TWI666307B - Resin composition for encapsulation, semiconductor device and structure - Google Patents

Abstract

The sealing resin composition of the present invention includes: an epoxy resin (A); a phenol aralkyl resin (B) having a biphenyl group; and a compound (C) having only one phenolic hydroxyl group; and the compound (C) ) Contains a compound represented by the following formula (1);

Description

Resin composition for sealing, semiconductor device, and structure

The present invention relates to a sealing resin composition, a semiconductor device, and a structure.

The semiconductor device is formed, for example, by sealing and molding a semiconductor element mounted on a substrate using a sealing resin composition. As such a sealing resin composition, for example, an epoxy resin composition containing an epoxy resin may be used.

Patent Document 1 describes a technique related to a phenol novolac condensate used as a hardener for an epoxy resin.

Patent Document 1: Japanese Unexamined Patent Publication No. 8-143648

In order to stably seal a semiconductor element, it is required to improve the moldability of the resin composition for sealing. The present inventor One of the indicators is to study the suppression of residual material retention during seal forming. The so-called residual material retention refers to the phenomenon that the residual material adheres to the plunger or the mold when the mold is opened in the sealing forming step, and cannot be removed by the automatic removal process of the forming machine, and the residual material remains. In this case, it is necessary to stop the seal forming and manually remove the residual material. Therefore, it is required to realize a sealing resin composition that can perform more stable sealing molding.

According to the present invention, there is provided a resin composition for sealing, comprising: an epoxy resin (A); a phenol aralkyl resin (B) having a biphenylene skeleton; and a compound having only one phenolic hydroxyl group (C) The compound (C) contains a compound represented by the following formula (1).

Furthermore, according to the present invention, there is provided a semiconductor device including: a base material; a semiconductor element mounted on the base material; and a sealing resin made of a hardened body of the sealing resin composition, and the semiconductor The components are sealed.

Furthermore, according to the present invention, there is provided a structure including: a base material; a plurality of semiconductor elements mounted on the base material; and a sealing resin made of a hardened body of the sealing resin composition. The plurality of semiconductor elements are sealed.

According to the present invention, sealing of a semiconductor element can be performed stably.

10‧‧‧ Substrate

20‧‧‧Semiconductor element

30‧‧‧sealing resin

40‧‧‧ bonding wire

50‧‧‧solder ball

100‧‧‧ semiconductor device

102‧‧‧ structure

The above-mentioned object and other objects, features, and advantages can be further clarified by the preferred embodiments described below and the following drawings attached thereto.

FIG. 1 is a sectional view showing an example of a semiconductor device according to this embodiment.

FIG. 2 is a cross-sectional view showing an example of a structure body according to this embodiment.

Hereinafter, embodiments will be described using drawings. In all drawings, the same constituent elements are denoted by the same reference numerals, and descriptions thereof are appropriately omitted.

The sealing resin composition according to this embodiment includes: an epoxy resin (A); a phenol aralkyl resin (B) having a biphenyl group; and a compound (C) having only one phenolic hydroxyl group. The compound (C) contains a compound represented by the following formula (1).

The present inventors have newly recognized that when a compound represented by the above formula (1) is contained as the compound (C) having only one phenolic hydroxyl group, retention of residues can be suppressed. This embodiment is based on such a new knowledge, and achieves the sealing resin composition containing the compound represented by said Formula (1). Thereby, stagnation of residual material can be suppressed, and the moldability of the resin composition for sealing can be improved. Therefore, the sealing of the semiconductor element can be performed stably.

Hereinafter, the sealing resin composition, the semiconductor device 100, and the structure 102 of this embodiment will be described in detail.

First, the sealing resin composition will be described.

The sealing resin composition is used to form a sealing resin that seals a semiconductor element mounted on a substrate. The sealing molding using the sealing resin composition is not particularly limited, and can be performed by, for example, a transfer molding method or a compression molding method. The base material is, for example, a wiring board such as a plug-in type or a lead frame. The semiconductor element is electrically connected to the base material by wire bonding, flip-chip connection, or the like.

The semiconductor device obtained by sealing a semiconductor element by sealing molding using a sealing resin composition is not particularly limited, and examples thereof include QFP (Quad Flat Package), SOP (Small Outline Package, small Package Size), BGA (Ball Grid Array), CSP (Chip Size Package), QFN (Quad Flat Non-leaded Package), SON (Small Outline Non- leaded Package (small size leadless package), LF-BGA (Lead Flame BGA, lead frame spherical grid array). In addition, the sealing resin composition of this embodiment is also related to a structure formed by molding a MAP (Mold Array Package) that has been widely used in molding of these packages in recent years. In this case, the above-mentioned structure is obtained by collectively sealing a plurality of semiconductor elements mounted on a substrate using a sealing resin composition.

The sealing resin composition includes: an epoxy resin (A); a phenol aralkyl resin (B) having a biphenyl group; and a compound (C) having only one phenolic hydroxyl group. Thereby, a sealing resin composition excellent in moldability can be realized.

(Epoxy (A))

As the epoxy resin (A), all monomers, oligomers, and polymers having two or more epoxy groups in one molecule can be used, and the molecular weight or molecular structure is not particularly limited.

In this embodiment, the epoxy resin (A) contains, for example, one or two or more selected from the following resins: biphenyl type epoxy resin; bisphenol A type epoxy resin, bisphenol F type epoxy resin, Bisphenol-type epoxy resins such as tetramethyl bisphenol F-type epoxy resin; 茋 -type epoxy resins; phenolic novolac-type epoxy resins, cresol novolac-type epoxy resins and other novolac-type rings Polyfunctional epoxy resins such as triphenol methane epoxy resin, alkyl modified triphenol methane epoxy resin, etc .; phenol aralkyl epoxy resin with phenylene skeleton, and biphenylene skeleton Aralkyl-based epoxy resins such as phenol aralkyl-based epoxy resins; naphthol-type rings such as dihydroxy naphthalene-type epoxy resins and epoxy resins obtained by etherifying a dimer of dihydroxy naphthalene with epoxypropyl group Oxygen resin; triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, etc. Core epoxy resin; crosslinked cyclic hydrocarbon compounds such as dicyclopentadiene modified phenol type epoxy resin and phenol type epoxy resin. Among these, from the viewpoint of improving the balance between moisture resistance reliability and moldability, it is more preferable to include at least one of a bisphenol type epoxy resin, a biphenyl type epoxy resin, and a phenol aralkyl type epoxy resin. It is particularly preferred to include at least one of a biphenyl type epoxy resin and a phenol aralkyl type epoxy resin.

As the epoxy resin (A), it is particularly preferable to use an epoxy resin containing an epoxy resin represented by the following formula (4), an epoxy resin represented by the following formula (5), and the following formula (6). At least one of the group consisting of epoxy resin.

(In formula (4), Ar ¹ represents a phenylene group or a naphthyl group, and when Ar ¹ is a naphthyl group, a glycidyl ether group may be bonded to any one of the α-position and the β-position. Ar ² represents a phenylene Any one of a radical, a biphenylene group, or a naphthyl group. _Ra and _Rb each independently represent a hydrocarbon group having 1 to 10 carbon atoms. G is an integer of 0 to 5 and h is an integer of 0 to 8. n ³ represents the degree of polymerization, and its average value is 1 to 3)

(In formula (5), a plurality of existing R _c each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N ⁵ represents a degree of polymerization, and an average value thereof is 0 to 4)

(In the formula (6), there are a plurality of R _d and R _e each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms of ⁶ .n represents the degree of polymerization, an average value of 0 to 4)

In this embodiment, the content of the epoxy resin (A) in the sealing resin composition is preferably 2% by mass or more, and more preferably 3% by mass, with respect to the entire sealing resin composition. the above. When the content of the epoxy resin (A) is at least the above-mentioned lower limit value, the fluidity of the sealing resin composition can be improved, and the moldability can be further improved.

On the other hand, the content of the epoxy resin (A) in the sealing resin composition is preferably 40% by mass or less, more preferably 30% by mass or less, based on the entire sealing resin composition. When the content of the epoxy resin (A) is equal to or less than the above-mentioned upper limit value, moisture resistance reliability and reflow resistance can be improved for a semiconductor device including a sealing resin formed using a sealing resin composition.

(Phenylaralkyl resin (B) with a biphenyl group)

The phenol aralkyl resin (B) having a biphenylene skeleton functions as a hardener that reacts with an epoxy resin to harden it. In this embodiment, as the phenol aralkyl resin (B) having a biphenyl group, it is more preferable to use the one represented by the following formula (7), and it is more preferable to use the one represented by the following formula (8). Thereby, the moldability of the sealing resin composition can be improved more effectively.

(In formula (7), R _f and R _g are hydrogen, alkyl or aryl group having 1 to 4 carbon atoms. Each R _f may be the same as or different from each other, and each R _g may be the same or different from each other. N ⁷ represents Degree of polymerization, whose average value is an integer from 1 to 5)

(In formula (8), n ⁸ represents the degree of polymerization, and the average value is an integer of 1 to 5)

In this embodiment, the content of the phenol aralkyl resin (B) having a biphenylene skeleton in the resin composition for sealing is preferably 1% by mass or more, more preferably, based on the entire resin composition for sealing. 3% by mass or more. When the content of the phenol aralkyl resin (B) having a biphenyl group is greater than or equal to the above-mentioned lower limit, the fluidity of the sealing resin composition can be improved, and the moldability can be further improved.

On the other hand, the content of the phenol aralkyl resin (B) having a stretched phenyl skeleton in the sealing resin composition is preferably 20% by mass or less, more preferably 10% by mass relative to the entire sealing resin composition. %the following. By setting the content of the phenol aralkyl resin (B) having a biphenyl group to be less than the above-mentioned upper limit value, it is possible to improve moisture resistance reliability and resistance to a semiconductor device including a sealing resin formed using a sealing resin composition. Resolderability.

The sealing resin composition according to this embodiment may further contain, as a hardener, components other than the phenol aralkyl resin (B) having a biphenyl group. Examples of other components include linear aliphatic diamines having 2 to 20 carbon atoms such as ethylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine, m-phenylenediamine, P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminediphenyl Phenylhydrazone, 4,4'-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, m-xylylenediamine, p-xylylenediamine , 1,1-bis (4-aminophenyl) cyclohexane, diamine diamine and other amines; aniline modified soluble phenol Soluble novolac phenol resins such as aldehyde resins or dimethyl ether soluble phenol resins; novolac phenol resins such as phenol novolac resin, cresol novolac resin, third butyl novolac resin, nonylphenol novolac resin ; Phenol aralkyl resins such as phenol aralkyl resins containing a phenylene skeleton; phenol resins having a condensed polycyclic structure such as a naphthalene skeleton or an anthracene skeleton; polyhydroxystyrene such as polyparahydroxystyrene; containing hexahydroortho Cyclic anhydrides such as phthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA), pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic acid Acid anhydrides such as aromatic anhydrides such as acids (BTDA); polythiol compounds such as polysulfides, thioesters, and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; organic resins such as polyester resins containing carboxylic acids Acids.

When a component other than the above-mentioned phenol aralkyl resin (B) having a stretched phenyl skeleton is contained as a hardener, it is preferable to contain 20% by mass or more of a stretched phenyl skeleton with respect to the entire hardener. The phenol aralkyl resin (B) preferably contains 30% by mass or more, and more preferably contains 50% by mass or more.

(Compound (C) having only one phenolic hydroxyl group)

The sealing resin composition contains a compound (C) having only one phenolic hydroxyl group. Thereby, the hardening characteristics of the resin composition for sealing can be adjusted, and the balance between formability and moisture resistance reliability can be improved more effectively. In addition, in this specification, the case where the compound (C) which has only one phenolic hydroxyl group is contained in the sealing resin composition means the case where it contains 1 ppm or more with respect to the whole sealing resin composition.

In this embodiment, the content of the compound (C) having only one phenolic hydroxyl group is preferably 1 ppm or more, and more preferably 5 ppm or more, based on the entire sealing resin composition. The content of the compound (C) having only one phenolic hydroxyl group is preferably based on the composition of the sealing resin. The total amount is 3,000 ppm or less, and more preferably 2500 ppm or less. By setting the content of the compound (C) in such a range, the crosslinked state of the resin hardened material in contact with the plunger or the mold can be maintained in an appropriate state, and the phenomenon of residual material retention can be effectively reduced.

The content of the compound (C) having only one phenolic hydroxyl group can be analyzed, for example, by gas chromatography. Hereinafter, the respective contents of the compound represented by the following formula (1), the compound (D) represented by the following formula (2), and the compound (E) represented by the following formula (3) are the same.

The compound (C) having only one phenolic hydroxyl group contains a compound represented by the following formula (1). With this, it is possible to suppress stagnation of residual material at the time of sealing molding, and to realize a sealing resin composition having excellent moldability. In addition, in this specification, the term "compound (C) contains a compound represented by the following formula (1)" means the case where it contains 1 ppm or more with respect to the whole compound (C).

In this embodiment, the content of the compound represented by the above formula (1) is preferably 10 ppm or more, more preferably 15 ppm or more, and even more preferably 25 ppm or more with respect to the entire sealing resin composition. When the content of the compound represented by the formula (1) is equal to or more than the above-mentioned lower limit, it is possible to effectively suppress the retention of residue during sealing molding, and further improve the moldability of the resin composition for sealing. In this way, in order to further effectively suppress the retention of residual materials, it is preferable that the compound represented by the above formula (1) is contained in the sealing resin composition in a certain amount or more. This can be achieved by synthesizing the compound (C) having only one phenolic hydroxyl group by the method of this embodiment described below.

On the other hand, the content of the compound represented by the formula (1) is preferably 300 ppm or less, more preferably 200 ppm or less, and even more preferably 100 ppm or less with respect to the entire sealing resin composition. When the content of the compound represented by the formula (1) is equal to or less than the above-mentioned upper limit value, it is possible to improve the balance between moldability and hardenability for the sealing resin composition.

In this embodiment, the compound (C) having only one phenolic hydroxyl group may further contain a compound other than the compound represented by the formula (1). Examples of such other components include a compound represented by the following formula (9) or a compound represented by the following formula (10). By further including such other components, the hardening characteristics of the resin composition for sealing can be adjusted more easily.

(Compound (D) represented by formula (2))

The sealing resin composition of the present embodiment may further contain, for example, a compound (D) represented by the following formula (2). Thereby, it is possible to more effectively suppress the stagnation of the residual material at the time of the seal forming, and to further improve the formability. In addition, the adjustment of the hardening characteristics can be made easier, which contributes to the balance between moldability and moisture resistance reliability. In addition, in this specification, the term "comprising compound (D) in the sealing resin composition" means that the compound (D) is contained in an amount of 1 ppm or more with respect to the entire sealing resin composition.

In this embodiment, the content of the compound (D) represented by the formula (2) is preferably 30 ppm or more, and more preferably 40 ppm or more, based on the entire sealing resin composition. The content of the compound (D) represented by the formula (2) is preferably 800 ppm or less, more preferably 500 ppm or less, based on the entire sealing resin composition. When the content of the compound (D) represented by the above formula (2) is within the above range, it is possible to more effectively suppress the retention of residual material during sealing molding, and to further improve the moldability of the resin composition for sealing. In addition, it is possible to improve the balance between moldability and hardenability for the resin composition for sealing.

(Compound (E) represented by formula (3))

The sealing resin composition of the present embodiment may further contain, for example, a compound (E) represented by the following formula (3). Thereby, it is possible to more effectively suppress the stagnation of the residual material at the time of the seal forming, and to further improve the formability. In addition, in this specification, the term "comprising compound (E) in the sealing resin composition" means that the compound (E) is contained in an amount of 1 ppm or more with respect to the entire sealing resin composition.

In this embodiment, the content of the compound (E) represented by the formula (3) is preferably 1 ppm or more, and more preferably 3 ppm or more, based on the entire sealing resin composition. The content of the compound (E) represented by the formula (3) is preferably based on the entire resin composition for sealing. It is 50 ppm or less, and more preferably 30 ppm or less. When the content of the compound (E) represented by the formula (3) is within the above-mentioned range, it is possible to more effectively suppress the retention of residue during sealing molding, and further improve the hardening characteristics of the resin composition for sealing.

In this embodiment, the sealing resin composition may contain a biphenyl compound having four or more aromatic rings as shown in the formula (1), the formula (2), and the formula (3). The phenolic hydroxyl group has as few as two or less, and the aromatic ring at least at one terminal does not have a phenolic hydroxyl group. It is presumed that this compound has the function of improving the release property of the plunger or the mold when the mold is opened. Based on this knowledge, the present inventors improved the mold release property at the time of mold opening of the sealing resin composition, thereby achieving suppression of residual material retention during sealing molding.

From this viewpoint, in order to more effectively suppress the retention of residual materials, it is particularly preferable to include the compound represented by the above formula (2) in addition to the compound (C) having only one phenolic hydroxyl group, that is, the compound represented by the above formula (1). (D) and at least one of the compounds (E) represented by the formula (3). Thereby, the sealing resin composition which can perform sealing molding more stably is realizable.

In this embodiment, for example, a reaction product obtained by polycondensing a phenol with a dihalomethylbiphenyl such as 4,4'-bischloromethylbiphenyl is subjected to a distillation and removal treatment of unreacted components, And water washing treatment, a mixture containing a phenol aralkyl resin (B) having a biphenyl group and a compound (C) having only one phenolic hydroxyl group can be obtained. At this time, by appropriately adjusting the conditions of the distillation removal treatment of the unreacted components and the water washing treatment, the above-mentioned mixture containing the compound represented by the above formula (1) can be obtained. In addition, the content of each of the compound (C) having only one phenolic hydroxyl group or the compound represented by the formula (1) can be controlled. In this embodiment, the distillation and removal processing of unreacted components can be performed, for example, by a method of removing low molecular weight components. As a method for removing low-molecular-weight components, for example, the temperature can be appropriately set by a general-purpose vacuum distillation method. It can be carried out at a degree of pressure or a reduced pressure, and can also be applied by methods such as steam distillation, molecular distillation, or fractionation and fractionation using a GPC column. In particular, in order to contain an appropriate amount of the compound represented by the above formula (1), it is also preferable to adopt the following method: After the low molecular weight component is temporarily removed by the above-mentioned ordinary method for removing the low molecular weight component, the low molecular weight to be removed is temporarily removed. The components were distilled and fractionated, and added to the matrix again. In the water washing treatment, for example, the operation (water washing) of removing the water layer after adding distilled water to the reaction product and shaking it may be performed several times. In addition, as the phenols, for example, one selected from phenol, cresol, methylphenol, n-propylphenol, xylenol, methylbutylphenol, cyclopentylphenol, and cyclohexylphenol may be used. 2 or more.

Furthermore, by further controlling the conditions of the distillation and removal treatment of unreacted components and the water washing treatment, a compound (D) represented by the above formula (2) can be obtained in addition to the compound represented by the above formula (1), and The above mixture of the compound (E) represented by the above formula (3). The content of each of the compound (D) represented by the formula (2) and the compound (E) represented by the formula (3) may be controlled.

(Filler (F))

The sealing resin composition may further contain, for example, a filler (F). As the filler (F), users of general epoxy resin compositions for semiconductor sealing can be used, and examples thereof include fused spherical silica, fused and broken silica, crystalline silica, talc, and alumina. , Titanium white, silicon nitride and other inorganic fillers, organic silicone powder, polyethylene powder and other organic fillers. Among these, it is particularly preferable to use fused spherical silica. These fillers may be used alone or in combination of two or more.

In addition, the shape of the filler (F) is not particularly limited, but it is preferably from the viewpoint of suppressing an increase in the melt viscosity of the resin composition for sealing and increasing the content of the filler. The amount is truly spherical and the particle size distribution is wide.

In this embodiment, the content of the filler (F) is preferably 35% by mass or more, more preferably 50% by mass or more, and even more preferably 65% by mass or more with respect to the entire sealing resin composition. When the content of the filler (F) is equal to or more than the above-mentioned lower limit value, the low hygroscopicity and the low thermal expansion property of the sealing resin formed using the sealing resin composition can be improved, and the moisture resistance reliability and the back resistance can be more effectively improved Weldability.

On the other hand, the content of the filler (F) is preferably 95% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less. When the content of the filler (F) is equal to or less than the above-mentioned upper limit value, it is possible to prevent the moldability from being lowered as the flowability of the sealing resin composition is lowered, and the bonding wire is shifted due to an increase in viscosity.

(Hardening accelerator (G))

The sealing resin composition may further contain, for example, a hardening accelerator (G). The hardening accelerator (G) may be one that accelerates the crosslinking reaction of the epoxy group of the epoxy resin (A) and the phenolic hydroxyl group of the phenol aralkyl resin (B) having a stretched phenyl skeleton. For example, it can be used For general sealing epoxy resin users.

In this embodiment, the hardening accelerator (G) may contain, for example, one or two or more compounds selected from the group consisting of organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, phosphine compounds, and quinone compounds. Compounds containing phosphorus atoms, such as adducts, adducts of amidine compounds and silane compounds; 1,8-diazabicyclo (5,4,0) undecene-7, dimethylbenzylamine, 2-methylimidazole, etc. Examples of compounds containing nitrogen atoms include fluorene or tertiary amines, and quaternary salts of fluorene or amines. Among these, from the viewpoint of improving the hardenability, it is more preferable to contain a compound containing a phosphorus atom. From the viewpoint of improving the balance between moldability and hardenability, it is more preferable to contain a tetra-substituted phosphonium compound and a phosphorobetaine compound. Latent compounds, adducts of phosphine compounds and quinone compounds, adducts of amidine compounds and silane compounds, and the like.

Examples of the organic phosphine that can be used in the sealing resin composition include primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine Tertiary phosphines such as phenylphosphine.

Examples of the tetra-substituted fluorene compound that can be used in the sealing resin composition include a compound represented by the following general formula (13).

(In the general formula (13), P represents a phosphorus atom. R ⁴ , R ⁵ , R ^6, and R ⁷ represent an aromatic group or an alkyl group. A represents that the aromatic ring has at least one member selected from a hydroxyl group, a carboxyl group, and a sulfur group. An anion of an aromatic organic acid having any functional group in an alcohol group. AH represents an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group on an aromatic ring. X and y are 1 to 3, z is 0 to 3, and x = y.)

The compound represented by the general formula (13) is obtained by, for example, operating as follows, but is not limited thereto. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed into an organic solvent and mixed uniformly, so that an aromatic organic acid anion is generated in the solution system. Then, after adding water, the compound represented by the general formula (13) can be precipitated. Among the compounds represented by the general formula (13), R ⁴ , R ⁵ , R ^6, and R ⁷ bonded to a phosphorus atom are preferably phenyl groups, and AH is a compound having a hydroxyl group on an aromatic ring, that is, phenols And A is the anion of the phenol. Examples of the phenols include monocyclic phenols such as phenol, cresol, resorcinol, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and hydroanthraquinone, bisphenol A, Bisphenols such as bisphenol F and bisphenol S, polycyclic phenols such as phenylphenol and biphenol.

Examples of the phosphorus betaine compound that can be used in the sealing resin composition include a compound represented by the following general formula (14).

(In the general formula (14), R ⁸ represents an alkyl group having 1 to 3 carbon atoms, and R ⁹ represents a hydroxyl group. F is a number of 0 to 5 and g is a number of 0 to 3.)

The compound represented by general formula (14) is obtained, for example, as follows. First, it is obtained by contacting a triaromatic substituted phosphine as a tertiary phosphine with a diazonium salt, and substituting the triaromatic substituted phosphine with a diazonium group of the diazonium salt. However, it is not limited to this.

Examples of the adduct of a phosphine compound and a quinone compound that can be used in the sealing resin composition include a compound represented by the following general formula (15).

(In the above general formula (15), P represents a phosphorus atom. R ¹⁰ , R ^11, and R ¹² represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may be the same as or different from each other. R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, which may be the same as or different from each other, and R ¹⁴ and R ¹⁵ may be bonded to form a cyclic structure.)

As the phosphine compound used as an adduct of a phosphine compound and a quinone compound, for example, triphenylphosphine, tri (alkylphenyl) phosphine, tri (alkoxyphenyl) phosphine, trinaphthylphosphine, tris ( Amidino) phosphine is equivalent to those having no substituents on the aromatic ring or having substituents such as alkyl groups and alkoxy groups. Examples of substituents such as alkyl groups and alkoxy groups include those having 1 to 6 carbon atoms. From the viewpoint of easy availability, triphenylphosphine is preferred.

Examples of the quinone compound used as an adduct of a phosphine compound and a quinone compound include benzoquinone and anthraquinones. Among them, p-benzoquinone is preferred in terms of storage stability.

As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing these in a solvent in which both the organic tertiary phosphine and benzoquinone are soluble. The solvent is preferably a ketone such as acetone or methyl ethyl ketone and has low solubility in the adduct. However, it is not limited to this.

Among the compounds represented by the general formula (15), in terms of reducing the thermal modulus of the hardened product of the resin composition for sealing, it is preferable that R ¹⁰ , R ^11, and R ¹² bonded to a phosphorus atom are Compounds in which phenyl and R ¹³ , R ¹⁴ and R ¹⁵ are hydrogen atoms are also compounds obtained by addition of 1,4-benzoquinone and triphenylphosphine.

Examples of the adduct of a sulfonium compound and a silane compound that can be used in the sealing resin composition include a compound represented by the following general formula (16).

(In the above general formula (16), P represents a phosphorus atom, and Si represents a silicon atom. R ¹⁶ , R ¹⁷ , R ^18, and R ¹⁹ each represent an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group, and may each other. The same or different. In the formula, R ²⁰ is an organic group bonded to the groups Y ² and Y ^{3. In the} formula, R ²¹ is an organic group bonded to the groups Y ⁴ and Y ^5. Y ² and Y ³ represent proton donating properties The base is a base from which protons are released, and the bases Y ² and Y ^{3 in the} same molecule are bonded to a silicon atom to form a chelate structure. Y ⁴ and Y ⁵ represent bases from which a proton donating group releases a proton. The groups Y ⁴ and Y ^{5 in the} same molecule are bonded to a silicon atom to form a chelate structure. R ²⁰ and R ²¹ may be the same as or different from each other, and Y ² , Y ³ , Y ^4, and Y ⁵ may be the same or different from each other. Different. Z ¹ is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.)

Examples of R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ in the general formula (16) include phenyl, tolyl, methoxyphenyl, hydroxyphenyl, naphthyl, hydroxynaphthyl, and fluorenyl , Methyl, ethyl, n-butyl, n-octyl, and cyclohexyl; among these, phenyl, tolyl, methoxyphenyl, hydroxyphenyl, hydroxynaphthyl, and the like have alkyl groups, Aromatic or unsubstituted aromatic groups having substituents such as alkoxy and hydroxyl groups.

In Formula (16), R ²⁰ is an organic group bonded to Y ² and Y ³ . Similarly, R ²¹ is an organic group bonded to the groups Y ⁴ and Y ⁵ . Y ² and Y ³ are proton-derived groups that release protons. The Y ² and Y ³ groups in the same molecule are bonded to silicon atoms to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are radicals in which proton donating groups release protons, and the radicals Y ⁴ and Y ^{5 in the} same molecule are bonded to silicon atoms to form a chelate structure. The radicals R ²⁰ and R ²¹ may be the same as or different from each other, and the radicals Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same or different from each other. The base represented by -Y ² -R ²⁰ -Y ³ -and Y ⁴ -R ²¹ -Y ⁵ -in the general formula (16) is a base constituted by a proton donor releasing two protons. As the proton donor, an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule is preferred, and an aromatic compound having at least two carboxyl groups or hydroxyl groups on adjacent carbons constituting an aromatic ring is more preferred, more preferably Examples of aromatic compounds having at least two hydroxyl groups on adjacent carbons constituting the aromatic ring include catechol, gallophenol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,2'- Biphenol, 1,1'-bis-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chlororanic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propylene glycol, glycerin, and the like; among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable.

In addition, Z ¹ in the general formula (16) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring. Specific examples of these include methyl, ethyl, propyl, butyl, and hexyl. And aliphatic hydrocarbon groups such as octyl, or aromatic hydrocarbon groups such as phenyl, fluorenyl, naphthyl, and biphenyl; glycidoxypropyl, mercaptopropyl, and aminopropyl; Reactive substituents such as mercapto, amine alkyl, and vinyl; among these, in terms of thermal stability, methyl, ethyl, phenyl, naphthyl, and biphenyl are more preferred.

As a method for producing an adduct of a sulfonium compound and a silane compound, a flask containing methanol is charged with a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene, followed by dissolution. A sodium methoxide-methanol solution was added dropwise with stirring at room temperature. Furthermore, a solution prepared by dissolving a tetrasubstituted phosphonium halide such as tetraphenylphosphonium bromide in methanol in advance was added dropwise thereto with stirring at room temperature, and then crystals were precipitated. The precipitated crystals were filtered, washed with water, and dried under vacuum to obtain an adduct of an amidine compound and a silane compound. However, it is not limited to this.

In this embodiment, the content of the hardening accelerator (G) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more with respect to the entire sealing resin composition. By making content of a hardening accelerator (G) more than the said lower limit, the hardenability at the time of sealing molding can be improved effectively.

On the other hand, the content of the hardening accelerator (G) is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less based on the entire sealing resin composition. When the content of the hardening accelerator (G) is equal to or less than the above-mentioned upper limit value, it is possible to improve the fluidity during sealing molding.

(Other ingredients (H))

If necessary, one or more of various additives such as a coupling agent, a release agent, an ion trapping agent, a low-stress component, a flame retardant, a colorant, and an antioxidant may be appropriately blended into the resin composition for sealing.

The coupling agent may include various silane-based compounds selected from, for example, epoxy silane, mercapto silane, amine silane, alkyl silane, ureido silane, vinyl silane, methacryl methanosilane, and the like One or two or more of known coupling agents such as compounds and aluminum / zirconium-based compounds. Among these, as the effect of the present invention is more effectively exhibited, it is more preferable to include an epoxy silane or an amino silane, and it is more preferable to include a secondary amine silane from the viewpoint of fluidity and the like. The release agent may include one or two or more kinds selected from natural waxes such as carnauba wax, synthetic waxes such as montan wax, higher fatty acids such as zinc stearate and metal salts thereof, and paraffin wax. The ion trapping agent contains, for example, aluminum magnesium carbonate. The low-stress component includes, for example, silicone rubber. The flame retardant may include one or two or more kinds selected from, for example, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene. The colorant includes, for example, carbon black.

As the sealing resin composition, for example, those obtained by mixing the above-mentioned components by a known method, and further performing melt-kneading using a kneading machine such as a roll, a kneader, or an extruder, and pulverizing after cooling, Those who are crushed to form an ingot after pulverization, and those who have appropriately adjusted the dispersion degree or fluidity as needed.

Next, the semiconductor device 100 will be described.

FIG. 1 is a cross-sectional view showing an example of a semiconductor device 100 according to this embodiment. The semiconductor device 100 includes a semiconductor package including a base material 10, a semiconductor element 20 mounted on the base material 10, and a sealing resin 30 that seals the semiconductor element 20. In Figure 1, an example The semiconductor device 100 may be a BGA package. In this case, a plurality of solder balls 50 are provided on the back surface of the base material 10 opposite to the front surface on which the semiconductor element 20 is mounted.

The semiconductor element 20 is electrically connected to the base material 10 via a bonding wire 40. On the other hand, the semiconductor element 20 may be mounted on the substrate 10 by flip-chip structure.

In this embodiment, the sealing resin 30 is composed of a hardened product of the above-mentioned sealing resin composition. This makes it possible to suppress the occurrence of residual material retention during the sealing of the semiconductor device 20. Therefore, more stable manufacturing of the semiconductor device 100 can be achieved. The sealing resin 30 is formed by sealing-molding a sealing resin composition using a known method such as a transfer molding method or a compression molding method.

Next, the structure 102 will be described.

FIG. 2 is a cross-sectional view showing an example of the structure body 102 according to this embodiment. The structure body 102 is a molded product formed by MAP molding. Therefore, by singulating each semiconductor element 20 in the structure body 102, a plurality of semiconductor packages can be obtained.

The structure body 102 includes a base material 10, a plurality of semiconductor elements 20, and a sealing resin 30. A plurality of semiconductor elements 20 are arranged on the base material 10. FIG. 2 illustrates a case where each semiconductor element 20 is electrically connected to the base material 10 via a bonding wire 40. However, the present invention is not limited to this, and each semiconductor element 20 may be mounted on the substrate 10 with a crystal structure. The base material 10 and the semiconductor element 20 can be the same as those exemplified in the semiconductor device 100.

The sealing resin 30 seals a plurality of semiconductor elements 20. The sealing resin 30 is made of a cured product of the above-mentioned sealing resin composition. This makes it possible to suppress the occurrence of residual material retention during the sealing molding. Therefore, the structure 102 and the semiconductor device obtained by singulating the structure 102 can be manufactured more stably. The sealing resin 30 is known, for example, by using a transfer molding method or a compression molding method. Methods A sealing resin composition is formed by sealing.

Examples

Next, an embodiment of the present invention will be described.

(Synthesis of phenol aralkyl resin (B) having a biphenyl group and a compound (C) having only one phenolic hydroxyl group) (Synthesis example 1)

First, a separable flask was equipped with a stirring device, a thermometer, a reflux cooler, and a nitrogen inlet. Next, weigh 517 parts by mass of phenol (a special reagent manufactured by Kanto Chemical Co., Ltd., "phenol", a melting point of 41 ° C, a molecular weight of 94, and a purity of 99.3%). 251 parts by mass of phenylbiphenyl (manufactured by Wako Pure Chemical Industries, Ltd., "4,4'-Dichloromethylbiphenyl", melting point of 126 ° C, purity of 95%, molecular weight of 251) was placed in the separable flask, and nitrogen gas was replaced on the side While heating, stirring was started while the phenol started to melt. Subsequently, after the reaction was performed at a temperature of 65 ° C. for 3 hours, the pressure was reduced to 90 kPa, and the reaction was performed at 80 ° C. for 1 hour. Then, the temperature in the system was lowered to 70 ° C., 6 parts by mass of trisodium citrate was added, and the mixture was stirred for 30 minutes. Next, 100 parts by mass of the heated distilled water was added, and the temperature was raised to 140 ° C., and then the unreacted components were distilled off at 1 kPa for 1 hour, and then the unreacted components were distilled off at 180 ° C. and 0.2 kPa for 1 hour. Furthermore, the fraction obtained by distillation removal of this unreacted component was stored. Further, the temporarily taken out product was uniformly dissolved in 500 parts by mass of toluene. This operation was carried out twice, and 150 parts by mass of distilled water was added to the separatory funnel. After shaking, the water layer was removed (washing). Then, the product obtained by distilling off toluene is analyzed by gas chromatography, and the above-mentioned unreacted components are washed with water and molecular distillation, thereby adding low molecular weight components and the like to the product. in this way, A phenol aralkyl resin (B) containing a biphenyl group, a compound (C) having only one phenolic hydroxyl group, a compound (D) represented by the following formula (2), and the following formula (3) were obtained. A mixture of the compound (E) shown.

The content of the compound (C) in the obtained mixture was 1.0% by mass based on the phenol aralkyl resin (B) having a biphenyl group. The compound (C) contains a compound represented by the following formula (1). The content of the compound represented by the following formula (1) was 720 ppm based on the phenol aralkyl resin (B) having a biphenyl group. The content of the compound (D) was 1900 ppm based on the phenol aralkyl resin (B) having a biphenyl group. The content of the compound (E) was 120 ppm based on the phenol aralkyl resin (B) having a biphenyl group. The content of each of the compound (C), the compound represented by the formula (1), the compound (D), and the compound (E) was analyzed by gas chromatography. Hereinafter, the same applies to Synthesis Examples 2 to 4.

(Synthesis example 2)

A compound (C) containing a phenol aralkyl resin (B) having a biphenyl group and a compound (C) having only one phenolic hydroxyl group was obtained in the same manner as in Synthesis Example 1 except that the addition amount of the unreacted components through molecular distillation was changed. A mixture of the compound (D) represented by the formula (2) and the compound (E) represented by the formula (3). The content of the compound (C) in the obtained mixture was 1.5% by mass based on the phenol aralkyl resin (B) having a biphenyl group. The compound (C) contains a compound represented by the formula (1). The content of the compound represented by the above formula (1) was 1,000 ppm based on the phenol aralkyl resin (B) having a biphenyl group. The content of the compound (D) was 2630 ppm based on the phenol aralkyl resin (B) having a biphenyl group. The content of the compound (E) was 160 ppm based on the phenol aralkyl resin (B) having a biphenyl group.

(Synthesis example 3)

A compound (C) containing a phenol aralkyl resin (B) having a biphenylene skeleton, a compound (C) having only one phenolic hydroxyl group, and A mixture of the compound (D) represented by the formula (2) and the compound (E) represented by the formula (3). The content of the compound (C) in the obtained mixture was 0.7% by mass based on the phenol aralkyl resin (B) having a biphenyl group. The compound (C) contains a compound represented by the formula (1). The content of the compound represented by the above formula (1) was 500 ppm based on the phenol aralkyl resin (B) having a biphenyl group. The content of the compound (D) was 1310 ppm based on the phenol aralkyl resin (B) having a biphenyl group. The content of the compound (E) was 80 ppm based on the phenol aralkyl resin (B) having a biphenyl group.

(Synthesis example 4)

First, to a flask equipped with a stirrer and a cooler, 564 parts by mass of phenol and bis (a 484 parts by mass of oxymethyl) biphenyl, and 15.4 parts by mass of diethyl sulfate were added dropwise thereto. Then, the temperature in the system was maintained at 160 ° C while reacting for 3 hours. During this period, the ethanol produced was distilled off. After completion of the reaction, cooling was performed, and washing with water was performed three times. The oil layer was separated, and unreacted phenol was distilled off under reduced pressure to obtain a mixture containing a phenol aralkyl resin (B) having a biphenyl group and a compound (C) having only one phenolic hydroxyl group. In addition, in this synthesis example, the addition of unreacted components through molecular distillation was not performed. The content of the compound (C) in the obtained mixture was 0.6% by mass based on the phenol aralkyl resin (B) having a biphenylene skeleton.

On the other hand, the compound (D) represented by the formula (2) and the compound (E) represented by the formula (3) are not contained in the mixture. Here, the term "not contained in the mixture" refers to a case where the content is less than 1 ppm with respect to the entire mixture. The compound (C) does not include the compound represented by the formula (1).

(Resin composition for sealing)

Regarding each of Examples 1 to 4 and Comparative Examples 1 to 2, the sealing resin composition was adjusted as follows. First, according to the composition shown in Table 1, using a mixer to mix the ingredients at 15-28 ° C, roll-kneading was performed at 70-100 ° C. Then, this was cooled and pulverized to obtain a sealing resin composition. Furthermore, the phenol aralkyl resin (B), the compound (C), the compound (D), and the compound (E) having a biphenyl group were obtained using Synthesis Example 1 in Example 1 and Example 2, respectively. The aforementioned mixture, the aforementioned mixture obtained in Synthesis Example 2 in Example 3, the aforementioned mixture obtained in Synthesis Example 3 in Example 4, and the aforementioned mixture obtained in Synthesis Example 4 in Comparative Example 1 and Comparative Example 2.

Details of each component in Table 1 are as follows. In addition, the components shown in Table 1 are adjusted. All the blending ratios refer to blending ratios (mass% or ppm) with respect to the entire sealing resin composition.

(Epoxy (A))

Epoxy resin 1: phenol aralkyl type epoxy resin containing phenylene skeleton (NC-2000, manufactured by Nippon Kayaku Co., Ltd.)

Epoxy resin 2: Biphenyl epoxy resin (YX4000K, manufactured by Mitsubishi Chemical Corporation)

(Phenylaralkyl resin (B) with a biphenyl group)

Phenol aralkyl resin having a stretched phenyl skeleton 1: Phenol aralkyl resin having a stretched phenyl skeleton synthesized by the above Synthesis Example 1 (B)

Phenol aralkyl resin with a stretched phenyl skeleton 2: Phenol aralkyl resin (B) with a stretched phenyl skeleton synthesized by the above Synthesis Example 2

Phenol aralkyl resin with a stretched phenyl skeleton 3: Phenol aralkyl resin with a stretched phenyl skeleton synthesized by the above Synthesis Example 3 (B)

Phenol aralkyl resin with a stretched phenyl skeleton 4: Phenol aralkyl resin (B) with a stretched phenyl skeleton synthesized by the above Synthesis Example 4

(Compound (C) having only one phenolic hydroxyl group)

Compound (C1): Compound (C) synthesized by the above Synthesis Example 1

Compound (C2): Compound (C) synthesized by the above Synthesis Example 2

Compound (C3): Compound (C) synthesized by the above Synthesis Example 3

Compound (C4): Compound (C) synthesized by the above Synthesis Example 4

(Filler (F))

Filler 1: spherical fused silica (manufactured by Denka Kogyo Co., Ltd., FB560 (average particle size: 30 μm))

Filler 2: spherical fused silica (manufactured by Admatechs Co., Ltd., SO-25R (average particle size 0.5 μm))

(Hardening accelerator (G))

Hardening accelerator 1: Compound represented by the following formula (11)

Hardening accelerator 2: Compound represented by the following formula (12)

[Synthesis method of hardening accelerator 1]

To a separable flask equipped with a cooling tube and a stirring device, 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 ml of acetone were added, and the reaction was performed at room temperature with stirring. The precipitated crystals were washed with acetone, and then filtered and dried to obtain a hardening accelerator 1 for dark green crystals.

[Synthesis method of hardening accelerator 2]

In a separable flask equipped with a cooling tube and a stirring device, 12.81 g (0.080 mol) of 2,3-dihydroxynaphthalene, 16.77 g (0.040 mol) of tetraphenylphosphonium bromide, and 100 ml of methanol were added and stirred Dissolve evenly. A sodium hydroxide solution prepared by dissolving 1.60 g (0.04 ml) of sodium hydroxide in 10 ml of methanol was slowly added dropwise to the flask, and then crystals were precipitated. The precipitated crystal was filtered, washed with water, and dried under vacuum to obtain a hardening accelerator 2.

(Other ingredients (H))

Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM-573)

Coupling agent 2: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)

Ion trapping agent: aluminum magnesium carbonate (manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4H)

Release agent 1: Carnauba wax (manufactured by Nikko Fine Products Co., Ltd., Nikko carnauba)

Release agent 2: Urethane modified oxidized polyethylene wax (manufactured by NIPPON SEIRO Co., Ltd., NSP-6010P)

Colorant: Carbon black (manufactured by Mitsubishi Chemical Corporation, MA-600)

(Formability evaluation)

For each of Examples 1 to 4 and Comparative Examples 1 to 2, the obtained sealing resin composition was subjected to a low-pressure transfer molding machine at a mold temperature of 175 ° C, an injection pressure of 100 kg / cm ² , and a preheating time of 3 seconds. Under the conditions of an injection time of 7 seconds and a hardening time of 45 seconds, an 80-pin four-sided flat package (80pQFP, Cu lead frame, package size 14mm × 20mm × 2.0mmt) was hermetically sealed until it reached 500 sets of full punch. Here, the number of times of manual removal of the residual material (residual material of the sealing resin composition) during mold opening in 500 sets of blanking is adhered to the plunger or the mold, and the number of residual materials is shown as the number of residual materials retained. in FIG. 1. Here, when the number of remaining materials is 2 or less, it can be evaluated that the moldability is good.

Claims (5)

A resin composition for sealing, comprising: an epoxy resin (A); a phenol aralkyl resin (B) having a biphenylene skeleton; and a compound (C) having only one phenolic hydroxyl group, the Compound (C) contains a compound represented by the following formula (1);

The sealing resin composition further contains a compound (D) represented by the following formula (2) and a compound (E) represented by the following formula (3), and the content of the compound (E) relative to the entire sealing resin composition, 1ppm or more and 50ppm or less,

The resin composition for sealing as claimed in item 1 of the patent application, wherein the content of the compound represented by the formula (1) is 10 ppm or more and 300 ppm or less with respect to the entire resin composition for sealing. The resin composition for sealing according to claim 1 or 2, wherein the content of the compound (C) is 1 ppm or more and 3000 ppm or less with respect to the entire resin composition for sealing. A semiconductor device comprising: a base material; a semiconductor element mounted on the base material; and a sealing resin: consisting of a cured product of the sealing resin composition according to any one of the patent application items 1 to 3, and The semiconductor element is sealed. A structure comprising: a base material; a plurality of semiconductor elements mounted on the base material; and a sealing resin: consisting of a hardened product of the sealing resin composition according to any one of claims 1 to 3, And the plurality of semiconductor elements are sealed.