KR102245604B1 - Epoxy resin composition - Google Patents

Abstract

The present invention relates to an epoxy resin composition applicable to a high-temperature driving power semiconductor encapsulant.

Description

Epoxy resin composition {Epoxy resin composition}

The present invention relates to an epoxy resin composition applicable to a high-temperature driving power semiconductor encapsulant.

Higher performance of power semiconductors increases the driving temperature, and thus high heat resistance is required for materials constituting the device. Among them, in particular, since the heat resistance of the encapsulant material that encapsulates a semiconductor device is highly required, the demand for a semiconductor encapsulant having a high glass transition temperature (Tg) is increasing in recent years.

Conventionally, an epoxy resin composition for semiconductor encapsulation, which mixes ortho cresol novolak type epoxy resin and a phenolic curing agent, has been applied, but such an encapsulant composition has a glass transition temperature of only about 175 °C, and the glass transition temperature is increased. There is a limit.

In order to implement a higher glass transition temperature, Korean Patent No. 10-0861324 applied an epoxy resin having a condensed cyclic polycyclic structure such as naphthalene or anthracene structure. However, the condensed cyclic epoxy resin has a high melt viscosity or a high softening point, so that the content of the filler cannot be set high, so it is vulnerable to deformation by heat and moisture penetration, and is vulnerable to cracking after curing. In addition, it has the disadvantage of insufficient electrical characteristics at a required high driving temperature. As another example, Korean Patent Application Publication No. 2014-0123065 discloses a technology for securing high heat resistance by optimizing the skeletal density of the resin by applying a biphenyl type resin. However, these biphenyl-type resins generally have a disadvantage of poor dielectric properties.

On the other hand, a method of implementing high glass transition ionicity and excellent electrical properties by using an acid anhydride resin as a curing agent has also been proposed. However, the acid anhydride-based resin having a high glass transition temperature has a high melting point, so it is difficult to apply it to the manufacturing process of a general epoxy resin encapsulant, and the filler content cannot be set high due to the high melting viscosity. Therefore, it is vulnerable to thermal deformation and moisture penetration at a high driving temperature, and is vulnerable to cracking after curing.

As described above, the development of a semiconductor encapsulant having a high glass transition temperature continues, but there is a problem that such encapsulant is vulnerable to cracking due to a high modulus of elasticity. In particular, in the case of high-performance power semiconductors driven at high temperatures, they are subjected to high internal thermal stress due to expansion and contraction due to rapid temperature changes, which is delamination or cracking between dissimilar materials inside the semiconductor. Is the main cause of the. In order to solve this problem, semiconductor encapsulants are required to have a low coefficient of thermal expansion and a low modulus of elasticity. In particular, silicon carbide (SiC) or gallium nitride (GaN)-based devices, which are new materials that have advantages such as high breakdown voltage, high current, and high temperature operation, are more susceptible to cracking than silicon (Si)-based devices that are currently mainstream. In addition, a low coefficient of thermal expansion and a low modulus of elasticity are further required.

Accordingly, there is a need for development of an epoxy resin composition having high heat resistance, a high content of a filler, a low coefficient of thermal expansion and a low modulus of elasticity, and excellent electrical properties at a high temperature.

The present invention provides an epoxy resin composition having high heat resistance, a low coefficient of thermal expansion, a low high temperature elastic modulus, and excellent high temperature electrical properties, which can be used as an encapsulant material for a high temperature driving power semiconductor.

The present invention provides an epoxy resin composition comprising a fluorene-containing epoxy resin, a curing agent, a filler, and a curing accelerator.

In addition, the present invention provides a semiconductor device encapsulated by using the above-described epoxy resin composition.

The epoxy resin composition according to the present invention has a high heat resistance, a low coefficient of thermal expansion and a low high-temperature elastic modulus, may contain a high content of a filler, and exhibit excellent electrical properties at a high temperature. The epoxy resin composition of the present invention may contain a filler in a high content of 80% or more, may have a glass transition temperature of 200° C. or more, and has excellent continuous workability at a temperature of 180° C. or less, which is a general semiconductor encapsulant use temperature. Accordingly, the epoxy resin composition of the present invention is suitable for application to an encapsulant of a high-temperature driving power semiconductor.

Hereinafter, the present invention will be described. However, it is not limited only by the following contents, and each component may be variously modified or selectively used as necessary. Therefore, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

<Epoxy resin composition>

The epoxy resin composition according to the present invention is an epoxy resin composition (EMC: Epoxy Molding Compound) for a semiconductor encapsulant, and includes a fluorene-containing epoxy resin, a curing agent, a curing accelerator, and a filler. In addition, if necessary, it may further include one or more additives commonly used in the art, such as a coupling agent, a colorant, a release agent, a modifier, a flame retardant, and a low stress agent.

Hereinafter, the composition of the epoxy resin composition will be described in detail.

Epoxy resin

Fluorene-containing epoxy resin

The epoxy resin composition according to the present invention includes a fluorene-containing epoxy resin. The method of preparing the fluorene-containing epoxy resin is not particularly limited, and may be prepared, for example, by reacting an epoxy resin or epichlorohydrin with a fluorene-containing compound. The reaction can be carried out in the presence of a catalyst, and can be carried out in a suitable solvent.

The epoxy resin is not particularly limited as long as it is a conventional epoxy resin known in the art. Non-limiting examples of usable epoxy resins include bisphenol A type epoxy resin, cresol novolac type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, anthracene epoxy resin, biphenyl type epoxy resin, Tetramethyl biphenyl-type epoxy resin, phenol novolac-type epoxy resin, bisphenol A novolac-type epoxy resin, bisphenol S novolac-type epoxy resin, biphenyl novolac-type epoxy resin, naphthol novolac-type epoxy resin, naphthol phenol co-condensation furnace Rock type epoxy resin, naphthol cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, triphenyl methane type epoxy resin, tetraphenyl ethane type epoxy resin, dicyclopentadiene type epoxy resin, dicyclo At least one of a pentadiene phenol addition reaction type epoxy resin, a phenol aralkyl type epoxy resin, a polyfunctional phenolic epoxy resin, and a naphthol aralkyl type epoxy resin may be mentioned, but is not limited thereto.

The type of the fluorene-containing compound is not particularly limited, but as an example, it may be a compound having a structure represented by the following formula (1).

<Formula 1>

In the above formula,

Each R ¹ is independently a cyano group, a halogen atom, or an alkyl group having 1 to 6 carbon atoms,

R ² is each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cycloalkyl group having 6 to 10 carbon atoms,

Each R ³ is independently an alkylene group having 1 to 4 carbon atoms,

l is each independently an integer of 0 to 4,

m is each independently an integer of 0 to 4,

n is each independently an integer of 0 to 5,

o is each independently an integer of 1 to 3,

n+o is an integer of 5 or less.

The fluorene-containing compound is, for example, 9,9-bis[4-(2-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis[4-(2-hydroxypropoxy)- 3-ethylphenyl)fluorene, 9,9-bis[4-(2-hydroxypropoxy)-3-propylphenyl)fluorene, 9,9-bis[4-(2-hydroxypropoxy)- 3-butylphenyl)fluorene, 9,9-bis(2-hydroxypropoxy-3-phenylphenyl)fluorene, 9,9-bis(2-hydroxypropoxy-benzylphenyl)fluorene, 9, 9-bis(2-hydroxypropoxy-tolylphenyl)fluorene, 9,9-bis(2-hydroxypropoxy-silylphenyl)fluorene, 9,9-bis[4-{2-(2- Hydroxypropoxy)propoxy}-3-methylphenyl]fluorene, 9,9-bis[4-{2-(2-hydroxypropoxy)propoxy}-3-ethylphenyl]fluorene, 9,9 -Bis[4-{2-(2-hydroxypropoxy)propoxy}-3-propylphenyl]fluorene, 9,9-bis[4-{2-(2-hydroxypropoxy)propoxy} -3-butylphenyl]fluorene, 9,9-bis[2-(2-hydroxypropoxy)propoxy-3-phenylphenyl]fluorene, 9,9-bis[2-(2-hydroxypro Foxy)propoxy-3-benzylphenyl]fluorene, 9,9-bis[2-(2-hydroxypropoxy)propoxy-3-tolylphenyl]fluorene, 9,9-bis[2-(2 -Hydroxypropoxy)propoxy-3-silylphenyl]fluorene, 9,9-bis-(3',4'-dihydroxyphenyl)-fluorene, 9,9-bis-(2',4 '-Dihydroxyphenyl)-fluorene, 9,9-bis-(3',5'-dihydroxyphenyl)-fluorene, 9,9-bis-(2',3'-dihydroxyphenyl )-Fluorene, 9,9-bis-(2',6'-dihydroxyphenyl)-fluorene, 9,9-bis-(2',5'-dihydroxyphenyl)-fluorene, 4 It may be one or more selected from the group consisting of -4'-(9-fluorenylidene)diphenol.

The type of solvent used for the reaction of the epoxy resin and the fluorene-containing compound is not particularly limited, and examples thereof include ether solvents such as dimethyl ether, diethyl ether, and tetrahydrofuran; Halogen-based solvents such as methylene chloride, chloroform, and carbon tetrachloride; Aromatic hydrocarbon solvents such as benzene, toluene, and xylene; And one or more of lower alcohols such as methanol and ethanol may be used.

The catalyst used for the reaction of the epoxy resin and the fluorene-containing compound may be, for example, one selected from metal hydroxides, metal carbonates, amines, and carboxylic acid metal salts, or a mixture thereof.

As an example, the fluorene-containing epoxy resin of the present invention includes an epoxy resin represented by the following formula (2).

<Formula 2>

In the above formula,

R1 to R2 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms,

n is an integer of 2 to 10.

The alkyl group having 1 to 6 carbon atoms means a straight-chain or branched hydrocarbon composed of 1 to 6 carbon atoms. Examples include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, and the like.

The alkoxy group having 1 to 6 carbon atoms means a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. Examples include, but are not limited to, methoxy, ethoxy, n-propaneoxy, and the like.

The R1 to R2 are the same as or different from each other, and each independently hydrogen, may be an alkyl group such as a methyl group, an ethyl group, or a propyl group, or an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group.

In the present invention, the fluorene-containing epoxy resin may further include an epoxy resin represented by the following Formula 3 in addition to the epoxy resin represented by Formula 2 above. When the epoxy resin of the following Formula 3 is mixed, the coefficient of thermal expansion and the high-temperature elastic modulus of the epoxy resin composition may be further lowered.

<Formula 3>

In the above formula,

Each of R1 to R2 is independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

The alkyl group having 1 to 6 carbon atoms means a straight-chain or branched hydrocarbon composed of 1 to 6 carbon atoms. Examples include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, and the like.

The alkoxy group having 1 to 6 carbon atoms means a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. Examples include, but are not limited to, methoxy, ethoxy, n-propaneoxy, and the like.

The R1 to R2 are the same as or different from each other, and each independently hydrogen, may be an alkyl group such as a methyl group, an ethyl group, or a propyl group, or an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group.

The epoxy resin represented by Formula 3 may be represented by the following Formula 3a.

<Formula 3a>

The fluorene-containing epoxy resin may have a melt viscosity of 3 poise or less at 150° C. measured using an ICI viscometer (Research Equip., TW 5NX), for example, 1 to 3 poise. The softening point of the fluorene-containing epoxy resin may be 100 °C or less, for example, 50 to 100 °C. Since the fluorene-containing epoxy resin has a low melt viscosity and softening point in the above-described range, it is excellent while including a high content of a filler, such as 80% by weight or more, such as 85 to 90% by weight, based on the total weight of the epoxy resin composition. It can have kneading properties.

The epoxy equivalent (EEW) of the fluorene-containing epoxy resin is not particularly limited. The epoxy equivalent of the fluorene-containing epoxy resin may be, for example, 150 to 400 g/eq, and in another example, 200 to 300 g/eq.

The fluorene-containing epoxy resin may be included in an amount of 30 to 100% by weight based on the total weight of the epoxy resin. When the fluorene-containing epoxy resin is contained in an amount of less than 30% by weight, a sufficiently high glass transition temperature cannot be secured or a low coefficient of thermal expansion and a low high-temperature elastic modulus cannot be secured. In addition, when mixed with other epoxy resins having a high glass transition temperature such as naphthalene type or anthracene type, it may be difficult to set a high content of the filler, and it may be difficult to achieve a dielectric constant of 5.5 or less at 200° C. after curing.

When the epoxy resin of the present invention contains the epoxy resin represented by Formula 3, the mixing ratio of the epoxy resin represented by Formula 2 and the epoxy resin represented by Formula 3 is 1: 0.1 to 1.5 weight ratio, for example 1: 0.8 To 1.2 weight ratio. When the epoxy resin represented by Chemical Formula 3 is mixed in the above-described ratio, the coefficient of thermal expansion and the high-temperature elastic modulus of the epoxy resin composition may be further lowered.

Epoxy resin having a non-condensed cyclic polycyclic structure and at least 3 functional groups

In addition to the fluorene-containing epoxy resin, the epoxy resin composition of the present invention may further include an epoxy resin having a non-condensed cyclic polycyclic structure and at least three functional groups.

When the non-condensed cyclic polycyclic structure and an epoxy resin having at least three functional groups are mixed, the melt viscosity of the epoxy resin composition may be lowered, and the glass transition temperature may be further increased. The epoxy resin having a non-condensed cyclic polycyclic structure and at least three functional groups may be represented by the following formula (4).

<Formula 4>

In the above formula,

R ₁ -R ₃ are each independently a C 1 to C 6 alkyl group or a C 1 to C 6 alkoxy group,

R ₄ -R ₁₉ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

The epoxy resin represented by Formula 4 may be represented by the following Formula 4a.

<Formula 4a>

In the above formula,

R1 to R3 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

The alkyl group having 1 to 6 carbon atoms means a straight-chain or branched hydrocarbon composed of 1 to 6 carbon atoms. Examples include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl, and the like.

The alkoxy group having 1 to 6 carbon atoms means a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. Examples include, but are not limited to, methoxy, ethoxy, n-propaneoxy, and the like.

The R1 to R3 are the same as or different from each other, and each independently may be an alkyl group such as a methyl group, an ethyl group, or a propyl group, or an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group.

When the epoxy resin of the present invention contains the epoxy resin represented by Formula 4, the mixing ratio of the epoxy resin represented by Formula 2 and the epoxy resin represented by Formula 4 is 1:0.1 to 1.5 weight ratio, for example 1: It may be from 0.8 to 1.2 weight ratio. When the epoxy resin represented by Chemical Formula 4 is mixed in the above-described ratio, the melt viscosity of the epoxy resin composition may be lowered, and the glass transition temperature may be further increased.

As another example, when the epoxy resin of the present invention contains the epoxy resin represented by Formula 4, the mixing ratio of the epoxy resin represented by Formula 2, the epoxy resin represented by Formula 3, and the epoxy resin represented by Formula 4 is 1 : 0.1 to 1.5: 0.1 to 1.5 weight ratio, for example, it may be 1: 0.8 to 1.2: 0.8 to 1.2 weight ratio. When the three types of epoxy resins are mixed in the above-described ratio, it is possible to lower the melt viscosity of the epoxy resin composition, increase the glass transition temperature, and further lower the thermal expansion coefficient and high-temperature elastic modulus.

The epoxy resin composition of the present invention may further include an epoxy resin commonly used in the art in addition to the above-described epoxy resin. For example, a polymer or oligomer containing at least two epoxy groups in one molecule, and a polymer or oligomer produced by a ring-opening reaction of the epoxy group can be used. For example, bisphenol A type, alicyclic type, linear aliphatic, (ortho) cresol novolac type, naphthol novolac type, biphenyl type, polyfunctional type, naphthalene type, anthracene type and dicyclopentadiene type epoxy resin alone or Two or more types may be mixed and used, and in particular, for realization of high heat resistance characteristics, at least one of (ortho) cresol novolac type epoxy resin and naphthalene type epoxy resin may be included, but is not limited thereto. The epoxy equivalent of the epoxy resin may be 120 to 280 g/eq, and a softening point may be 50 to 120°C.

The epoxy resin may be included in an amount of 2 to 15% by weight, for example 5 to 10% by weight, based on the total weight of the epoxy resin composition. If the content of the epoxy resin is less than 2% by weight, adhesiveness, electrical insulation, flowability, and moldability may be deteriorated, and if the content exceeds 15% by weight, it is difficult to form a cured product, and the reliability of the semiconductor is increased due to an increase in moisture absorption. It becomes poor, and strength may decrease due to a decrease in the relative content of the filler.

Hardener

In the present invention, the curing agent includes a benzoxazine-based compound as a component that reacts with the epoxy resin, which is the main resin, and cures the composition. The benzoxazine-based compound may be represented by the following formula (5).

<Formula 5>

In the above formula,

X is an alkylene group having 1 to 10 carbon atoms,

R ₂₀ -R ₂₇ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms.

The softening point of the benzoxazine-based resin represented by Chemical Formula 5 may be 100°C or less, for example, 50 to 100°C.

The benzoxazine-based resin represented by Formula 5 may be represented by the following Formula 5a.

<Formula 5a>

The benzoxazine compound represented by Formula 5 may be included in an amount of 15 to 100% by weight based on the total weight of the curing agent. When the benzoxazine compound of Formula 5 is contained in an amount of less than 15% by weight, a sufficiently high glass transition temperature may not be secured.

When the benzoxazine compound represented by Formula 5 is used alone as a curing agent, the blending ratio with the epoxy resin is in the range of 0.5 to 1.1 equivalents of the active group in the benzoxazine capable of reacting to 1 equivalent of the epoxy group in the total epoxy resin. For example, it may be a ratio in the range of 0.7 to 0.9 equivalents. If the benzoxazine active group for 1 equivalent of the epoxy group is less than 0.5 equivalent, the curability is low and continuous workability becomes weak, and the strength of the cured product may also become weak. On the other hand, if it exceeds 1.1 equivalent, the adhesive property of the cured product is lowered and the water resistance is weakened, so that the high temperature, high humidity reliability of the package (PKG) may be weak.

In the present invention, the curing agent may further include a curing agent commonly used in semiconductor encapsulants in addition to the benzoxazine compound represented by Chemical Formula 5. The curing agent further included is not particularly limited as long as it is a curing agent capable of reacting with an epoxy resin, but a curing agent excellent in physical properties such as moisture resistance, heat resistance, and storage properties, for example, a phenol resin-based curing agent may be used in combination.

As the phenolic resin-based curing agent, one containing two or more phenolic hydroxy groups that react with the epoxy resin component and proceed with curing in the molecular structure may be used, for example, a phenol novolac resin, a xylac resin, a cresol novolac resin, At least one polyhydric phenol compound selected from the group consisting of phenol alkyl resins, various novolac resins synthesized from bisphenol A, and dihydrobiphenyl may be used.

When the benzoxazine compound and a phenol resin-based curing agent are used together as a curing agent, the blending ratio with the epoxy resin is in the range of 0.7 to 1.2 equivalents of active groups in the curing agent capable of reacting to 1 equivalent of epoxy groups in the total epoxy resin, for example, 0.8 to 1.1 equivalents. It can be a ratio that becomes a range. When the active group of the curing agent for 1 equivalent of the epoxy group is less than 0.7 equivalent, the curing speed of the epoxy resin composition becomes slow, and when it exceeds 1.2 equivalent, the strength of the cured product after final curing may decrease. In addition, high-temperature thermal decomposition may occur due to an unreacted epoxy group or a curing agent outside the above equivalent range.

The curing agent may be included in an amount of 1 to 15% by weight, for example, 2 to 10% by weight, based on the total weight of the epoxy resin composition. If the content of the curing agent is less than 1% by weight, problems may occur in curability and moldability, and if the content exceeds 15% by weight, reliability may decrease due to an increase in moisture absorption, and the strength of the cured product may be relatively lowered.

Filler

In the present invention, the filler is a component for improving the strength of the encapsulant and lowering the moisture absorption, and a filler applicable in the art may be used without limitation. For example, a filler such as silica, silica nitride, alumina, aluminum nitride, boron nitride, etc. may be used alone or in combination of two or more, but is not limited thereto. The form of the filler is also not particularly limited, and both angular and spherical fillers may be used.

The average particle diameter of the filler is not particularly limited, but may be, for example, 5 to 30 μm. When considering the filling property in the mold, the maximum particle diameter of the filler may be 180 µm or less, for example, 150 µm or less.

The filler may be included in an amount of 80% by weight or more, for example, 80 to 90% by weight, based on the total weight of the epoxy resin composition. For example, based on the flowability of 30 inches or more, the filler may contain 80% by weight or more, for example, 80 to 88% by weight, and the filler based on the flowability of 20 inches or more and less than 30 inches, the filler is up to 90% by weight, e.g. For example, 88 to 90% by weight may be included. If the content of the filler is less than 80% by weight, the strength decreases due to an increase in moisture absorption, and adhesion may decrease after the reflow soldering process.If the content of the filler exceeds 90% by weight, the viscosity increases and the flowability decreases, resulting in moldability. This can be bad.

Hardening accelerator

The curing accelerator of the present invention may be used without particular limitation as long as it is commonly used in the art. For example, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole, amine compounds such as triethylamine, tributylamine, and benzyldimethylamine, Tertiary amine compounds such as 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undec-7-ene, and phenylphosphine Organic phosphine compounds such as pin, diphenylphosphine, triphenylphosphine, tributylphosphine, and tri(p-methylphenyl)phosphine may be used alone or in combination of two or more, but are not limited thereto. .

The content of the curing accelerator may be 0.05 to 1.0% by weight, for example, 0.05 to 0.5% by weight, based on the total weight of the epoxy resin composition. If the content of the curing accelerator is less than 0.05% by weight, curability may decrease, and if the content exceeds 1.0% by weight, flowability may decrease due to overcuring.

additive

The epoxy resin composition according to the present invention may additionally include additives generally used in the epoxy resin composition for semiconductor encapsulation within a range not departing from its purpose. Non-limiting examples of additives that can be used include coupling agents, colorants, release agents, modifiers, flame retardants, low stress agents, or mixtures of two or more thereof.

The epoxy resin composition of the present invention may exhibit excellent flame retardancy by itself due to the high filler content, but may further include a flame retardant in order to further improve the flame retardancy. Metal hydroxides as flame retardants; Phosphorus and nitrogen-containing organic compounds (e.g., resorcinol diphosphate, phosphate, phenoxyphosphazene, melamine cyanurate, and phenol melamine resin) may be used alone or in combination of two or more, but are limited thereto. no.

In addition, the epoxy resin composition of the present invention may further include a coupling agent such as epoxysilane-based, aminosilane-based, mercaptosilane-based, acrylicsilane-based, and vinylsilane-based for stable dispersion of organic and inorganic materials.

In addition, the epoxy resin composition of the present invention includes colorants such as carbon black and Bengala, hydrotalcite-based ion trapping agents, long-chain fatty acids, metal salts of long-chain fatty acids, paraffin wax, carnauba wax, release agents such as polyethylene wax, modifiers, and It may further include one or more additives selected from low stress agents such as modified silicone resin and modified polybutadiene.

The additive may be appropriately added within the content range known in the art, for example, 0.05 to 5% by weight based on the total weight of the epoxy resin composition, but is not limited thereto.

The epoxy resin composition according to the present invention can be prepared by a conventional method known in the art, for example, a melt-kneading method using a half-bari mixer, a kneader, a roll, a single-screw or twin-screw extruder, and a cone. For example, after uniformly mixing each component as described above, melt-mixing at a temperature of 80 to 130°C using a heat kneader, cooling to room temperature, pulverizing into a powder state, and blending By doing so, an epoxy resin composition can be obtained.

The epoxy resin composition according to the present invention has high heat resistance, a low coefficient of thermal expansion and a low high-temperature elastic modulus, and may include a high content of a filler (eg, 80% by weight or more). The epoxy resin composition of the present invention may have a glass transition temperature of 200° C. or higher, and a flowability (175° C., 70 kgf/㎠) of 25 inches or more, for example, 30 to 50 inches, which is a general semiconductor encapsulant use temperature. It can show excellent continuous workability below 180 ℃. In addition, the epoxy resin composition exhibits excellent electrical properties at high temperatures, and for example, the dielectric constant at 200° C. after curing may be 5.5 or less, for example, 4.0 to 5.5. In addition, the epoxy resin composition of the present invention may have an elastic modulus (260° C.) of 1.5 Gpa or less, for example, 1.2 Gpa or less.

Accordingly, the epoxy resin composition of the present invention is suitable for application to an encapsulant of a high-temperature driving power semiconductor.

<Semiconductor element>

The present invention provides a semiconductor device encapsulated by using the above-described epoxy resin composition.

The semiconductor device may be a transistor, a diode, a microprocessor, a semiconductor memory, a power semiconductor, or the like.

The method of encapsulating a semiconductor device using the epoxy resin composition of the present invention may be performed according to a conventional method in the art, such as a transfer mold, a compression mold, or an injection mold.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to the examples in any sense.

[Example 1-15]

After mixing each component according to the composition shown in Table 1 below, using a melt kneader (Kneader) to melt and mix at a temperature of 100 to 130 ℃, cooled to room temperature, pulverized into a powder state, and then subjected to a blending process Examples Epoxy resin compositions of 1-15 were obtained (unit:% by weight).

[Comparative Example 1-4]

An epoxy resin composition of Comparative Example 1-4 was obtained in the same manner as in Example, except for the composition shown in Table 2 below (unit: wt%).

A-1: Epoxy resin of Formula 2 (R1=R2=hydrogen group, n=4) (softening point: 95°C, epoxy equivalent: 260 g/eq, melt viscosity (150°C): 3 poise)

A-2: Epoxy resin of Formula 2 (R1=R2=methyl group, n=7) (softening point: 92°C, epoxy equivalent: 266 g/eq, melt viscosity (150°C): 2.8 poise)

A-3: Epoxy resin of Formula 4 (R1=R2=R3=methyl group) (softening point: 65°C, epoxy equivalent: 230 g/eq, melt viscosity (150°C): 2 poise)

A-4: Epoxy resin of formula 3 (softening point: 65 ℃, epoxy equivalent: 250 g/eq, melt viscosity (150 ℃): 2.5 poise)

A-5: naphthalene-type epoxy resin (softening point: 75°C, epoxy equivalent: 203 g/eq, melt viscosity (150°C): 4 poise)

B-1: Benzooxazine of formula 5a (softening point: 78°C)

B-2: polyfunctional phenolic resin (softening point: 83°C)

B-3: Phenol novolac resin (softening point: 84°C)

C: silica (SiO ₂ ) (average particle diameter: 19.9 μm)

D: imidazole type (2MZ, Shikoku Chemical)

E-1: Carbon black

E-2: Carnauba wax (CAR-WAX, KAHL GMBH&CO.KG)

E-3: Epoxy silane (S-510, CHISSO Corporation)

E-4: Aluminum hydroxide

[Experimental Example-Evaluation of Physical Properties]

The physical properties of the epoxy resin compositions prepared in Examples 1-15 and Comparative Examples 1-4 were measured as follows, and the results are shown in Table 3-4 below. Specimens for the evaluation of physical properties were prepared by molding the epoxy resin composition powder prepared in each of the Examples and Comparative Examples at 175°C for 120 seconds by a transfer molding method, followed by curing at 190°C for 6 hours.

Spiral flow

Epoxy resin compositions prepared according to each of the Examples and Comparative Examples were evaluated using a mold for evaluation according to EMMI-1-66, and flowability was measured using a transfer molding press at 175° C. and 70 kgf/cm 2.

Glass transition temperature (Tg) / coefficient of thermal expansion (CTE)

Specimens of the same size were molded and measured using TMA (Thermo-mechanical Analyzer). TA's'TMA Q400' was used to measure from room temperature to 300°C at a temperature increase rate of 10°C/min, and the glass transition temperature was calculated using an onset point technique. In addition, the coefficient of thermal expansion was measured based on the 80 to 120°C section.

Dielectric constant (Dk)

Using a circular specimen having a diameter of 30 mm and a thickness of 2 mm, the dielectric constant was measured from 30° C. to 240° C. after post-curing. Measurement conditions were 1 Hz and AC 1.5V.

Modulus of elasticity

Specimens of the same size were molded and measured using a dynamic-mechanical analyzer (DMA). A storage modulus measured from room temperature to 300°C at a temperature increase rate of 10°C/min was used using Perkin Elmer's'DMA8000'.

As can be seen from the results of Table 3-4, it can be seen that the epoxy resin composition according to the embodiment exhibits excellent overall physical properties compared to the epoxy resin composition of the comparative example. Specifically, it can be seen that the epoxy resin composition of the embodiment according to the present invention has a high glass transition temperature after curing, exhibits excellent heat resistance, low coefficient of thermal expansion and high temperature elasticity, and exhibits excellent electrical properties at high temperatures.

Claims (9)

As an epoxy resin composition comprising an epoxy resin, a curing agent, a filler and a curing accelerator,
The epoxy resin includes a fluorene-containing epoxy resin,
The fluorene-containing epoxy resin is an epoxy resin composition comprising an epoxy resin represented by the following formula (2):
<Formula 2>

In the above formula,
R1 to R2 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms,
n is an integer of 2 to 10. delete The epoxy resin composition of claim 1, wherein the fluorene-containing epoxy resin further comprises an epoxy resin represented by the following Formula 3:
<Formula 3>

In the above formula,
R1 to R2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. The epoxy resin composition according to claim 1, wherein the fluorene-containing epoxy resin has a melt viscosity of 3 poise or less at 150° C., a softening point of 50 to 100° C., and an epoxy equivalent of 150 to 400 g/eq. The epoxy resin composition according to claim 1, comprising 30 to 100% by weight of the fluorene-containing epoxy resin based on the total weight of the epoxy resin. The epoxy resin composition of claim 1, wherein the epoxy resin further comprises an epoxy resin represented by Formula 4:
<Formula 4>

In the above formula,
R ₁ -R ₃ are each independently a C 1 to C 6 alkyl group or a C 1 to C 6 alkoxy group,
R ₄ -R ₁₉ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. The method of claim 3, wherein the epoxy resin further comprises an epoxy resin represented by the following formula (4),
The epoxy resin composition in which the mixing ratio of the epoxy resin represented by Formula 2, the epoxy resin represented by Formula 3, and the epoxy resin represented by Formula 4 is 1: 0.1 to 1.5: 0.1 to 1.5 weight ratio:
<Formula 4>

In the above formula,
R ₁ -R ₃ are each independently a C 1 to C 6 alkyl group or a C 1 to C 6 alkoxy group,
R ₄ -R ₁₉ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. The method of claim 1, wherein the glass transition temperature is 200°C or higher, the dielectric constant at 200°C after curing is 5.5 or lower, the flowability (175°C, 70 kgf/cm2) is 25 inches or more, and the elastic modulus (260°C) Epoxy resin composition of 1.5 Gpa or less. A semiconductor device encapsulated by using the epoxy resin composition according to any one of claims 1, 3 to 8.