition for semiconductor encapsulation further comprises at least one of a curing accelerator, a coupling agent, a releasing agent and a colorant.
A semiconductor device sealed with the epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 8.