WO2019132176A1 - Thermoplastic resin composition for sealing semiconductor device and semiconductor device sealed using same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition for sealing a semiconductor device, the composition containing a maleimide compound, a benzoxazine compound, a compound of chemical formula 4, and an inorganic filler, and to a semiconductor device sealed using the same.

Description

A thermosetting resin composition for sealing a semiconductor element and a semiconductor element sealed using the composition

TECHNICAL FIELD The present invention relates to a thermosetting resin composition for sealing semiconductor devices and a semiconductor device sealed with the composition. More particularly, the present invention relates to a thermosetting resin composition for sealing a semiconductor element which is excellent in curing degree, fluidity and storage stability, and a semiconductor element sealed using the composition.

Recently, a package for a power device is considering changing the chip specification from Si to SiC. A semiconductor device for a power device using an SiC chip can operate stably even under a high temperature environment of 200 占 폚 or more and therefore a sealing material of such a semiconductor device is also required to have a high heat resistance of 200 占 폚 or more. A resin composition for sealing of a combination of an epoxy resin and a phenol curing agent has been widely used as a sealing material of a conventional semiconductor device. However, the conventional sealing material has a glass transition temperature of about 230 캜 and satisfies the heat resistance required in current power device packages I can not do that. Recently, research and commercialization of a combination of a maleimide compound and a benzoxazine compound or a combination of a maleimide compound, a benzoxazine compound and an epoxy resin have been actively pursued in order to satisfy heat resistance characteristics required in a package for a power device. The cured product of the thermosetting resin resin composition for sealing a semiconductor element has a high glass transition temperature and a high heat resistance temperature, an excellent electrical property and flame retardancy, a low thermal decomposition property, and a low curing shrinkage and a low thermal expansion coefficient. However, in the case of the above thermosetting resin composition, the reactivity is much slower than the combination of the epoxy resin and the phenol curing agent. Therefore, in order to secure the quick curing property required for the semiconductor device sealing material, the curing should be performed well in a short curing time.

SUMMARY OF THE INVENTION A thermosetting resin composition for sealing a semiconductor device which is excellent in curing degree, fluidity and storage stability.

Another object of the present invention is to provide a semiconductor device sealed with the above-mentioned thermosetting resin composition.

The thermosetting resin composition for sealing a semiconductor device of the present invention includes a maleimide compound, a benzoxazine compound, a compound represented by the following formula (4), and an inorganic filler:

≪ Formula 4 >

R ₄ , R ₅ , R ₆ , R ₇ , W, Z, l, m and n are as defined in the description of the present invention.

The present invention provides a semiconductor device sealed with a thermosetting resin composition for sealing a semiconductor device according to the present invention.

The present invention A thermosetting resin composition for sealing a semiconductor device which is excellent in curing degree, fluidity and storage stability.

The present invention provides a semiconductor device sealed with a thermosetting resin composition as described above.

It is preferable that the mold curing time of the thermosetting resin composition for sealing a semiconductor element formed by the transfer molding method is within 100 seconds at the set temperature. In this case, the curing property of the thermosetting resin composition for sealing a semiconductor element is favorable, and in particular, it becomes easy to mold a thermosetting resin composition for sealing a semiconductor element and to obtain a cured product. Therefore, it is preferable to apply a curing catalyst suitable for the combination of a maleimide compound and a benzoxazine compound or a combination of a maleimide compound, a benzoxazine compound, and an epoxy resin in order to satisfy such required characteristics. For example, the curing catalyst may contain one or more components selected from the group consisting of an imidazole-based catalyst, a phosphorus-based catalyst, a boron-based catalyst, a Lewis acid, and an acid catalyst. However, since there is a problem that the reaction rate of the thermosetting resin composition is very low, an imidazole-based catalyst having a high reaction rate has been used so far as a material for sealing semiconductor devices. However, when the imidazole-based catalyst having a fast reaction time is used, there is a problem that the storage stability is lowered when the composition is allowed to stand at room temperature, and the toughness of the composition using the imidazole-based catalyst is lowered.

The present inventors have found that the curing degree, fluidity and storage stability of the thermosetting resin composition containing the maleimide compound, the benzoxazine compound and the inorganic filler are improved by incorporating the specific compound of the general formula (4).

Hereinafter, the constituent components of the thermosetting resin composition for sealing semiconductor devices according to the present invention will be described in detail.

Maleimide compound

The maleimide compound is preferably a maleimide compound having at least two maleimide groups in the molecule.

In one embodiment, the maleimide compound may comprise a maleimide compound of formula 1:

≪ Formula 1 >

(In the formula 1,

n ₁ is an integer of 0 or more and 10 or less,

X ₁ each independently represents an alkylene group having 1 or more carbon atoms and 10 or less carbon atoms, a group represented by the following formula (A), -SO ₂ -, -CO-, an oxygen atom or a single bond,

≪ Formula (A)

(Wherein Y is a hydrocarbon group having 6 or more carbon atoms and 30 or less carbon atoms having an aromatic ring and n ₂ is an integer of 0 or more)

R ₁ each independently represents a hydrocarbon group having 1 to 6 carbon atoms,

a is independently an integer of 0 to 4,

b is independently an integer of 0 or more and 3 or less.

X ₁ is an alkylene group having 1 or more carbon atoms and 10 or less carbon atoms, preferably 1 or more carbon atoms and 7 or less carbon atoms, and more preferably 1 or more carbon atoms and 3 or less carbon atoms, and is not particularly limited, A chain alkylene group is preferred. Specific examples of the straight chain alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decaneylene group, a trimethylene group, A methylene group, and a hexamethylene group. In addition, specifically, as the alkyl group of the branched chain is -C (CH _{3) 2} - (isopropylene _{group), -CH (CH 3) -} , -CH (CH 2 CH 3) -, -C (CH 3) ( CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) ₂ -; _{-CH (CH 3) CH 2 -} , -CH (CH 3) CH (CH 3) -, -C (CH 3) 2 CH 2 -, -CH (CH 2 CH 3) CH 2 -, -C (CH ₂ CH ₃ ) ₂ -CH ₂ -, and the like.

Each R ₁ is preferably independently an aliphatic hydrocarbon group having 1 to 6 carbon atoms and an aliphatic hydrocarbon group having 1 to 2 carbon atoms, specifically, a methyl group or an ethyl group.

a is independently an integer of 0 or more and 4 or less, or an integer of 0 or more and 2 or less, more preferably 0. B is independently an integer of 0 or more and 3 or less, more preferably 0 or 1,

n ₁ is an integer of 0 or more and 10 or less, an integer of 0 or more and 6 or less, an integer of 0 or more and 4 or less, or an integer of 0 or more and 3 or less. Further, it is more preferable that the maleimide compound contains at least a compound having n ₁ of 1 or more in the formula (1).

In the above formula (A), Y is a hydrocarbon group having 6 or more carbon atoms and 30 or less carbon atoms having an aromatic ring, and n ₂ is an integer of 0 or more. The hydrocarbon group having 6 or more carbon atoms and 30 or less carbon atoms having the aromatic ring may be composed solely of an aromatic ring or may have a hydrocarbon group other than an aromatic ring. Y may be an aromatic ring or two or more aromatic rings, and when two or more aromatic rings are the same, these aromatic rings may be the same or different. The aromatic ring may be either a monocyclic structure or a polycyclic structure. Specific examples of the hydrocarbon group having 6 or more and 30 or less carbon atoms having an aromatic ring include benzene, biphenyl, naphthalene, anthracene, fluorene, phenanthrene, indacene, terphenyl, acenaphthylene, Of a compound having an aromatic group by removing two hydrogen atoms from the nucleus. These aromatic hydrocarbon groups may have a substituent. Here, the aromatic hydrocarbon group having a substituent means that a part or all of the hydrogen atoms constituting the aromatic hydrocarbon group are substituted with a substituent. As the substituent, for example, an alkyl group can be mentioned. The alkyl group as the substituent is preferably a linear alkyl group. It is particularly preferable that the number of carbon atoms is 1 or more and 10 or less, 1 or more and 6 or less, or 1 or more and 4 or less. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl and sec-butyl. n ₂ is an integer of 0 or more and 10 or less, an integer of 0 or more and 6 or less, an integer of 0 or more and 4 or less, or an integer of 0 or more and 3 or less.

Y may preferably have a group excluding two hydrogen atoms from benzene or naphthalene, and the group represented by the formula (A) may preferably be a group represented by any one of the following formulas (A1) and (A2).

≪ Formula (A1)

≪

(In the formulas (A1) and (A2), R ₄ is independently a hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, and e is an integer independently of 0 or more and 4 or less.

In one embodiment, the maleimide compound of Formula 1 is a compound wherein X ₁ is a linear or branched alkylene group having ₁ to 3 carbon atoms and R ₁ is a hydrocarbon group having 1 or 2 carbon atoms , a is an integer of 0 or more and 2 or less, b is 0 or 1, and n ₁ is an integer of 0 or more and 4 or less.

Preferred examples of the maleimide compound represented by Formula 1 include maleimide compounds represented by Formula 1-1:

≪ Formula 1-1 >

(In the above formula (1-1), n ₁ is an integer of 0 or more and 10 or less).

The maleimide compound of the present invention may contain a maleimide compound of a different kind from the maleimide compound of the above formula (1).

In one embodiment, the maleimide compound is, for example, 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2-bis [4- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylene bismaleimide, N, N ' (4-maleimidophenyl) sulfone, 3,3-dimethyl-5, 5-diethyl (2-ethylhexyl) -4,4-diphenylmethane bismaleimide, and bisphenol A diphenyl ether bismaleimide; a compound having two or more maleimide groups in the molecule such as polyphenylmethane maleimide; Compounds and the like.

In other embodiments, the maleimide compounds include 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, hexamethylenediamine bismaleimide, N, N'-1,2- Aliphatic maleimide compounds such as maleimide, N, N'-1,3-propylene bismaleimide and N, N'-1,4-tetramethylene bismaleimide; Imide-extended bismaleimide, and the like. Of these, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, imide-extended bismaleimide is particularly preferred. The maleimide compound may be used alone or in combination of two or more.

Preferably, the maleimide compound of Formula 1 may be used.

Maleimide compound The weight average molecular weight of (Mw) may be from about 2,500 up to about 400, at least about 4,000 or less, preferably about 800 or more. Within the above range, handling and fluidity can be ensured.

The maleimide compound may be prepared by reacting a maleimide compound with an amine compound, or may use a commercially available product.

The maleimide compound may be included in the thermosetting resin composition for sealing a semiconductor element in an amount of about 1 wt% to about 25 wt%, for example, about 3 wt% to about 20 wt%. Within this range, there may be a dielectric constant reduction and a glass transition temperature synergistic effect.

Benzoxazine compound

Benzoxazine compounds may include one or more of the following compounds of Formula 2, compounds of Formula 3A, and compounds of Formula 3B:

(2)

(In the formula 2,

X ₂ is an alkylene group having 1 or more carbon atoms and 10 or less carbon atoms, a hydrocarbon group having 6 or more carbon atoms and 30 or less carbon atoms having a group represented by the formula A, -SO ₂ -, -CO-, an oxygen atom, a single bond or an aromatic ring Lt; / RTI &

R ₂ each independently represents a hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms,

and c is independently an integer of 0 or more and 4 or less.

≪ Formula 3 >

≪ Formula 3B >

(In the above formulas (3A) and (3B)

X ₃ is an alkylene group having 1 or more carbon atoms and 10 or less carbon atoms, a group represented by the formula A, -SO ₂ -, -CO-, an oxygen atom, a single bond or an aromatic ring, A hydrocarbon group,

R ₃ is independently a hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms,

and d is independently an integer of 0 to 5).

X ₂ and X ₃ each independently represent an alkylene group having at least 1 carbon atom and not more than 10 carbon atoms, preferably not less than 1 but not more than 7, more preferably not less than 1 and not more than 3, but is not particularly limited, and linear or branched An alkylene group is preferred. Specific examples of the straight chain alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decaneylene group, a trimethylene group, A methylene group, and a hexamethylene group. In addition, specifically, as the alkyl group of the branched chain is -C (CH _{3) 2} - (isopropylene _{group), -CH (CH 3) -} , -CH (CH 2 CH 3) -, -C (CH 3) ( CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) ₂ -; _{-CH (CH 3) CH 2 -} , -CH (CH 3) CH (CH 3) -, -C (CH 3) 2 CH 2 -, -CH (CH 2 CH 3) CH 2 -, -C (CH ₂ CH ₃ ) ₂ -CH ₂ -, and the like.

X ₂ and X ₃ may be a hydrocarbon group having 6 or more carbon atoms and 30 or less carbon atoms having an aromatic ring such as phenyl, biphenyl, fluorene, naphthalenyl, and the like.

Each of R ₂ and R ₃ is preferably an aliphatic hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, and an aliphatic hydrocarbon group having 1 or 2 carbon atoms, specifically, a methyl group or an ethyl group.

c and d are each independently an integer of 0 or more and 5 or less, or an integer of 0 or more and 2 or less, more preferably 0.

Preferable specific examples of the benzoxazine compound may include, for example, at least one of the following formulas (2-1), (2-2), (2-3), (3-1)

≪ Formula (2-1)

≪ Formula (2-2)

<Formula 2-3>

(Wherein R is a hydrocarbon group having 1 to 6 carbon atoms)

&Lt; Formula 3-1 >

(3-2)

<Formula 3-3>

Benzoxazine photo-compounds can be prepared by conventional methods known to those skilled in the art or commercially available products can be used.

The benzoxazine compound may be included in the thermosetting resin composition for sealing semiconductor devices in an amount of about 0.1 wt% to about 10 wt%, for example, about 0.5 wt% to about 5 wt%. Within this range, there may be a dielectric constant reducing effect.

The compound of formula 4

The compound of formula (IV) can improve the cure degree, storage stability and fluidity of a composition comprising a maleimide compound, a benzoxazine compound and an inorganic filler. In addition, the compound of Formula 4 can increase the toughness of a composition comprising a maleimide compound and a benzoxazine compound and an inorganic filler:

&Lt; Formula 4 >

(In the formula 4,

R ₄ , R ₅ , R ₆ and R ₇ are each independently a substituted or unsubstituted C 1 to C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C 6 to C 30 aromatic hydrocarbon group, A substituted C1 to C30 aliphatic hydrocarbon group or a substituted or unsubstituted C1 to C30 aromatic hydrocarbon group containing a hetero atom,

W and Z each independently represent a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group containing a hetero atom Or a substituted or unsubstituted C1 to C30 aromatic hydrocarbon group containing a hetero atom,

l is an integer of 0 to 4,

m is an integer of 1 to 6,

and n is an integer of 1 to 5).

Preferably, R ₄ , R ₅ , R ₆ , and R ₇ in Formula 4 may be a C6 to C30 aryl group unsubstituted or substituted with a hydroxy group. "Substituted" for R ₄ , R ₅ , R ₆ , and R ₇ in Formula 4 is one in which at least one hydrogen atom is substituted with a C 6 to C 10 aryl group, a hydroxy group, a cyano group (CN) it means.

Preferably, W in Formula 4 may be a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group. For W in Formula 4, "substituted" means that at least one hydrogen atom is replaced by an aryl group, a hydroxy group, a cyano group, or a C1 to C10 alkyl group. The C6 to C30 aromatic hydrocarbon group may be an C6 to C30 aryl group or an C6 to C30 aryl ketone group. In embodiments, the C6 to C30 aromatic hydrocarbon group may be a phenyl group or a benzophenone group.

Preferably, Z in Formula 4 may be a substituted or unsubstituted C6 to C30 aryl group. In an embodiment, the C6 to C30 aryl group may be a phenyl group, a biphenyl group, a fluorenyl group or bis (phenyl) fluorenyl. "Substituted" for Z in the above formula (4) means that at least one hydrogen atom is substituted with a C6 to C10 aryl group, a hydroxy group , a cyano group or a C1 to C10 alkyl group.

In one embodiment, the compound of Formula 4 may comprise one or more of the following Formulas 4-1 to 4-6:

<Formula 4-1>

<Formula 4-2>

<Formula 4-3>

<Formula 4-4>

<Formula 4-5>

<Formula 4-6>

The compound of formula (IV) can be prepared by a conventional method known to a person skilled in the art.

The compound of Formula 4 is included in the thermosetting resin composition for sealing a semiconductor device in an amount of about 0.01 wt% to about 5 wt%, for example, about 0.02 wt% to about 1.5 wt%, such as about 0.05 wt% to about 1 wt% . Within the above range, there may be an effect of high curing degree, excellent storage stability, and excellent fluidity.

Inorganic filler

The inorganic filler is intended to improve the mechanical properties of the composition and achieve low stress. The inorganic filler may be any inorganic filler commonly used in semiconductor encapsulants and is 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, spherical fused silica having an average particle diameter of about 5 to about 3 占 퐉 and about 50 to about 99% by weight of spherical fused silica having an average particle diameter of about 0.001 to about 1 占To about 100% by weight, based on the total filler, of a fused silica mixture comprising from about 1% to about 50% by weight of the composition. Further, the maximum particle diameter can be adjusted to any one of about 45 탆, about 55 탆, and about 75 탆, depending on the application. Since the spherical fused silica may contain conductive carbon as a foreign substance on the surface of the silica, 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 embodiments, the inorganic filler may comprise from about 70 wt% to about 95 wt%, such as from about 75 wt% to about 94 wt%, or from about 80 wt% to about 93 wt%, of the thermosetting resin composition for encapsulating semiconductor devices . Within this range, there can be obtained an effect of ensuring the fluidity and reliability of the composition.

The thermosetting resin composition for sealing a semiconductor device may further include at least one of a coupling agent, a releasing agent, a colorant, an antioxidant, a flame retardant, and a stress relaxation agent.

Coupling agent

The coupling agent is for improving the interface strength by reacting with a maleimide compound, a benzoxazine compound and an inorganic filler, and may be, for example, a silane coupling agent. The silane coupling agent is not particularly limited as long as it reacts with the maleimide compound, the benzoxazine compound and the inorganic filler to improve the interface strength between the maleimide compound and the benzoxazine compound and the inorganic filler. Specific examples of the silane coupling agent include epoxy silane, aminosilane, ureidosilane, mercapto silane, and alkyl silane. The coupling agent may be used alone or in combination.

The coupling agent may be included in the thermosetting resin composition for encapsulating semiconductor devices in an amount of about 0.01 wt% to about 5 wt%, preferably about 0.05 wt% to about 3 wt%. The strength of the cured product of the thermosetting resin composition for sealing semiconductor devices can be improved in the above range.

Release agent

As the releasing 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 release agent may be included in the thermosetting resin composition for sealing a semiconductor element in an amount of about 0.1 wt% to about 1 wt%.

coloring agent

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

The colorant may be included in the thermosetting resin composition for encapsulating semiconductor devices in an amount of about 0.01 wt% to about 1 wt%, preferably about 0.05 wt% to about 0.5 wt%.

Stress relieving agent

The stress relieving agent may include a silicone-based compound such as silicone oil.

The stress relieving agent may be included in the thermosetting resin composition for encapsulating semiconductor devices in an amount of about 0.01 wt% to about 5 wt%, preferably about 0.05 wt% to about 3 wt%.

The thermosetting resin composition for sealing a semiconductor device of the present invention may contain an antioxidant such as Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane; A flame retardant such as aluminum hydroxide, and the like may be further added as needed.

The thermosetting resin composition for sealing a semiconductor device of the present invention may further comprise an epoxy resin.

Epoxy resin

As the epoxy resin, epoxy resins generally used for sealing semiconductor devices can be used and are not particularly limited. Specifically, as the epoxy resin, an epoxy compound containing two or more epoxy groups in the molecule can be used. For example, the epoxy resin is an epoxy resin obtained by epoxidating a condensate of phenol or alkyl phenol and hydroxybenzaldehyde, a phenol aralkyl type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a multifunctional epoxy Resin, naphthol novolak type epoxy resin, novolak type epoxy resin of bisphenol A / bisphenol F / bisphenol AD, glycidyl ether of bisphenol A / bisphenol F / bisphenol AD, bishydroxybiphenyl type epoxy resin, dicyclopenta Diene-based epoxy resins, and biphenyl-type epoxy resins. More specifically, the epoxy resin may include at least one of a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, a cresol novolak type epoxy resin, and a multifunctional epoxy resin. Most preferably, a polyfunctional epoxy resin can be used as the epoxy resin.

An epoxy resin having an epoxy equivalent of 100 g / eq to 500 g / eq can be used in consideration of the curing properties. Within the above range, the degree of curing can be increased.

The epoxy resin may be used alone or in combination. The epoxy resin may contain other components such as a maleimide compound, a benzoxazine compound, a curing accelerator, a releasing agent, a coupling agent, and a stress relieving agent, and a line such as a melt master batch It can also be used in the form of an additional compound made by the reaction.

The epoxy resin may be included in the thermosetting resin composition for sealing a semiconductor device in an amount of about 20% by weight or less, for example, about 0.5% by weight to about 10% by weight, specifically about 0.5% by weight to about 5% by weight. Within this range, the curability of the composition may not be deteriorated.

The thermosetting resin composition for sealing a semiconductor device is prepared by uniformly mixing the above components uniformly at a predetermined mixing ratio using a Hensel mixer or Lodige mixer and then kneading the mixture in a roll- kneaded in a kneader, and then cooled and pulverized to obtain a final powder product.

The thermosetting resin composition of the present invention as described above is usefully applied to semiconductor devices, particularly semiconductor devices mounted on mobile displays or automobile fingerprint recognition sensors. As a method of sealing a semiconductor element using the thermosetting 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.

The semiconductor device according to the present invention can be sealed with the thermosetting resin composition for sealing semiconductor devices of the present invention.

The semiconductor device according to the present invention may include a semiconductor element sealed with the thermosetting resin composition for sealing a semiconductor device of the present invention.

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.

Production Example 1

100 g of triphenylphosphine, 60 g of 4-bromophenol and 3.7 g of NiBr ₂ were placed in a 1 L round bottom flask, and 130 g of ethylene glycol was added thereto, followed by reaction at 180 ° C for 6 hours to obtain a phenol-substituted phosphonium bromide salt. 21.4 g of 2,4-dihydroxybenzophenone and 18.4 g of 2,2-biphenol were placed in 50 g of MeOH, 21.6 g of 25% sodium methoxide solution was added, and the mixture was completely dissolved while reacting at room temperature for 30 minutes. 43.5 g of the above-prepared phenol-substituted phosphonium bromide salt, which had been previously dissolved in 50 g of methanol, was gradually added to the mixed solution, and further reacted for 1 hour. 300 g of distilled water was then added. The resulting white solid was filtered to give 68 g. As a result of NMR measurement, it was confirmed to be a compound of the following formula 4-5. (2H, d), 7.32 (2H, d), 7.28 (2H, d), 7.70 (2H, dd), 6.34 (1H, d), 6.21 (1H, s), 7.02-7.24 )

<Formula 4-5>

Production Example 2

23.0 g of 2,3,4-trihydroxybenzophenone and 12.4 g of pyrogallol were placed in 50 g of MeOH, 21.6 g of 25% sodium methoxide solution was added, and the mixture was completely dissolved while reacting at room temperature for 30 minutes. To this mixed solution, 41.9 g of tetraphenylphosphonium bromide previously dissolved in 50 g of methanol was slowly added thereto, followed by further reaction for 1 hour, and then 300 g of distilled water was added. The resulting brown solid was filtered to yield 61 g. As a result of NMR measurement, it was confirmed to be a compound of the following formula 4-4. (1H, d), 6.55-6.50 (2H, m), 7.60 (2H, d), 7.32-7.27 m), &lt; / RTI &gt; 6.06 (2H, d)

<Formula 4-4>

Production Example 3

After dissolving 19.8 g of terephthalic acid in 237 mL of 1M NaOH aqueous solution, 30.1 g of pyrogallol previously dissolved in 100 mL of methanol and 100 g of tetraphenylphosphonium bromide were gradually added thereto, and the reaction was continued for 1 hour. The resulting precipitate was filtered and dried to give a pale brown solid 106 g of tetravalent phosphonium salt represented by the formula (5) was obtained.

&Lt; Formula 5 >

Production Example 4

1.7 g of catechol was dissolved in 50 ml of methanol and stirred at room temperature. 1.8 g NaOMe (20% in MeOH) was added dropwise. The mixture was stirred for 1 hour at room temperature and 1.7 g of Titanium (IV) butoxide was added. After stirring the mixture for 3 hours at room temperature, 4.3 g of (4-hydroxyphenyl) triphenyl-phosphonium bromide was dissolved in 5.0 mL of MeOH and reacted at room temperature for about 2 hours. After the reaction was completed, the insoluble solid was removed by filtration, and the solvent of the obtained solution was removed at a low pressure to obtain a compound represented by the following formula (6) and confirmed by NMR data.

(6)

^{1 H NMR (400 MHz, DMSO} ) 7.93-7.86 (m, 6H), 7.80-7.63 (m, 24H), 7.20-7.13 (m, 4H), 6,68 (m, 4H), 6.16 (m, 6H ), 5.94 (m, 6 H) ppm; ¹³ C NMR (100 MHz, DMSO) 158.0, 144.5, 138.7, 137.4, 137.2, 128.9, 128.8, 122.8, 117.3, 115.9 ppm; ³¹ P NMR (166 MHz, DMSO) 24.20 ppm; LC-MS m / z = 1082 (M ^&lt; ⁺ &gt;); Anal. Calcd for C ₆₆ H ₅₂ O ₈ P ₂ Ti: C, 73.20; H, 4.84. Found: C, 73.38; H, 4.59.

Production Example 5

41.9 g of tetraphenylphosphonium bromide and 55 g of ethylenediaminetetraacetic acid chelated iron (III) sodium salt were dissolved in 200 mL of ethanol and 200 mL of distilled water, respectively. The two solutions were mixed and reacted at 25 ° C for 24 hours. After that, ethanol and water were removed by distillation under reduced pressure, and dichloromethane was added again. Then, dichloromethane was distilled under reduced pressure to obtain 54.0 g of a pale red powder of the following formula (7).

&Lt; Formula 7 >

Production Example 6

100 g of catechol and 200 mL of dichloromethane were placed in a 1 L round bottom flask, and 85 mL of TEA (triethylamine) was added. A solution of 63 mL of chlorodiphenylphosphate in 200 mL of DCM was slowly added dropwise to the previously prepared solution. After further reaction at room temperature for 3 hours, the resulting solid was filtered, washed with water and dried to obtain 125 g of a white solid (p1) in the form of an ammonium salt. Next, 50 g of p1 was added to a 1 L round bottom flask, 100 mL of MeOH was added, and 20 mL of a 5 M aqueous NaOH solution was added while mixing, followed by heating at 60 DEG C for 30 minutes. When p1 was completely dissolved, 46 g of tetraphenylphosphonium bromide dissolved in 100 mL of MeOH was added dropwise and reacted for 2 hours. Thereafter, the temperature was lowered to room temperature, and 500 mL of distilled water was dropped. The resulting solid was filtered with a filter, washed with water and dried to obtain 61 g of a tetravalent phosphonium salt of the following formula (8) as a white solid.

(8)

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

Maleimide compound

(A) polyfunctional maleimide, BMI-2300, Daiwakasei DKK Industry. Compounds of the formula

(n is an integer of 1 to 10)

Benzoxazine compound

(B) P-d type benzoxazine, available from Shikoku Chemicals. Compounds of the formula

Epoxy resin

(C) Multifunctional epoxy resin, EPPN-501HY, Nippon Kayaku

The compound of formula 4

(D1) Compound of formula 4-5 of Preparation Example 1

(D2) To a solution of the compound of formula 4-4

Inorganic filler

(E) A 9: 1 mixture of spherical fused silica having an average particle diameter of 18 mu m and spherical fused silica having an average particle diameter of 0.5 mu m

coloring agent

(F) Carbon black MA-600, manufactured by Matsusita Chemical Co.

Coupling agent

(G) mercaptopropyltrimethoxysilane, KBM-803, Shinetsu

Release agent

(H) Carnauba wax

Other compounds

(D3) Triphenyl phosphine, Hokko Chemical

(D4) TPP-K, Hokko Chemical Co.

(D5) To a solution of the compound of formula 5

(D6) To a solution of the compound of formula 6

(D7) To a solution of the compound of formula 7

(D8) To a solution of the compound of formula 8

Examples and Comparative Examples

Each of the above components was weighed according to the composition (unit: parts by weight) 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 90 ° C to 110 ° C using a continuous kneader, followed by cooling and pulverization, thereby preparing a thermosetting resin composition for sealing a semiconductor device.

	Example				Comparative Example
	One	2	3	4	One	2	3	4	5	6	7	8
(A)	10.4	10.4	10.4	10.4	10.4	10.4	10.4	10.4	10.4	10.4	10.4	10.4
(B)	2.6	1.3	2.6	1.3	2.6	1.3	2.6	1.3	2.6	2.6	2.6	2.6
(C)	-	1.3	-	1.3	-	1.3	-	1.3	-	-	-	-
(D1)	0.5	0.5	-	-	-	-	-	-	-	-	-	-
(D2)	-	-	0.5	0.5	-	-	-	-	-	-	-	-
(D3)	-	-	-	-	0.5	0.5	-	-	-	-	-	-
(D4)	-	-	-	-	-	-	0.5	0.5	-	-	-	-
(D5)	-	-	-	-	-	-	-	-	0.5	-	-	-
(D6)	-	-	-	-	-	-	-	-	-	0.5	-	-
(D7)	-	-	-	-	-	-	-	-	-	-	0.5	-
(D8)	-	-	-	-	-	-	-	-	-	-	-	0.5
(E)	85.5	85.5	85.5	85.5	85.5	85.5	85.5	85.5	85.5	85.5	85.5	85.5
(F)	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
(G)	0.4	0.4	0.4	0.4	0.4	0.4	0.4	0.4	0.4	0.4	0.4	0.4
(H)	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3

The physical properties of the compositions of the examples and comparative examples thus prepared were measured according to the following properties evaluation methods. The measurement results are shown in Tables 2 and 3.

Property evaluation method

(1) Hardness (Shore D hardness): Using a MPL (Multi Plunger System) molding machine equipped with a mold for a TQFP (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 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 padding on the mold. The higher the value, the better the degree of cure.

(2) Fluidity (Spiral flow): The composition was injected into a mold for spiral flow measurement according to EMMI-1-66 at a molding temperature of 175 캜 and a molding pressure of 70 kgf / cm ² using a low pressure transfer molding press, (Length of idle motion) (unit: inch) was measured. The higher the measured value, the better the fluidity.

(3) Storage stability: The flow length was measured in the same manner as in the fluidity measurement in (2) at intervals of 24 hours while the composition was stored in a constant temperature and humidity setter at 25 ° C / 50RH% for 1 week, Percentage (%) was obtained. The larger this percentage value, the better the storage stability.

		Example
		One	2	3	4
Degree of hardening	50s	64	68	68	70
	60s	72	74	76	78
	70s	76	78	80	82
	80s	80	80	82	84
	90s	80	80	82	84
liquidity		68	72	70	72
Storage stability	24hr	96	97	97	96
	48hr	92	92	93	93
	72hr	88	89	87	89

		Comparative Example
		One	2	3	4	5	6	7	8
Degree of hardening	50s	Uncured	Uncured	Uncured	Uncured	Uncured	Uncured	Uncured	Uncured
	60s	55	60	Uncured	Uncured	Uncured	Uncured	Uncured	Uncured
	70s	60	64	Uncured	Uncured	35	Uncured	Uncured	Uncured
	80s	64	68	Uncured	Uncured	48	Uncured	40	Uncured
	90s	65	70	Uncured	Uncured	65	Uncured	52	Uncured
liquidity		45	48	-	-	65	-	70	-
Storage stability	24hr	88	88	-	-	96	-	98	-
	48hr	72	75	-	-	90	-	94	-
	72hr	68	64	-	-	85	-	90	-

As shown in Table 2, the thermosetting resin composition for sealing a semiconductor device of the present invention had a high degree of curing and was excellent in storage stability and fluidity.

On the other hand, as shown in Table 3, Comparative Example 1 or 2 including phosphine which is not a phosphonium salt had a problem of lowering of hardenability and storage stability. Comparative Example 3 or 4 including a phosphine other than a phosphonium salt was not cured within 90 seconds.

Comparative Example 6 or 8 containing a phosphonium salt other than the compound of the formula (4) was not cured within 90 seconds. Comparative Example 5 or 7 containing a phosphonium salt other than the compound of the formula (4) had a problem of lowering the curing degree although the curing was possible within 90 seconds.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (9)

1. A thermosetting resin composition for sealing a semiconductor device, comprising: a maleimide compound, a benzoxazine compound, a compound represented by the following formula (4), and an inorganic filler:

   &Lt; Formula 4 >

   

   (In the formula 4,

   R ₄ , R ₅ , R ₆ and R ₇ are each independently a substituted or unsubstituted C 1 to C 30 aliphatic hydrocarbon group, a substituted or unsubstituted C 6 to C 30 aromatic hydrocarbon group, A substituted C1 to C30 aliphatic hydrocarbon group or a substituted or unsubstituted C1 to C30 aromatic hydrocarbon group containing a hetero atom,

   W and Z each independently represent a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group, a substituted or unsubstituted C6 to C30 aromatic hydrocarbon group, a substituted or unsubstituted C1 to C30 aliphatic hydrocarbon group containing a hetero atom Or a substituted or unsubstituted C1 to C30 aromatic hydrocarbon group containing a hetero atom,

   l is an integer of 0 to 4,

   m is an integer of 1 to 6,

   and n is an integer of 1 to 5).
2. The thermosetting resin composition for sealing a semiconductor device according to claim 1, wherein the compound of Formula 4 is contained in the thermosetting resin composition for sealing a semiconductor device in an amount of about 0.01 wt% to about 5 wt%.
3. The thermosetting resin composition for sealing a semiconductor device according to claim 1, wherein the compound of formula (4) comprises at least one of the following formulas (4-1) to (4-6)

   <Formula 4-1>

   

   <Formula 4-2>

   

   <Formula 4-3>

   

   <Formula 4-4>

   

   <Formula 4-5>

   

   <Formula 4-6>

   

   .
4. The thermosetting resin composition for sealing a semiconductor device according to claim 1, wherein the maleimide compound comprises a maleimide compound represented by the following formula (1)

   &Lt; Formula 1 >

   

   (In the formula 1,

   n ₁ is an integer of 0 or more and 10 or less,

   X ₁ each independently represents an alkylene group having 1 or more carbon atoms and 10 or less carbon atoms, a group represented by the following formula (A), -SO ₂ -, -CO-, an oxygen atom or a single bond,

   &Lt; Formula (A)

   

   (Wherein Y is a hydrocarbon group having 6 or more carbon atoms and 30 or less carbon atoms having an aromatic ring and n ₂ is an integer of 0 or more)

   R ₁ each independently represents a hydrocarbon group having 1 to 6 carbon atoms,

   a is independently an integer of 0 to 4,

   b are each independently an integer of 0 to 3).
5. The thermosetting resin composition for sealing a semiconductor device according to claim 1, wherein the benzoxazine compound comprises at least one compound selected from the group consisting of a compound represented by the following general formula (2), a compound represented by the following general formula (3A)

   (2)

   

   (In the formula 2,

   X ₂ is an alkylene group having 1 or more carbon atoms and 10 or less carbon atoms, a hydrocarbon group having 6 or more carbon atoms and 30 or less carbon atoms having a group represented by the formula A, -SO ₂ -, -CO-, an oxygen atom, a single bond or an aromatic ring Lt; / RTI &

   R ₂ each independently represents a hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms,

   and c is independently an integer of 0 or more and 4 or less.

   &Lt; Formula 3 >

   

   &Lt; Formula 3B >

   

   (In the above formulas (3A) and (3B)

   X ₃ is an alkylene group having 1 or more carbon atoms and 10 or less carbon atoms, a group represented by the formula A, -SO ₂ -, -CO-, an oxygen atom, a single bond or an aromatic ring, A hydrocarbon group,

   R ₃ is independently a hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms,

   and d is independently an integer of 0 to 5).
6. The thermosetting resin composition for sealing semiconductor devices according to claim 1, wherein the thermosetting resin composition for sealing semiconductor devices comprises about 1 wt% to about 25 wt% of the maleimide compound, about 0.1 wt% to about 10 wt% of the benzoxazine compound, From about 0.01 wt% to about 5 wt%, and from about 70 wt% to about 95 wt% of the inorganic filler.
7. The thermosetting resin composition for sealing a semiconductor element according to claim 1, wherein the thermosetting resin composition for sealing a semiconductor element further comprises an epoxy resin.
8. The thermosetting resin composition according to claim 7, wherein the epoxy resin is contained in the thermosetting resin composition for sealing the semiconductor element in an amount of about 0.5 wt% to about 10 wt%.
9. A semiconductor device sealed with the use of the thermosetting resin composition for sealing a semiconductor element according to any one of claims 1 to 8.