CN107406580B

CN107406580B - Resin composition for sealing, semiconductor device, and structure

Info

Publication number: CN107406580B
Application number: CN201580077279.6A
Authority: CN
Inventors: 吉田显二
Original assignee: Sumitomo Dianwood Co Ltd
Current assignee: Sumitomo Dianwood Co Ltd
Priority date: 2015-05-29
Filing date: 2015-05-29
Publication date: 2020-01-24
Anticipated expiration: 2035-05-29
Also published as: KR20180013847A; CN107406580A; WO2016194034A1; KR102367125B1

Abstract

The sealing resin composition contains an epoxy resin (A) and a phenol aralkyl resin having a biphenylene skeleton (A)B) And a compound (C) having only one phenolic hydroxyl group, the compound (C) containing a compound represented by the following formula (1).

Description

Resin composition for sealing, semiconductor device, and structure

Technical Field

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

Background

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

Patent document 1 describes a technique relating to a phenol novolac condensate used as a curing agent for an epoxy resin.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 8-143648

Disclosure of Invention

Technical problem to be solved by the invention

In order to stably seal a semiconductor element, it is required to improve moldability of a resin composition for sealing. The present inventors investigated suppression of sticking of residue at the time of seal molding as one of indexes for evaluating moldability of a resin composition for seal molding. The residue adhesion means a phenomenon that the residue adheres to the plunger or the mold when the mold is opened in the seal molding process, and cannot be removed even by the automatic removal process of the molding machine, and the residue remains. In this case, the seal molding is stopped and the residue needs to be manually removed. Therefore, it is desired to realize a resin composition for sealing which can perform more stable sealing molding.

Means for solving the problems

According to the present invention, there is provided a sealing resin composition 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).

Further, according to the present invention, there is provided a semiconductor device including: a substrate; a semiconductor element mounted on the substrate; and a sealing resin which is a cured product of the sealing resin composition and seals the semiconductor element.

Further, according to the present invention, there is provided a structure comprising: a substrate; a plurality of semiconductor elements mounted on the substrate; and a sealing resin which is a cured product of the sealing resin composition and seals the plurality of semiconductor elements.

Effects of the invention

According to the present invention, the semiconductor element can be stably sealed.

Drawings

The above and other objects, features and advantages will become more apparent from the following description of preferred embodiments and the accompanying drawings attached hereto.

Fig. 1 is a cross-sectional view showing an example of a semiconductor device according to the present embodiment.

Fig. 2 is a cross-sectional view showing an example of the structure according to the present embodiment.

Detailed Description

Hereinafter, embodiments will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and the description thereof is omitted as appropriate.

The sealing resin composition according to the present embodiment contains 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 inventor newly obtains the following findings: when the compound represented by the above formula (1) is contained as the compound (C) having only one phenolic hydroxyl group, adhesion of residue can be suppressed. The present embodiment has realized a sealing resin composition containing the compound represented by the above formula (1) based on such a novel finding. This can suppress sticking of the residue and improve the moldability of the sealing resin composition. Therefore, the semiconductor element can be stably sealed.

The sealing resin composition, the semiconductor device 100, and the structure 102 according to the present embodiment will be described in detail below.

First, a resin composition for sealing will be described.

The sealing resin composition is used for forming a sealing resin for sealing a semiconductor element mounted on a base material. 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 an interposer 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 seal molding using the sealing resin composition is not particularly limited, and examples thereof include QFP (Quad Flat Package), SOP (Small Outline Package), BGA (Ball Grid Array), CSP (Chip SizePackage), QFN (Quad Flat Package), SON (Small Outline Non-leaded Package), and LF-BGA (Lead BGA leadframe Package). The sealing resin composition according to the present embodiment also relates to a structure formed by MAP (Mold Array Package) molding, which has been widely used in the molding of these packages in recent years. In this case, the structure is obtained by collectively sealing a plurality of semiconductor elements mounted on a base material with a sealing resin composition.

The sealing resin composition contains an epoxy resin (A), a phenol aralkyl resin (B) having a biphenylene skeleton, and a compound (C) having only one phenolic hydroxyl group. This enables to obtain a sealing resin composition having excellent moldability.

(epoxy resin (A))

As the epoxy resin (a), all monomers, oligomers, and polymers having 2 or more epoxy groups in 1 molecule can be used, and the molecular weight and the molecular structure thereof are not particularly limited.

In the present embodiment, the epoxy resin (a) contains a compound selected from, for example, biphenyl type epoxy resins; bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol F epoxy resin, and tetramethylbisphenol F epoxy resin; stilbene type epoxy resins; novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; multifunctional epoxy resins such as trisphenol methane type epoxy resin and alkyl-modified trisphenol methane type epoxy resin; aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a phenylene skeleton and phenol aralkyl type epoxy resins having a biphenylene skeleton; naphthol type epoxy resins such as dihydroxynaphthalene type epoxy resins and epoxy resins obtained by glycidyletherifying a dimer of dihydroxynaphthalene; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; one or more kinds of bridge-connected cyclic hydrocarbon compound-modified novolac epoxy resins such as dicyclopentadiene-modified novolac epoxy resin. Among them, from the viewpoint of improving the balance between the moisture resistance reliability and the moldability, it is more preferable to contain at least one of a bisphenol type epoxy resin, a biphenyl type epoxy resin and a phenol aralkyl type epoxy resin, and it is particularly preferable to contain at least one of a biphenyl type epoxy resin and a phenol aralkyl type epoxy resin.

As the epoxy resin (a), an epoxy resin containing at least one selected from the group consisting of an epoxy resin represented by the following formula (4), an epoxy resin represented by the following formula (5), and an epoxy resin represented by the following formula (6) is particularly preferably used.

(in formula (4), Ar¹Represents phenylene or naphthylene, in Ar¹In the case of naphthylene group, a glycidyl ether group may be bonded at either of the α -position and the β -position. Ar (Ar)²Represents any one of phenylene, biphenylene and naphthylene. R_aAnd R_bEach independently represents 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 is³Represents a degree of polymerization, and the average value thereof is 1 to 3)

(in the formula (5), there are a plurality of R_cEach independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. n is⁵Represents a degree of polymerization, and the average value thereof is 0 to 4)

(in the formula (6), there are a plurality of R_dAnd R_eEach independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. n is⁶Represents a degree of polymerization, and the average value thereof is 0 to 4)

In the present 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 or more, relative to the entire sealing resin composition. When the content of the epoxy resin (a) is not less than the lower limit value, the flowability 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, and more preferably 30% by mass or less, relative to the entire sealing resin composition. By setting the content of the epoxy resin (a) to the upper limit or less, the moisture resistance reliability and reflow resistance of the semiconductor device including the sealing resin formed using the sealing resin composition can be improved.

(phenol aralkyl resin (B) having a biphenylene skeleton)

The phenol aralkyl resin (B) having a biphenylene skeleton functions as a curing agent which reacts with the epoxy resin to cure the epoxy resin. In the present embodiment, as the phenol aralkyl resin (B) having a biphenylene skeleton, a resin represented by the following formula (7) is more preferably used, and a resin represented by the following formula (8) is particularly preferably used. This can more effectively improve the moldability of the sealing resin composition.

(in the formula (7), R_fAnd R_gIs hydrogen, alkyl with 1-4 carbon atoms or aryl. Each R_fMay be the same or different from each other, and each R_gMay be the same or different from each other. n is⁷Represents a polymerization degree, and has an average value of 1 to 5

(in the formula (8), n⁸Represents a polymerization degree, and has an average value of 1 to 5

In the present embodiment, the content of the phenol aralkyl resin (B) having a biphenylene skeleton in the sealing resin composition is preferably 1% by mass or more, and more preferably 3% by mass or more, relative to the entire sealing resin composition. When the content of the phenol aralkyl resin (B) having a biphenylene skeleton is not less than the lower limit value, the flowability 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 biphenylene skeleton in the sealing resin composition is preferably 20% by mass or less, and more preferably 10% by mass or less, with respect to the entire sealing resin composition. By setting the content of the phenol aralkyl resin (B) having a biphenylene skeleton to the upper limit or less, the moisture resistance reliability and reflow resistance of the semiconductor device including the sealing resin formed using the sealing resin composition can be improved.

The sealing resin composition according to the present embodiment may further contain, as a curing agent, other components than the phenol aralkyl resin (B) having a biphenylene skeleton. Examples of the other component include amines such as linear aliphatic diamines having 2 to 20 carbon atoms, e.g., ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine, m-phenylenediamine, p-phenylenediamine, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylpropane, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylsulfone, 4 ' -diaminodicyclohexyl, bis (4-aminophenyl) phenylmethane, 1, 5-diaminonaphthalene, m-xylylenediamine, p-xylylenediamine, 1-bis (4-aminophenyl) cyclohexane, and dicyandiamide; resol-type phenolic resins such as aniline-modified resol resin and dimethyl ether resol resin; novolak-type phenol resins such as phenol novolak resin, cresol novolak resin, tert-butylphenol novolak resin, and nonylphenol novolak resin; phenol aralkyl resins such as phenol aralkyl resins having a phenylene skeleton; a phenol resin having a condensed polycyclic structure such as a naphthalene skeleton or an anthracene skeleton; polyoxyethylene such as poly (p-oxystyrene); acid anhydrides including alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic dianhydride (PMDA) and Benzophenone Tetracarboxylic Dianhydride (BTDA), and the like; polythiol compounds such as polysulfides, thioesters and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; and organic acids such as carboxylic acid-containing polyester resins.

When the curing agent contains other components than the phenol aralkyl resin (B) having a biphenylene skeleton, the phenol aralkyl resin (B) having a biphenylene skeleton is contained in an amount of preferably 20 mass% or more, more preferably 30 mass% or more, and still more preferably 50 mass% or more of the entire curing agent.

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

The sealing resin composition contains a compound (C) having only one phenolic hydroxyl group. This enables adjustment of the curing characteristics of the sealing resin composition, thereby more effectively improving the balance between moldability and moisture resistance reliability. In the present specification, the term "compound (C) having only one phenolic hydroxyl group" as contained in the sealing resin composition means that the compound (C) is contained in an amount of 1ppm or more based on the entire sealing resin composition.

In the present embodiment, the content of the compound (C) having only one phenolic hydroxyl group is preferably 1ppm or more, and more preferably 5ppm or more, with respect to the entire sealing resin composition. The content of the compound (C) having only one phenolic hydroxyl group is preferably 3000ppm or less, more preferably 2500ppm or less, based on the entire sealing resin composition. When the content of the compound (C) is in such a range, the crosslinked state of the cured resin in contact with the plunger or the mold can be maintained in an appropriate state, and the phenomenon of sticking of the residue can be efficiently reduced.

Further, the content of the compound (C) having only one phenolic hydroxyl group can be analyzed by, for example, gas chromatography. Hereinafter, the same applies to the content of each 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).

The compound (C) having only one phenolic hydroxyl group contains a compound represented by the following formula (1). This can suppress sticking of a residue during seal molding, and can realize a resin composition for sealing having excellent moldability. In the present specification, the compound (C) containing a compound represented by the following formula (1) means a compound (C) containing 1ppm or more of the whole compound (C).

In the present embodiment, the content of the compound represented by the above formula (1) is preferably 10ppm or more, more preferably 15ppm or more, and further preferably 25ppm or more, with respect to the entire sealing resin composition. When the content of the compound represented by the formula (1) is not less than the lower limit value, the adhesion of the residue during the seal molding can be effectively suppressed, and the moldability of the sealing resin composition can be further improved. In order to further effectively suppress the adhesion of the residue, it is preferable that the sealing resin composition contains a compound represented by the above formula (1) in an amount of at least a certain amount. This can be achieved by synthesizing the compound (C) having only one phenolic hydroxyl group by the method according to the present embodiment described later.

On the other hand, the content of the compound represented by the above formula (1) is preferably 300ppm or less, more preferably 200ppm or less, and particularly preferably 100ppm or less, with respect to the entire sealing resin composition. By setting the content of the compound represented by the formula (1) to the upper limit or less, the balance between moldability and curability of the sealing resin composition can be improved.

In the present embodiment, the compound (C) having only one phenolic hydroxyl group may further contain a compound other than the compound represented by the above formula (1). Examples of such other components include a compound represented by the following formula (9) and a compound represented by the following formula (10). By further containing such other components, it is possible to further easily adjust the curing characteristics of the sealing resin composition.

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

The sealing resin composition according to the present embodiment may further contain, for example, a compound (D) represented by the following formula (2). This can more effectively suppress sticking of the residue during seal molding, and further improve the moldability. In addition, adjustment of the curing characteristics can be further facilitated, and the balance between moldability and moisture resistance reliability can be improved. In the present specification, the term "compound (D)" contained in the sealing resin composition means that the compound (D) is contained in an amount of 1ppm or more based on the entire sealing resin composition.

In the present embodiment, the content of the compound (D) represented by the above formula (2) is preferably 30ppm or more, more preferably 40ppm or more, with respect to the entire sealing resin composition. The content of the compound (D) represented by the above formula (2) is preferably 800ppm or less, more preferably 500ppm or less, with respect to the entire sealing resin composition. When the content of the compound (D) represented by the formula (2) is within the above range, the adhesion of the residue during the seal molding can be more effectively suppressed, and the moldability of the sealing resin composition can be further improved. In addition, the balance between moldability and curability of the sealing resin composition can be improved.

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

The sealing resin composition according to the present embodiment may further contain, for example, a compound (E) represented by the following formula (3). This can more effectively suppress sticking of the residue during seal molding, and further improve the moldability. In the present specification, the term "compound (E)" contained in the sealing resin composition means that the compound (E) is contained in an amount of 1ppm or more based on the entire sealing resin composition.

In the present embodiment, the content of the compound (E) represented by the above formula (3) is preferably 1ppm or more, more preferably 3ppm or more, with respect to the entire sealing resin composition. The content of the compound (E) represented by the above formula (3) is preferably 50ppm or less, more preferably 30ppm or less, based on the entire sealing resin composition. When the content of the compound (E) represented by the formula (3) is within the above range, the curing properties of the sealing resin composition can be further improved while the adhesion of the residue during the sealing molding can be more effectively suppressed.

In the present embodiment, the resin composition for sealing may contain a biphenyl compound having 4 or more aromatic rings, as represented by the above formula (1), the above formula (2) and the above formula (3), and having at least 2 phenolic hydroxyl groups, and the aromatic ring at least one end thereof does not have a phenolic hydroxyl group. Such a compound is presumed to have a function of improving releasability from a plunger or a mold at the time of mold opening. The present inventors have found that the releasability of the sealing resin composition at the time of opening the mold is improved based on such findings, and that the adhesion of the residue at the time of seal molding is suppressed.

From such a viewpoint, in order to more effectively suppress the adhesion of the residue, it is particularly preferable that at least one of the compound (D) represented by the above formula (2) and the compound (E) represented by the above formula (3) is contained in addition to the compound represented by the above formula (1) which is the compound (C) having only one phenolic hydroxyl group. This enables the realization of a resin composition for sealing which can be more stably sealed and molded.

In the present embodiment, a mixture containing a phenol aralkyl resin (B) having a biphenylene skeleton and a compound (C) having only one phenolic hydroxyl group can be obtained by subjecting a reaction product obtained by polycondensing a phenol with a bishalomethylbiphenyl such as 4, 4' -bischloromethylbiphenyl to a distillation removal treatment of unreacted components and a washing treatment with water. In this case, the mixture containing the compound represented by the above formula (1) can be obtained by appropriately adjusting the conditions of the distillation removal treatment and the water washing treatment of the unreacted components. In addition, the content of each of the compound (C) having only one phenolic hydroxyl group and the compound represented by the above formula (1) can also be controlled. In the present embodiment, the distillation removal treatment of the unreacted components can be performed by a method of removing, for example, low molecular weight components. The removal of the low molecular weight components can be carried out by appropriately setting the temperature and the degree of reduced pressure in, for example, a general method of reduced pressure distillation, or a method such as steam distillation, molecular distillation, or separation or interception using a GPC column or the like can be used. In particular, in order to contain an appropriate amount of the compound represented by the above formula (1) and the like, the following method is also preferably employed: after the low molecular weight components are once removed by the above-mentioned ordinary method for removing low molecular weight components, the removed low molecular weight components are distilled and fractionated, and then added again to the mother substance. In the washing treatment, for example, an operation (washing with water) of adding distilled water to the reaction product and shaking and then removing the water layer may be performed several times. The phenol may be 1 or 2 or more selected from phenol, cresol, methylphenol, n-propylphenol, xylenol, methylbutylphenol, cyclopentylphenol, and cyclohexylphenol.

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

(Filler (F))

The sealing resin composition may further contain a filler (F), for example. As the filler (F), fillers used in general epoxy resin compositions for encapsulating semiconductors can be used, and examples thereof include: inorganic fillers such as fused spherical silica, fused and pulverized silica, crystalline silica, talc, alumina, titanium white, and silicon nitride; organic fillers such as organosiloxane powder and polyethylene powder. Among these fillers, fused spherical silica is particularly preferably used. These fillers can be used alone in 1, also can be used simultaneously more than 2.

The shape of the filler (F) is not particularly limited, and is preferably spherical as much as possible and has a broad particle size distribution in order to suppress an increase in melt viscosity of the sealing resin composition and to increase the content of the filler.

In the present embodiment, the content of the filler (F) is preferably 35% by mass or more, more preferably 50% by mass or more, and particularly preferably 65% by mass or more, relative to the entire sealing resin composition. When the content of the filler (F) is not less than the lower limit, the sealing resin formed using the sealing resin composition can have improved low moisture absorption and low thermal expansion, and moisture resistance reliability and reflow resistance can be more effectively improved.

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 particularly preferably 90% by mass or less. When the content of the filler (F) is not more than the upper limit value, it is possible to suppress a decrease in moldability associated with a decrease in fluidity of the sealing resin composition, a misalignment of a bonding line due to a high viscosity, and the like.

(curing Accelerator (G))

The sealing resin composition may further contain a curing accelerator (G), for example. The curing accelerator (G) may be any one that can accelerate the crosslinking reaction between the epoxy group of the epoxy resin (a) and the phenolic hydroxyl group of the phenol aralkyl resin (B) having a biphenylene skeleton, and for example, a curing accelerator used in a general epoxy resin composition for sealing can be used.

In the present embodiment, the curing accelerator (G) may contain a phosphorus atom-containing compound selected from, for example, organic phosphines, tetra-substituted phosphonium compounds, phosphate betaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds, and the like; 1 or 2 or more of nitrogen atom-containing compounds such as amidines and tertiary amines exemplified by 1, 8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine and 2-methylimidazole, and quaternary salts of the amidines and amines. Among them, from the viewpoint of improving curability, a phosphorus atom-containing compound is more preferably included. Further, from the viewpoint of improving the balance between moldability and curability, compounds having latency such as tetra-substituted phosphonium compounds, phosphate betaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds are more preferably contained.

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

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

(in the above general formula (13), P represents a phosphorus atom. R⁴、R⁵、R⁶And R⁷Represents an aromatic group or an alkyl group. A represents an anion of an aromatic organic acid having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group on an aromatic ring. AH represents an aromatic organic acid having at least one functional group selected from any one of a hydroxyl group, a carboxyl group and a thiol group in an aromatic ring. x and y are numbers of 1 to 3, z is a number of 0 to 3, and x is y)

The compound represented by the general formula (13) is obtained, for example, as follows, but is not limited thereto. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent, and the mixture is uniformly mixed to form an aromatic organic acid anion in the solution system. Next, when water is added, the compound represented by the general formula (13) can be precipitated. Preferably, in the compound represented by the general formula (13), R bonded to a phosphorus atom⁴、R⁵、R⁶And R⁷Is a phenyl group, AH is a phenol which is a compound having a hydroxyl group on an aromatic ring, and A is an 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 anthracenediol, bisphenols such as bisphenol a, bisphenol F, and bisphenol S, and polycyclic phenols such as phenylphenol and biphenol.

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

(in the above general formula (14), R⁸Represents an alkyl group having 1 to 3 carbon atoms, R⁹Represents a hydroxyl group. f is a number of 0 to 5, g is a number of 0 to 3)

The compound represented by the general formula (14) is obtained, for example, as follows. First, a tertiary phosphine, which is a triaryl-substituted phosphine, is brought into contact with a diazonium salt, and the tertiary phosphine is obtained through a step of substituting the triaryl-substituted phosphine with the diazonium group of the diazonium salt. But is not limited thereto.

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

(in the above general formula (15), P represents a phosphorus atom. R¹⁰、R¹¹And R¹²The alkyl group having 1 to 12 carbon atoms or the aryl group having 6 to 12 carbon atoms may be the same or different. R¹³、R¹⁴And R¹⁵Each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R may be the same or different¹⁴And R¹⁵Can be bonded to form a ring structure)

The phosphine compound used as the adduct of the phosphine compound and the quinone compound is preferably a phosphine compound having an unsubstituted or substituted alkyl or alkoxy group on the aromatic ring, such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, or tris (benzyl) phosphine, and examples of the substituted alkyl or alkoxy group include those having 1 to 6 carbon atoms. From the viewpoint of easy availability, triphenylphosphine is preferred.

Further, as the quinone compound used in the adduct of the phosphine compound and the quinone compound, benzoquinones and anthraquinones can be mentioned, and among them, p-benzoquinone is preferable from the viewpoint of storage stability.

As a method for producing an adduct of a phosphine compound and a quinone compound, an adduct can be obtained by bringing an organic tertiary phosphine and a benzoquinone into contact with each other in a solvent capable of dissolving both of them and mixing them. The solvent may be a solvent having low solubility of the adduct in ketones such as acetone and methyl ethyl ketone. But is not limited thereto.

From the viewpoint of reducing the thermal elastic modulus of a cured product of the sealing resin composition, it is preferable that R bonded to a phosphorus atom in the compound represented by the general formula (15)¹⁰、R¹¹And R¹²Is phenyl, and R¹³、R¹⁴And R¹⁵A compound having a hydrogen atom, that is, a compound obtained by adding 1, 4-benzoquinone to triphenylphosphine.

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

(in the above general formula (16), P represents a phosphorus atom, Si represents a silicon atom, R¹⁶、R¹⁷、R¹⁸And R¹⁹Each represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and may be the same or different from each other. In the formula R²⁰Is a group Y²And Y³A bonded organic group. In the formula R²¹Is a group Y⁴And Y⁵A bonded organic group. Y is²And Y³Represents a group formed by proton donation of a protonic group, and a group Y in the same molecule²And Y³Bonding with silicon atoms to form a chelate structure. Y is⁴And Y⁵Represents a group formed by proton donation of a protonic group, and a group Y in the same molecule⁴And Y⁵Bonding with silicon atoms to form a chelate structure. R²⁰And R²¹May be the same or different from each other, Y²、Y³、Y⁴And Y⁵May be the same or different from each other. Z¹Is an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring)

In the general formula (16), R is¹⁶、R¹⁷、R¹⁸And R¹⁹Examples thereof include phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, naphthyl, hydroxynaphthyl, benzyl, methyl, ethyl, n-butyl, n-octyl, cyclohexyl and the like, and among these, aromatic groups having a substituent such as alkyl, alkoxy, hydroxyl and the like or unsubstituted aromatic groups such as phenyl, methylphenyl, methoxyphenyl, hydroxyphenyl, hydroxynaphthyl and the like are more preferable.

In the general formula (16), R²⁰Is a radical of and Y²And Y³A bonded organic group. Likewise, R²¹Is a group Y⁴And Y⁵A bonded organic group. Y is²And Y³The group Y in the same molecule being a group formed by donating a proton to a protic group²And Y³Bonding with silicon atoms to form a chelate structure. Likewise, Y⁴And Y⁵The group Y in the same molecule being a group formed by donating a proton to a protic group⁴And Y⁵Bonding with silicon atoms to form a chelate structure. Radical R²⁰And R²¹The radicals Y being identical or different from one another²、Y³、Y⁴And Y⁵May be the same or different from each other. In the general formula (16), the group represented by-Y²-R²⁰-Y³-and Y⁴-R²¹-Y⁵The group represented by (E-O) -is composed of a group formed by releasing 2 protons from a proton donor, and the proton donor is preferably an organic acid having at least 2 carboxyl groups or hydroxyl groups in the molecule, more preferably an aromatic compound having at least 2 carboxyl groups or hydroxyl groups on adjacent carbons constituting an aromatic ring, and still more preferably an aromatic compound having at least 2 hydroxyl groups on adjacent carbons constituting an aromatic ring, and examples thereof include catechol, pyrogallol, 1, 2-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2 '-biphenol, 1' -bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acidFormic acid, chloroquinonic acid, tannic acid, 2-hydroxybenzyl alcohol, 1, 2-cyclohexanediol, 1, 2-propanediol, glycerol and the like, and among these, catechol, 1, 2-dihydroxynaphthalene and 2, 3-dihydroxynaphthalene are more preferable.

In addition, Z in the general formula (16)¹Specific examples thereof include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl and octyl, aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl, and reactive substituent groups such as alkyl groups and vinyl groups having a glycidyloxy group, a mercapto group and an amino group, such as glycidoxypropyl, mercaptopropyl and aminopropyl.

A method for producing an adduct of a phosphonium compound and a silane compound includes dissolving a silane compound such as phenyltrimethoxysilane and a proton donor such as 2, 3-dihydroxynaphthalene in a flask containing methanol, and then adding a sodium methoxide-methanol solution dropwise thereto at room temperature with stirring. Further, a solution prepared by dissolving a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide in methanol is dropped thereto under stirring at room temperature, and crystals are precipitated. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain an adduct of a phosphonium compound and a silane compound. However, the present invention is not limited thereto.

In the present embodiment, the content of the curing accelerator (G) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more, relative to the entire sealing resin composition. By setting the content of the curing accelerator (G) to the lower limit or more, the curability at the time of seal molding can be effectively improved.

On the other hand, the content of the curing accelerator (G) is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, relative to the entire sealing resin composition. When the content of the curing accelerator (G) is not more than the above upper limit, the fluidity at the time of seal molding can be improved.

(other component (H))

If necessary, 1 or more of various additives such as a coupling agent, a release agent, an ion scavenger, a low-stress component, a flame retardant, a colorant, and an antioxidant can be appropriately blended in the sealing resin composition.

The coupling agent may contain 1 or 2 or more kinds selected from known coupling agents such as various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, and methacryl silane, titanium compounds, aluminum chelate compounds, and aluminum/zirconium compounds. Among these, as a coupling agent which more effectively exhibits the effects of the present invention, it is more preferable to contain an epoxysilane or an aminosilane, and from the viewpoint of fluidity and the like, it is particularly preferable to contain a secondary aminosilane. The release agent may contain 1 or 2 or more kinds selected from, for example, natural waxes such as carnauba wax, synthetic waxes such as montanate wax, higher fatty acids such as zinc stearate, metal salts thereof, and paraffin wax. The ion scavenger contains, for example, hydrotalcite. The low stress component contains, for example, silicone rubber. The flame retardant may contain 1 or 2 or more selected from, for example, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene. The colorant contains, for example, carbon black.

As the sealing resin composition, there can be used: for example, a composition obtained by mixing the above components by a known method, further melt-kneading the mixture by a kneading machine such as a roll, a kneader or an extruder, cooling the mixture, and then pulverizing the cooled mixture; a composition which is tableted and formed into a tablet shape after pulverization; and a composition obtained by appropriately adjusting the dispersion degree, the fluidity, and the like as needed.

Next, the semiconductor device 100 will be explained.

Fig. 1 is a cross-sectional view showing an example of a semiconductor device 100 according to the present embodiment. The semiconductor device 100 is a semiconductor package including a substrate 10, a semiconductor element 20 mounted on the substrate 10, and a sealing resin 30 sealing the semiconductor element 20. Fig. 1 illustrates a case where the semiconductor device 100 is a BGA package. In this case, a plurality of solder balls 50 are provided on the back surface of the base material 10 on the side opposite to the surface on which the semiconductor element 20 is mounted.

The semiconductor element 20 is electrically connected to the substrate 10 via bonding wires 40. On the other hand, the semiconductor element 20 may be flip-chip mounted on the substrate 10.

In the present embodiment, the sealing resin 30 is composed of a cured product of the above-described sealing resin composition. This can prevent the occurrence of adhesion of the residue when the semiconductor element 20 is sealed. Therefore, more stable manufacturing of the semiconductor device 100 can be achieved. The sealing resin 30 is formed by sealing and molding the sealing resin composition by 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 102 according to the present embodiment. The structure 102 is a molded product formed by MAP molding. Therefore, the structure body 102 is singulated for each semiconductor element 20 to obtain a plurality of semiconductor packages.

The structure 102 includes a base 10, a plurality of semiconductor elements 20, and a sealing resin 30. A plurality of semiconductor elements 20 are arranged on the substrate 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 semiconductor elements 20 are not limited thereto, and may be flip-chip mounted on the substrate 10. The same base material and semiconductor element as those exemplified for the semiconductor device 100 can be used for the base material 10 and the semiconductor element 20.

The sealing resin 30 seals the plurality of semiconductor elements 20. The sealing resin 30 is composed of a cured product of the above-described sealing resin composition. This can suppress the occurrence of sticking of the cull at the time of seal molding. Therefore, the structure 102 and the semiconductor device obtained by singulating the structure can be manufactured more stably. The sealing resin 30 is formed by sealing and molding the sealing resin composition by a known method such as a transfer molding method or a compression molding method.

Examples

Next, examples of the present invention will be explained.

(Synthesis of phenol aralkyl resin (B) having biphenylene skeleton and Compound (C) having Only one phenolic hydroxyl group)

(Synthesis example 1)

First, a separate flask was equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet. Then, 517 parts by mass of phenol (special grade reagent "phenol" manufactured by Kanto chemical Co., Ltd., melting point 41 ℃, molecular weight 94, purity 99.3%) and 251 parts by mass of 4,4 '-bischloromethylbiphenyl (manufactured by Wako pure chemical industries, Ltd. "4, 4' -bischloromethylbiphenyl", melting point 126 ℃, purity 95%, molecular weight 251) pulverized in advance into particles were weighed in the separable flask, and heating was performed while substituting nitrogen gas, and stirring was started simultaneously with the start of melting of phenol. Then, the reaction was carried out at 80 ℃ for 1 hour under reduced pressure to 90kPa after allowing the system to react at 65 ℃ for 3 hours. Subsequently, the temperature in the system was decreased to 70 ℃, 6 parts by mass of trisodium citrate was added thereto, and the mixture was stirred for 30 minutes. Then, 100 parts by mass of heated distilled water was added and the temperature was raised to 140 ℃, and then the unreacted components were distilled off under the condition of 1kPa for 1 hour, and further under the condition of 180 ℃ and 0.2kPa for 1 hour. Further, the fraction obtained by the distillation removal of the unreacted components was stored. Further, the product taken out once was uniformly dissolved in 500 parts by mass of toluene. An operation (water washing) of transferring it to a separatory funnel, adding 150 parts by mass of distilled water, shaking, and then removing the aqueous layer was performed 2 times. Then, the product obtained by distilling off toluene was analyzed by gas chromatography, and a product obtained by washing the unreacted components with water and removing low molecular weight components by molecular distillation, etc. was added to the product. Thus, a mixture containing a phenol aralkyl resin (B) having a biphenylene skeleton, a compound (C) having only one phenolic hydroxyl group, a compound (D) represented by the following formula (2), and a compound (E) represented by the following formula (3) was obtained.

In the obtained mixture, the content of the compound (C) was 1.0 mass% with respect to the phenol aralkyl resin (B) having a biphenylene skeleton. The compound (C) contains a compound represented by the following formula (1). The content of the compound represented by the following formula (1) was 720ppm with respect to the phenol aralkyl resin (B) having a biphenylene skeleton. The content of the compound (D) was 1900ppm with respect to the phenol aralkyl resin (B) having a biphenylene skeleton. The content of the compound (E) was 120ppm with respect to the phenol aralkyl resin (B) having a biphenylene skeleton. In addition, the contents of each of the compound (C), the compound represented by the formula (1), the compound (D), and the compound (E) were analyzed by gas chromatography. The same applies to synthesis examples 2 to 4 below.

(Synthesis example 2)

A mixture containing a phenol aralkyl resin (B) having a biphenylene skeleton, a compound (C) having only one phenolic hydroxyl group, a compound (D) represented by the above formula (2), and a compound (E) represented by the above formula (3) was obtained in the same manner as in synthesis example 1, except that the amount of the unreacted component subjected to molecular distillation was changed. In the obtained mixture, the content of the compound (C) was 1.5% by mass with respect to the phenol aralkyl resin (B) having a biphenylene skeleton. Further, the compound (C) contains a compound represented by the above formula (1). The content of the compound represented by the above formula (1) was 1000ppm with respect to the phenol aralkyl resin (B) having a biphenylene skeleton. The content of the compound (D) was 2630ppm with respect to the phenol aralkyl resin (B) having a biphenylene skeleton. The content of the compound (E) was 160ppm with respect to the phenol aralkyl resin (B) having a biphenylene skeleton.

(Synthesis example 3)

A mixture containing a phenol aralkyl resin (B) having a biphenylene skeleton, a compound (C) having only one phenolic hydroxyl group, a compound (D) represented by the above formula (2), and a compound (E) represented by the above formula (3) was obtained in the same manner as in synthesis example 1, except that the amount of the unreacted component subjected to molecular distillation was changed. In the obtained mixture, the content of the compound (C) was 0.7% by mass with respect to the phenol aralkyl resin (B) having a biphenylene skeleton. Further, the compound (C) contains a compound represented by the above formula (1). The content of the compound represented by the above formula (1) was 500ppm with respect to the phenol aralkyl resin (B) having a biphenylene skeleton. The content of the compound (D) was 1310ppm with respect to the phenol aralkyl resin (B) having a biphenylene skeleton. The content of the compound (E) was 80ppm with respect to the phenol aralkyl resin (B) having a biphenylene skeleton.

(Synthesis example 4)

First, 564 parts by mass of phenol and 484 parts by mass of bis (methoxymethyl) biphenyl were charged in a flask equipped with a stirrer and a cooler, and 15.4 parts by mass of diethyl sulfate was added dropwise thereto. Then, the reaction was carried out for 3 hours while maintaining the temperature in the system at 160 ℃. During this time, the alcohol formed is distilled off. After the reaction, the reaction mixture was cooled and washed with water 3 times. The oil layer was separated, and the unreacted phenol was distilled off by distillation under reduced pressure, whereby a mixture containing a phenol aralkyl resin (B) having a biphenylene skeleton and a compound (C) having only one phenolic hydroxyl group was obtained. In addition, in this synthesis example, no unreacted component subjected to molecular distillation was added. In the obtained mixture, the content of the compound (C) was 0.6 mass% with respect to the phenol aralkyl resin (B) having a biphenylene skeleton.

On the other hand, the compound (D) represented by the above formula (2) and the compound (E) represented by the above formula (3) are not contained in the above mixture. The term "not contained in the mixture" means that the content of the mixture is less than 1ppm based on the whole mixture. In addition, the compound (C) does not contain a compound represented by the above formula (1).

(sealing resin composition)

For examples 1 to 4 and comparative examples 1 to 2, sealing resin compositions were prepared as follows. First, the components were mixed at 15 to 28 ℃ using a mixer according to the formulation shown in table 1, and then roll-kneaded at 70 to 100 ℃. Subsequently, the resultant was cooled and pulverized to obtain a sealing resin composition. In addition, with respect to the phenol aralkyl resin (B) having a biphenylene skeleton, the compound (C), the compound (D) and the compound (E), the above-mentioned mixture obtained in synthesis example 1 was used in examples 1 and 2, the above-mentioned mixture obtained in synthesis example 2 was used in example 3, the above-mentioned mixture obtained in synthesis example 3 was used in example 4, and the above-mentioned mixture obtained in synthesis example 4 was used in comparative examples 1 and 2.

The details of each component in table 1 are as follows. The blending ratios of the respective components shown in table 1 all refer to the blending ratio (mass% or ppm) with respect to the entire sealing resin composition.

(epoxy resin (A))

Epoxy resin 1: phenylaralkyloxy epoxy resins having a phenylene skeleton (NC-2000, manufactured by Nippon Kagaku Co., Ltd.)

Epoxy resin 2: biphenyl epoxy resin (YX4000K, manufactured by Mitsubishi chemical Co., Ltd.)

(phenol aralkyl resin (B) having a biphenylene skeleton)

Phenol aralkyl resin having a biphenylene skeleton 1: phenol aralkyl resin (B) having a biphenylene skeleton synthesized by Synthesis example 1 above

Phenol aralkyl resin having a biphenylene skeleton 2: phenol aralkyl resin (B) having a biphenylene skeleton synthesized by the above Synthesis example 2

Phenol aralkyl resin having a biphenylene skeleton 3: phenol aralkyl resin (B) having a biphenylene skeleton synthesized by Synthesis example 3

Phenol aralkyl resin containing a biphenylene skeleton 4: phenol aralkyl resin (B) having a biphenylene skeleton synthesized by Synthesis example 4 above

(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 (FB 560 (average particle diameter: 30 μm), manufactured by electrochemical engineering Co., Ltd.)

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

(curing Accelerator (G))

Curing accelerator 1: a compound represented by the following formula (11)

Curing accelerator 2: a compound represented by the following formula (12)

[ Synthesis method of curing Accelerator 1 ]

A separable flask equipped with a cooling tube and a stirrer was charged with benzoquinone 6.49g (0.060mol), triphenylphosphine 17.3g (0.066mol) and acetone 40ml, and reacted at room temperature with stirring. The precipitated crystals were washed with acetone, filtered, and dried to obtain curing accelerator 1 as dark green crystals.

[ Synthesis method of curing Accelerator 2 ]

A separable flask equipped with a cooling tube and a stirrer was charged with 12.81g (0.080mol) of 2, 3-dihydroxynaphthalene, 16.77g (0.040mol) of tetraphenylphosphonium bromide and 100ml of methanol, and the mixture was stirred to be dissolved uniformly. A sodium hydroxide solution prepared by dissolving 1.60g (0.04ml) of sodium hydroxide in 10ml of methanol was gradually dropped into the flask to precipitate crystals. The precipitated crystal was filtered, washed with water, and vacuum-dried to obtain curing accelerator 2.

(other component (H))

Coupling agent 1: n-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by shin-Etsu chemical Co., Ltd.)

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

An ion scavenger: hydrotalcite (DHT-4H, manufactured by Kyoho chemical industry Co., Ltd.)

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

And (2) release agent: urethane-modified oxidized polyethylene wax (NSP-6010P, manufactured by Japan ceresin Co., Ltd.)

Colorant: carbon black (Mitsubishi chemical corporation, MA-600)

(evaluation of moldability)

The sealing resin compositions obtained in examples 1 to 4 and comparative examples 1 to 2 were used, respectively, to prepare a sealing resin composition, which was then injected into a mold at a mold temperature of 175 ℃ and an injection pressure of 100kg/cm using a low-pressure transfer molding machine²An 80-lead Quad Flat Package (80pQFP, Cu lead frame, Package size 14 mm. times.20 mm. times.2.0 mmt) was sealed and molded to a shot size (shot) of 500 under the conditions of preheating for 3 seconds, injection time of 7 seconds, and curing time of 45 seconds. Here, the number of times of manually removing the residue (residue of the sealing resin composition) from the plunger or the mold during mold opening by adhering the residue to the plunger or the mold at 500 shots is shown in table 1 as the residue adhesion number. Here, the number of remaining material adhering was 2 or less, and it was evaluated that the moldability was good.

Claims

1. A sealing resin composition characterized by comprising:

an epoxy resin (A);

a phenol aralkyl resin (B) having a biphenylene skeleton;

a compound (C) having only one phenolic hydroxyl group;

a compound (D) represented by the following formula (2); and

a compound (E) represented by the following formula (3),

the compound (C) contains a compound represented by the following formula (1):

the content of the compound represented by the formula (1) is 10 to 300ppm based on the whole sealing resin composition,

the content of the compound (D) represented by the formula (2) is 30 to 800ppm based on the whole sealing resin composition,

the content of the compound (E) represented by the formula (3) is 1 to 50ppm with respect to the entire sealing resin composition.

2. The resin composition for sealing according to claim 1, characterized in that:

the content of the compound (C) is 1ppm to 3000ppm with respect to the entire sealing resin composition.

3. The resin composition for sealing according to claim 1 or 2, characterized in that:

further contains a filler (F).

4. The resin composition for sealing according to claim 3, characterized in that:

the filler (F) contains one or more selected from the group consisting of fused spherical silica, fused pulverized silica, crystalline silica, talc, alumina, titanium white and silicon nitride.

5. The resin composition for sealing according to claim 3, characterized in that:

the content of the filler (F) is 35 to 95 mass% based on the entire sealing resin composition.

6. The resin composition for sealing according to claim 1 or 2, characterized in that:

further contains a curing accelerator (G).

7. The resin composition for sealing according to claim 6, characterized in that:

the curing accelerator (G) contains 1 or 2 or more kinds selected from a phosphorus atom-containing compound and a nitrogen atom-containing compound.

8. The resin composition for sealing according to claim 6, characterized in that:

the content of the curing accelerator (G) is 0.05 to 1.0 mass% based on the entire sealing resin composition.

9. A semiconductor device is characterized by comprising:

a substrate;

a semiconductor element mounted on the base material; and

an encapsulating resin which is composed of a cured product of the encapsulating resin composition according to any one of claims 1 to 8 and encapsulates the semiconductor element.

10. A structure body is characterized by comprising:

a substrate;

a plurality of semiconductor elements mounted on the base material; and

a sealing resin which is composed of a cured product of the sealing resin composition according to any one of claims 1 to 8 and seals the plurality of semiconductor elements.