JP6686428B2 - Epoxy resin composition and semiconductor device - Google Patents

Description

  The present invention relates to an epoxy resin composition and a semiconductor device.

  In recent years, in the market trend of miniaturization, weight reduction, and high functionality of electronic devices, semiconductor devices have been highly integrated and thinned year by year, and have been used conventionally as surface mounting of semiconductor devices is promoted. Instead of the lead frame, the semiconductor element is mounted on a substrate such as an organic substrate or a ceramic substrate, the substrate and the semiconductor element are electrically connected by a connecting member, and then the semiconductor element and the connecting member are molded and sealed by a molding material. The transition to area-mounted semiconductor devices that can be obtained by stopping is progressing. Typical examples of the area mounting type semiconductor device include a BGA (ball grid array) or a CSP (chip scale package) for further miniaturization.

  For such a sealing material, it is required to appropriately select materials such as an epoxy resin, a curing agent, and a curing accelerator according to various purposes. For example, the curing accelerator is used for the purpose of accelerating the crosslinking reaction of the epoxy resin, and tetraphenylphosphine (TPP) is generally used. This technique is described in the following Patent Documents 1 to 3.

  Further, the curing temperature of the encapsulant is generally designed to be 175 ° C. Therefore, in the conventional sealing materials, the characteristics of the sealing material such as moldability and fluidity are evaluated at 175 ° C. as shown in Patent Documents 1 to 3 below.

JP, 2012-67252, A JP, 2006-131653, A JP, 2008-45086, A

However, as a result of examination by the present inventor, in the epoxy resin composition described in the above literature, a curing condition at a lower temperature (for example, 120 ° C. to 130 ° C.) than the conventional curing temperature of 175 ° C. In this case, it was found that there is room for improvement in low temperature curability.
Under low temperature conditions, the crosslinking reaction of the epoxy resin described in the above document becomes difficult to proceed. On the other hand, a method of increasing the curability in a low temperature environment by increasing the addition amount of TPP (curing accelerator), which is generally excellent in latency, can be considered. However, it has been found that the epoxy resin composition thickens and storage stability decreases as the amount of TPP added increases.

  As a result of various studies, the present inventor has found that the use of biphenol type phosphine as a curing accelerator can achieve both the low temperature curability and the storage stability. Further intensive research based on such knowledge, by premising a combination of a specific epoxy resin and a phenol resin, while maintaining low-temperature curability and storability, further improvement of the properties of the epoxy resin composition The inventors have found that the above can be stably realized and have completed the present invention.

（上記一般式（１）中、Ｒ_ｐ１〜Ｒ_ｐ４は、それぞれ独立して、炭素数１〜６の炭化水素基、又は置換もしくは無置換の炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ_ａ１〜Ｒ_ａ１６は、それぞれ独立して、水素原子、又はヒドロキシ基、又は炭素数１〜６の炭化水素基、又は炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ_ａ１〜Ｒ_ａ４、Ｒ_ａ５〜Ｒ_ａ８、Ｒ_ａ９〜Ｒ_ａ１２、およびＲ _ａ１３ 〜Ｒ _ａ１６ は、それぞれのグループ内で互いに結合して環状構造を形成してもよい。Ｘ、Ｙは１〜３の整数であり、Ｚは０〜３の整数であり、かつＸ＝Ｙである。）
According to the invention,
An epoxy resin composition comprising an epoxy resin (A), a phenol resin (B), and a curing accelerator (C),
A combination of the epoxy resin (A), which is a biphenylaralkyl-type epoxy resin, and the phenol resin (B), which is a biphenylaralkyl-type phenol resin, or the epoxy resin (A) and triphenylmethane, which are triphenylmethane-type epoxy resins. Including any of a combination with the phenol resin (B) which is a type phenol resin,
An epoxy resin composition is provided in which the curing accelerator (C) contains a biphenol type phosphine having a structure represented by the following general formula (1).

(In the general formula (1), R _{p1 to} R _p4 are each independently a hydrocarbon group having 1 to 6 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms. R _{a1 to} R _a16 each independently represent a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 6 to 14 carbon atoms. R _{a1 to} R _a4 , R _{a5 to} R _a8 , R _{a9 to} R _a12 , and R _{a13 to} R _a16 , which are aromatic hydrocarbon groups, may be the same or different from each other. May be bonded to each other to form a cyclic structure. X and Y are integers of 1 to 3, Z is an integer of 0 to 3, and X = Y.)

Further, according to the present invention, a semiconductor element,
A semiconductor device comprising a sealing member for sealing the semiconductor element,
There is provided a semiconductor device in which the sealing member is composed of a cured product of the epoxy resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition excellent in low temperature curability and storage stability, and the semiconductor device using the same can be provided.

It is sectional drawing which shows an example of the semiconductor device in this embodiment. It is sectional drawing which shows an example of the structure in this embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same constituents will be referred to with the same numerals, and the description thereof will not be repeated.

（上記一般式（１）中、Ｒ_ｐ１〜Ｒ_ｐ４は、それぞれ独立して、炭素数１〜６の炭化水素基、又は置換もしくは無置換の炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ_ａ１〜Ｒ_ａ１６は、それぞれ独立して、水素原子、又はヒドロキシ基、又は炭素数１〜６の炭化水素基、又は炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ_ａ１〜Ｒ_ａ４、Ｒ_ａ５〜Ｒ_ａ８、Ｒ_ａ９〜Ｒ_ａ１２、およびＲ_ａ１３〜Ｒ_ａ１６は、ぞれぞれのグループ内で互いに結合して環状構造を形成してもよい。Ｘ、Ｙは１〜３の整数であり、Ｚは０〜３の整数であり、かつＸ＝Ｙである。） The epoxy resin composition according to this embodiment contains an epoxy resin (A), a phenol resin (B), and a curing accelerator (C).
The epoxy resin composition is a combination of an epoxy resin (A) which is a biphenylaralkyl type epoxy resin and a phenol resin (B) which is a biphenylaralkyl type phenol resin, or an epoxy resin (A) which is a triphenylmethane type epoxy resin. And a phenol resin (B) which is a triphenylmethane type phenol resin.
Further, the curing accelerator (C) contains a biphenol type phosphine having a structure represented by the following general formula (1).

(In the general formula (1), R _{p1 to} R _p4 are each independently a hydrocarbon group having 1 to 6 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms. R _{a1 to} R _a16 each independently represent a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 6 to 14 carbon atoms. R _{a1 to} R _a4 , R _{a5 to} R _a8 , R _{a9 to} R _a12 , and R _{a13 to} R _a16 are aromatic hydrocarbon groups, which may be the same or different from each other. May combine with each other to form a cyclic structure within the group of X., X and Y are integers of 1 to 3, Z is an integer of 0 to 3, and X = Y.

The present inventor has conducted various studies on a low-temperature curing accelerator that realizes low-temperature curing, and as a result, the OH groups fixed in the biphenol-type phosphine that is the curing accelerator (C) of the present embodiment have been fixed. Instead, he came to pay attention to the structure in which the shaft could rotate. Although the detailed mechanism is not clear, the structure in which the OH groups can rotate about the axis makes it easy for the interaction with the cation (such as ionic bond and hydrogen bond) to be dissociated by thermal vibration, so that it cures even in a low temperature environment. It is thought that it becomes possible to accelerate the reaction.
Further, by using the biphenol type phosphine excellent in low-temperature curability, it is possible to reduce the amount of addition for obtaining desired curability. As a result, the epoxy resin composition of the present embodiment can have excellent storage stability.
As a result of further diligent studies based on such knowledge on low-temperature curing, as a result of the biphenol-type phosphine (curing accelerator (C)) having a predetermined structure, the epoxy resin (A) and the phenol resin (B) were specified. It has been found that the combination can stably improve the characteristics of the epoxy resin composition while maintaining the low temperature curability and the storage stability. For example, by using the epoxy resin composition of the present embodiment, it becomes possible to further suppress the warpage of the semiconductor package.

  The components of the epoxy resin composition of this embodiment will be described in detail.

[Epoxy resin (A)]
The epoxy resin (A) of this embodiment contains a triphenylmethane type epoxy resin or a biphenylaralkyl type epoxy resin.

（上記一般式（４）および（５）中、Ｒ_１０、Ｒ_１１、およびＲ_１２は炭素数１〜６の炭化水素基又は炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。ａおよびｃは０〜３の整数、ｂは０〜４の整数であり、互いに同じであっても異なっていてもよい。Ｘ_１は、単結合または下記一般式（５Ａ）、（５Ｂ）、または（５Ｃ）のいずれかで表される基を示す。下記一般式（５Ａ）、（５Ｂ）および（５Ｃ）中、Ｒ_１３、Ｒ_１４、Ｒ_１５およびＲ_１６は炭素数１〜６の炭化水素基または炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。ｄは０〜２の整数であり、ｅ、ｆおよびｇは０〜４の整数であり、互いに同じであっても異なっていてもよい。）

The triphenylmethane type epoxy resin contains a structural unit represented by the following general formula (4) and / or the following general formula (5).

(In the general formulas (4) and (5), R ₁₀ , R ₁₁ , and R ₁₂ are a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and are the same as each other. A and c are integers of 0 to 3, b is an integer of 0 to 4 and may be the same or different from each other, X ₁ is a single bond or the following general formula. A group represented by any one of formulas (5A), (5B), and (5C): R ₁₃ , R ₁₄ , R ₁₅ and R in the following general formulas (5A), (5B) and (5C). ₁₆ is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms and may be the same or different from each other, d is an integer of 0 to 2, and e, f and g are integers of 0 to 4 and may be the same or different from each other.)

（Ｘ_２は、水素原子または下記式（６Ｂ）で表される基を示す。）

The biphenyl aralkyl type epoxy resin contains a structural unit represented by the following general formula (6).

(X ₂ represents a hydrogen atom or a group represented by the following formula (6B).)

  The epoxy resin (A) of the present embodiment may include other epoxy resin. Examples of other epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol type epoxy resins and other bisphenol type epoxy resins, stilbene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins. , Naphthalene-type epoxy resin, dicyclopentadiene-type epoxy resin, dihydroxybenzene-type epoxy resin, and the like, epoxy resins produced by reacting epichlorohydrin with hydroxyl groups such as phenols and phenol resins, naphthols, or, In addition, epoxy resins such as alicyclic epoxy resins that are epoxidized by oxidizing olefins with peracid, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, etc. are listed. It is. These can be used alone or in combination of two or more.

  The lower limit of the content of the epoxy resin (A) of the present embodiment is, for example, preferably 1% by weight or more, more preferably 3% by weight or more, and more preferably 5% by weight, based on 100% by weight of the entire epoxy resin composition. The above is more preferable. In addition, the upper limit of the content of the epoxy resin (A) is, for example, preferably 90% by weight or less, more preferably 80% by weight or less, and 70% by weight or less based on 100% by weight of the entire epoxy resin composition. More preferable. By setting the content of the epoxy resin (A) within the above preferable range, low hygroscopicity and low temperature curability can be improved. Further, by setting the content of the epoxy resin (A) within the above more preferable range, the solder crack resistance of the obtained semiconductor device can be improved. In the present embodiment, the improvement of the solder crack resistance means that the obtained semiconductor device, for example, in solder dipping or solder reflow step, causes cracks or peeling defects even when exposed to high temperatures. It shows difficult characteristics.

  In the present embodiment, the content based on the entire resin composition refers to the content based on the entire components of the resin composition excluding the solvent, when the solvent is included.

  Further, the lower limit of the content of the biphenylaralkyl type epoxy resin or the triphenylmethane type epoxy resin is, for example, preferably 85% by weight or more, more preferably 90% by weight or more, based on the whole epoxy resin (A). It is more preferably at least wt%. Thereby, the warp of the package can be sufficiently suppressed. On the other hand, the upper limit of the content of the biphenylaralkyl type epoxy resin or the triphenylmethane type epoxy resin is not particularly limited with respect to the entire epoxy resin (A), but may be, for example, 100% by weight or less, and 99% by weight. It may be the following, or may be 98% by weight or less.

[Phenolic resin (B)]
The phenol resin (B) of the present embodiment contains a triphenylmethane type phenol resin or a biphenylaralkyl type phenol resin.

（上記一般式（７）および（８）中、Ｒ_１７、Ｒ_１８、およびＲ_１９は炭素数１〜６の炭化水素基又は炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。Ｙ_３は、水酸基を示す。ｈおよびｊは０〜３の整数、ｉは０〜４の整数であり、互いに同じであっても異なっていてもよい。Ｙ_１は、単結合または下記一般式（８Ａ）、（８Ｂ）、または（８Ｃ）のいずれかで表される基を示す。一般式（８Ａ）〜（８Ｃ）中のＲ_２０、Ｒ_２１、Ｒ_２２およびＲ_２３は炭素数１〜６の炭化水素基または炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。ｋは０〜２の整数であり、ｌ、ｍおよびｎは０〜４の整数であり、互いに同じであっても異なっていてもよい。）

The triphenylmethane type phenol resin contains a structural unit represented by the following general formula (7) and / or the following general formula (8).

(In the general formulas (7) and (8), R ₁₇ , R ₁₈ , and R ₁₉ are a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and are the same as each other. Y ₃ represents a hydroxyl group, h and j are integers of 0 to 3, i is an integer of 0 to 4, and they may be the same or different. ₁ represents a single bond or a group represented by any of the following general formulas (8A), (8B), or (8C): R ₂₀ , R ₂₁ , and R in the general formulas (8A) to (8C). ₂₂ and R ₂₃ are hydrocarbon groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 14 carbon atoms and may be the same or different from each other, and k is an integer of 0 to 2. , L, m and n are integers of 0 to 4 and may be the same or different from each other.)

（Ｙ_２は、水素原子または下記式（９Ｂ）で表される基を示す。）

The biphenylaralkyl-type phenol resin contains a structural unit represented by the following general formula (9).

(Y ₂ represents a hydrogen atom or a group represented by the following formula (9B).)

  The phenol resin (B) of the present embodiment can contain other phenol resins. Examples of the other phenol resin include phenol novolac resin, cresol novolac resin, bisphenol resin, trisphenol resin, xylylene-modified novolac resin, terpene-modified novolac resin, and dicyclopentadiene-modified phenol resin. These can be used alone or in combination of two or more.

  The lower limit of the content of the phenol resin (B) of the present embodiment is, for example, preferably 1 wt% or more, more preferably 2 wt% or more, and further preferably 3 wt% with respect to 100 wt% of the entire epoxy resin composition. The above is more preferable. In addition, the upper limit of the content of the phenol resin (B) is, for example, preferably 60% by weight or less, more preferably 50% by weight or less, and 40% by weight or less with respect to 100% by weight of the entire epoxy resin composition. More preferable. By setting the content of the above-mentioned phenol resin (B) within the above-mentioned preferred range, low hygroscopicity and low-temperature curability can be improved. Further, by setting the content of the phenol resin (B) within the above preferable range, the solder crack resistance of the obtained semiconductor device can be improved.

  Further, the lower limit of the content of the biphenylaralkyl-type phenol resin or the triphenylmethane-type phenol resin is, for example, preferably 95% by weight or more, more preferably 96% by weight or more, based on the whole phenol resin (B). It is more preferably at least wt%. Thereby, the warp of the package can be sufficiently suppressed. On the other hand, the upper limit of the content of the biphenylaralkyl-type phenol resin or the triphenylmethane-type phenol resin is not particularly limited with respect to the entire phenol resin (B), but may be, for example, 100% by weight or less, and 99% by weight. It may be the following, or may be 98% by weight or less.

（上記一般式（１）中、Ｒ_ｐ１〜Ｒ_ｐ４は、それぞれ独立して、炭素数１〜６の炭化水素基、又は置換もしくは無置換の炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ_ａ１〜Ｒ_ａ１６は、それぞれ独立して、水素原子、又はヒドロキシ基、又は炭素数１〜６の炭化水素基、又は炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。Ｒ_ａ１〜Ｒ_ａ４、Ｒ_ａ５〜Ｒ_ａ８、Ｒ_ａ９〜Ｒ_ａ１２、およびＲ_ａ１３〜Ｒ_ａ１６は、ぞれぞれのグループ内で互いに結合して環状構造を形成してもよい。Ｘ、Ｙは１〜３の整数であり、Ｚは０〜３の整数であり、かつＸ＝Ｙである。） [Curing accelerator (C)]
The curing accelerator (C) of the present embodiment contains a biphenol type phosphine having a structure represented by the following general formula (1).

(In the general formula (1), R _{p1 to} R _p4 are each independently a hydrocarbon group having 1 to 6 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms. R _{a1 to} R _a16 each independently represent a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 6 to 14 carbon atoms. R _{a1 to} R _a4 , R _{a5 to} R _a8 , R _{a9 to} R _a12 , and R _{a13 to} R _a16 are aromatic hydrocarbon groups, which may be the same or different from each other. May combine with each other to form a cyclic structure within the group of X., X and Y are integers of 1 to 3, Z is an integer of 0 to 3, and X = Y.

（上記一般式（２）中、Ｒ_ａ１７〜Ｒ_２４は、それぞれ独立して、水素原子、又は水酸基、又は炭素数１〜６の炭化水素基、又は炭素数６〜１４の芳香族炭化水素基であり、互いに同じであっても異なっていてもよい。） Moreover, as a preferable example of the curing accelerator (C), a biphenol type phosphine having a structure represented by the following general formula (2) can be used.

(In the general formula (2), R _{a17 to} R ₂₄ are each independently a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms. And may be the same or different from each other.)

Further, as a more preferable example of the curing accelerator (C), biphenol type phosphine having a structure represented by the following formula (3) can be used.

  The lower limit of the content of the curing accelerator (C) of the present embodiment is, for example, preferably 0.05% by weight or more, and more preferably 0.08% by weight or more based on 100% by weight of the entire epoxy resin composition. Preferably, 0.1% by weight or more is more preferable. Further, the upper limit of the content of the curing accelerator (C) is, for example, preferably 15% by weight or less, more preferably 13% by weight or less, and more preferably 10% by weight or less with respect to 100% by weight of the entire epoxy resin composition. Is more preferable. By setting the content of the curing accelerator (C) to be the lower limit value or more, the low temperature curability can be improved. Further, by setting the content of the curing accelerator (C) to be equal to or less than the upper limit value, it is possible to improve storability and fluidity.

  As a method for producing the curing accelerator (C) which is a biphenol type phosphine of the present embodiment, for example, biphenol and phosphonium having a predetermined structure represented by the general formula (1) are used in an organic solvent such as methanol. Mix and add sodium hydroxide dropwise with stirring the mixture. After continuing stirring for a predetermined time, water is added, suction filtration, washing with water, and drying are carried out to obtain the biphenol type phosphine of the present embodiment.

[Inorganic filler (D)]
The epoxy resin composition of this embodiment may further include an inorganic filler (D).

  The inorganic filler (D) of the present embodiment is not particularly limited, but examples thereof include fused crushed silica, fused silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, talc, clay, glass fiber. Etc. These can be used alone or in combination of two or more. Among these, as the inorganic filler (D), fused silica is particularly preferable. Since fused silica has poor reactivity with the curing accelerator (C), it prevents the curing reaction of the epoxy resin composition from being hindered even when a large amount is incorporated into the epoxy resin composition of the present embodiment. be able to. Further, by using fused silica as the inorganic filler (D), the reinforcing effect of the obtained semiconductor device is further improved.

  The shape of the inorganic filler (D) may be, for example, granular, lumpy, scale-like or the like, but among them, granular (particularly spherical) is preferable.

  The lower limit of the average particle diameter of the inorganic filler (D) of this embodiment is, for example, preferably 1 μm or more, more preferably 5 μm or more. The upper limit of the average particle diameter of the inorganic filler (D) is preferably 100 μm or less, more preferably 35 μm or less. By setting the average particle diameter of the inorganic filler (D) within the above range, it is possible to enhance the filling property and suppress an increase in the melt viscosity of the epoxy resin composition.

  The lower limit of the content of the inorganic filler (D) of the present embodiment is, for example, preferably 40% by weight or more, more preferably 50% by weight or more, and 60% by weight with respect to 100% by weight of the entire epoxy resin composition. % Or more is more preferable. In addition, the upper limit of the content of the inorganic filler (D) is, for example, preferably 99% by weight or less, more preferably 95% by weight or less, and 90% by weight or less with respect to 100% by weight of the entire epoxy resin composition. Is more preferable. By setting the content of the inorganic filler (D) to be the lower limit value or more, it is possible to suppress the warpage of the package molded using the epoxy resin composition of the present embodiment, and to suppress the moisture absorption amount and the strength. Can be reduced. Further, by setting the content of the inorganic filler (D) to be equal to or less than the above upper limit, the fluidity of the epoxy resin composition of the present embodiment can be enhanced and the moldability can be improved.

  The epoxy resin composition of the present embodiment may contain other additives, if necessary, in addition to the compounds (A) to (D). Other additives include, for example, coupling agents such as γ-glycidoxypropyltrimethoxysilane, colorants such as carbon black, brominated epoxy resins, antimony oxide, flame retardants such as phosphorus compounds, silicone oil, and silicone. A low stress component such as rubber, a natural wax, a synthetic wax, a higher fatty acid or a metal salt thereof, a releasing agent such as paraffin, and various additives such as an antioxidant can be used. You may use these 1 type (s) or 2 or more types.

  The method for producing the epoxy resin composition of the present embodiment is, for example, a method in which the compounds (A) to (D), and, if necessary, other additives are mixed at room temperature using a mixer, and then heated rolls are used. It is obtained by heating and kneading with a heating kneader, cooling and pulverizing.

  The epoxy resin composition of the present embodiment can be used, for example, as a sealing resin composition used for sealing electronic components such as semiconductor elements.

  The semiconductor device of this embodiment has a structure in which a semiconductor element is sealed with a cured product of the epoxy resin composition of this embodiment. The semiconductor device of the present embodiment can be obtained, for example, by using a molding method such as transfer molding, compression molding, or injection molding to cure-mold the epoxy resin composition and seal electronic components such as semiconductor elements. .

  The semiconductor device of this embodiment is not particularly limited, but for example, SIP (Single Inline Package), HSIP (SIP with Heatsink), ZIP (Zig-zag Inline Package), DIP (Dual Inline Package), SDIP (DIP). Inline Package, SOP (Small Outline Package), SSOP (Shrink Small Outline Package), TSOP (Thin Small Outline Package), SOJ (Small Outline Qage), SOJ (Small Outline Qage). Pitc ), TQFP (Thin Quad Flat Package), QFJ (PLCC) (Quad Flat J-leaded Package), it is possible to BGA (Ball Grid Array) or the like is exemplified.

Next, the semiconductor device 100 will be described with reference to FIG.
FIG. 1 is a cross-sectional view showing an example of the semiconductor device 100.

  A semiconductor device 100 includes a substrate 10, a semiconductor element 20 mounted on one surface of the substrate 10, and a sealing resin layer 30 that seals the one surface of the substrate 10 and the semiconductor element 20. It is a package. That is, the semiconductor device 100 is a single-sided sealed semiconductor package in which the other surface of the substrate 10 opposite to the one surface is not sealed by the sealing resin layer 30. The sealing resin layer 30 is made of a cured product of the epoxy resin composition of this embodiment. As a result, the linear expansion coefficient of the sealing resin layer 30 during heating can be increased, so that the difference in the linear expansion coefficient between the sealing resin layer 30 and the substrate 10 during heating can be reduced. Therefore, the warp of the entire semiconductor device 100 can be suppressed when used in a high temperature environment.

  In the present embodiment, the upper surface of the semiconductor element 20 may be covered with the sealing resin layer 30 (FIG. 1) or may be exposed from the sealing resin layer 30 (not shown).

  In the example shown in FIG. 1, the substrate 10 is an organic substrate. A plurality of solder balls 12, for example, are provided on the back surface of the substrate 10 opposite to the front surface (mounting surface) on which the semiconductor element 20 is mounted. The semiconductor element 20 is flip-chip mounted on the substrate 10, for example. The semiconductor element 20 is electrically connected to the substrate 10 via a plurality of bumps 22, for example. As a modification, the semiconductor element 20 may be electrically connected to the substrate 10 via a bonding wire.

  In the present example shown in FIG. 1, the gap between the semiconductor element 20 and the substrate 10 is filled with, for example, an underfill 32. As the underfill 32, for example, a film-like or liquid underfill material can be used. The underfill 32 and the sealing resin layer 30 may be made of different materials, but may be made of the same material. The epoxy resin composition of this embodiment can be used as a mold underfill material. Therefore, the underfill 32 and the sealing resin layer 30 can be made of the same material and can be formed in the same step. Specifically, the sealing step of sealing the semiconductor element 20 with the epoxy resin composition and the filling step of filling the gap between the substrate 10 and the semiconductor element 20 with the epoxy resin composition are the same step (collective). Can be implemented in.

In the present embodiment, the thickness of the sealing resin layer 30 is, for example, from the mounting surface of the substrate 10 (one surface opposite to the surface on which the bumps 12 for external connection are formed). It may be the shortest distance to the surface. The thickness of the encapsulating resin layer 30 refers to the thickness of the encapsulating resin layer 30 based on the one surface of the substrate 10 in the normal direction of the one surface on which the semiconductor element 20 is mounted. In this case, the upper limit of the thickness of the sealing resin layer 30 may be 0.4 mm or less, 0.3 mm or less, and 0.2 mm or less, for example. On the other hand, the lower limit of the thickness of the sealing resin layer 30 is not particularly limited, but may be, for example, 0 mm or more (exposed type), or 0.01 mm or more.
The upper limit of the thickness of the substrate 10 may be, for example, 0.8 mm or less, or 0.4 mm or less. On the other hand, the lower limit of the thickness of the substrate 10 is not particularly limited, but may be 0.1 mm or more, for example.
According to the present embodiment, the semiconductor package can be made thinner in this way. Further, even in the case of a thin semiconductor package, the warp of the semiconductor device 100 can be suppressed by forming the sealing resin layer 30 using the epoxy resin composition according to this embodiment. Further, in the present embodiment, for example, the thickness of the sealing resin layer 30 can be set to be equal to or less than the thickness of the substrate 10. Thereby, the semiconductor device 100 can be thinned more efficiently.

Next, the structure 102 will be described.
FIG. 2 is a cross-sectional view showing an example of the structure 102. The structure 102 is a molded product formed by MAP molding. Therefore, a plurality of semiconductor packages can be obtained by dividing the structure 102 into individual semiconductor elements 20.

  The structure body 102 includes a substrate 10, a plurality of semiconductor elements 20, and a sealing resin layer 30. The plurality of semiconductor elements 20 are arranged on one surface of the substrate 10. FIG. 2 illustrates the case where each semiconductor element 20 is flip-chip mounted on the substrate 10. In this case, each semiconductor element 20 is electrically connected to the substrate 10 via the plurality of bumps 22. On the other hand, each semiconductor element 20 may be electrically connected to the substrate 10 via a bonding wire. The substrate 10 and the semiconductor element 20 may be the same as those exemplified in the semiconductor device 100.

  In the example shown in FIG. 2, the gap between each semiconductor element 20 and the substrate 10 is filled with, for example, an underfill 32. As the underfill 32, for example, a film-like or liquid underfill material can be used. On the other hand, the above-mentioned epoxy resin composition can also be used as a mold underfill material. In this case, the sealing of the semiconductor element 20 and the filling of the gap between the substrate 10 and the semiconductor element 20 are collectively performed.

  The sealing resin layer 30 seals the semiconductor elements 20 and the one surface of the substrate 10. In this case, the other surface of the substrate 10 opposite to the one surface is not sealed by the sealing resin layer 30. The sealing resin layer 30 is composed of a cured product of the epoxy resin composition described above. Thus, the warp of the structure body 102 or a semiconductor package obtained by dividing the structure body 102 into individual pieces can be suppressed. The encapsulating resin layer 30 is formed, for example, by encapsulating the epoxy resin composition by a known method such as a transfer molding method or a compression molding method. In the present embodiment, the upper surface of each semiconductor element 20 may be sealed with the sealing resin layer 30 as shown in FIG. 2 or may be exposed from the sealing resin layer 30 (not shown). ).

  Although the case where the epoxy resin composition of the present invention is used as a sealing material for a semiconductor device has been described in the present embodiment, the use of the epoxy resin composition of the present invention is not limited to this.

  Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various configurations other than the above may be adopted.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the description of these examples. Unless otherwise specified, "parts" and "%" shown below are "parts by weight" and "% by weight", respectively.

The components used in each Example and each Comparative Example are shown below.
(Preparation of epoxy resin composition)
First, the raw materials blended according to Table 1 were mixed at room temperature in a mortar and then melt-mixed for 3 minutes on a hot plate at 120 ° C. After cooling, it was ground again in a mortar at room temperature to obtain an epoxy resin composition.
Details of each component in Table 1 are as follows. The unit in Table 1 is% by weight.

エポキシ樹脂２：下記式（９）で表されるトリフェニルメタン型エポキシ樹脂（三菱化学（株）製１０３２Ｈ−６０、エポキシ当量１６３ｇ／ｅｑ） Epoxy resin (A)
Epoxy resin 1: Phenol aralkyl type epoxy resin having a biphenylene skeleton represented by the following formula (8) (NC-3000 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 276 g / eq, softening point 57 ° C.)

Epoxy resin 2: triphenylmethane type epoxy resin represented by the following formula (9) (Mitsubishi Chemical Corporation 1032H-60, epoxy equivalent 163 g / eq)

フェノール樹脂２：下記式（１１）で表されるトリフェニルメタン骨格を有するフェノール樹脂（明和化成（株）製ＭＥＨ−７５００、水酸基当量９７ｇ／ｅｑ、軟化点１１０℃）

Phenolic resin (B)
Phenol resin 1: Phenol aralkyl resin having a biphenylene skeleton represented by the following formula (10) (GPH-65 manufactured by Nippon Kayaku Co., hydroxyl equivalent 196 g / eq, softening point 65 ° C.)

Phenol resin 2: Phenolic resin having a triphenylmethane skeleton represented by the following formula (11) (MEH-7500 manufactured by Meiwa Kasei Co., hydroxyl group equivalent 97 g / eq, softening point 110 ° C.)

硬化促進剤２：下記式（１３）で表されるビフェノール型ホスフィン
５０ｍＬのビーカーに撹拌子を入れ、３，３'，５，５'−テトラ−ｔｅｒｔ−ブチル−２，２'−ジヒドロキシビフェノール、水酸化ナトリウムを予めイオン交換水で溶解した溶液（５Ｎ水酸化ナトリウム水溶液）、メタノールを仕込み、９０℃まで加熱し、内部が溶解した後に、攪拌しながら、テトラフェニルホスホニウムブロマイドのメタノール溶液を添加した。９０℃で２時間程度攪拌した後、白色沈殿を得た。さらに水を添加し、沈殿物を濾過、水洗、乾燥して、白色結晶であるビフェノール型ホスフィンを得た。

硬化促進剤３：トリフェニルホスフィン（ＴＰＰ）（ケイ・アイ化成（株）製、ＰＰ３６０） Curing accelerator (C)
Curing accelerator 1: Biphenol-type phosphine represented by the following formula (12): A stirrer was placed in a 500 mL beaker, 2,2'-biphenol, tetraphenylphosphonium bromide, and methanol were charged, and the inside was dissolved and then stirred. Meanwhile, a solution (5N aqueous sodium hydroxide solution) in which sodium hydroxide was previously dissolved in ion-exchanged water was added. After stirring at room temperature for about 2 hours, a white precipitate was obtained. Water was further added, and the precipitate was filtered, washed with water and dried to obtain white crystals of biphenol type phosphine.

Curing accelerator 2: Biphenol type phosphine represented by the following formula (13): A stirrer was placed in a 50 mL beaker, and 3,3 ', 5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenol, A solution of sodium hydroxide previously dissolved in ion-exchanged water (5N sodium hydroxide aqueous solution) and methanol were charged and heated to 90 ° C. After the inside was dissolved, a methanol solution of tetraphenylphosphonium bromide was added with stirring. . After stirring at 90 ° C. for about 2 hours, a white precipitate was obtained. Water was further added, and the precipitate was filtered, washed with water and dried to obtain white crystals of biphenol type phosphine.

Curing accelerator 3: triphenylphosphine (TPP) (PP360, manufactured by KAI Kasei Co., Ltd.)

Inorganic filler (D)
Inorganic filler 1: fused spherical silica (manufactured by Micron Corp., TS-13-006, average particle diameter 28 μm, specific surface area 2.5 m ² / g)
Inorganic filler 2: fused spherical silica (manufactured by Tatsumori Co., Ltd., MSR-SC3-TS, average particle size 17 μm, specific surface area 2.2 m ² / g)

(Additive)
Curing retarder 1: 2,3-dihydroxynaphthalene (manufactured by Air Water Co., Ltd.)
Silane coupling agent 1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
Colorant 1: Carbon black (MA600, manufactured by Mitsubishi Chemical Corporation)
Release agent 1: Carnauba wax (Nikko Fine Co., Ltd., Nikko carnauba, melting point 83 ° C.)
Release Agent 2: Oxidized Polyethylene (Clariant, PED191)
Ion scavenger 1: hydrotalcite (Kyowa Chemical Industry Co., Ltd., DHT-4H)
Low-stressing agent 1: Alkanecarboxylic acid-2,2-bis [4- (2,3-epoxypropoxy) phenyl] propane-poly (dimethylsiloxane) polycondensate (Sumitomo Bakelite Co., Ltd.)
Low-stressing agent 2: Carboxyl group-terminated butadiene / acrylonitrile copolymer (PTI Japan Co., Ltd., CTBN1008-SP)

  Each of the examples and comparative examples was evaluated for the epoxy resin composition as follows.

(Curast @ 125 ℃)
The curast torque of the epoxy resin composition was measured with the use of a curast meter (manufactured by A & D Co., Ltd., curast meter WP type) at a mold temperature of 125 ° C., and 15 minutes after the start of measurement. The measured curast torque value was used as the saturation torque value. The tablets used were 4.3 g of the epoxy resin composition placed in a 25 mmφ mold and tableted for 5 t for 1 minute. Furthermore, the epoxy resin composition tested the sample immediately after tablet production, and tested the sample after storing it in a 25 degreeC thermostat for 48 hours. The rise time of curast was observed from the time when about 60% of the reactive functional groups had reacted. Further, the slope of the tangent line of the curast curve after 2 minutes from the rising time was calculated.

(DSC)
A differential scanning calorimeter (DSC-6100 manufactured by Seiko Instruments Inc.) was used to measure 10 mg of the epoxy resin composition under a nitrogen stream at a heating rate of 10 ° C./min.

(Minimum melt viscosity)
The minimum melt viscosity was measured using (1) viscometer or (2) rectangular channel pressure measurement.
(1) Viscometer: The minimum melt viscosity was measured for a tablet-shaped epoxy resin composition using a cone plate type viscometer (manufactured by Toa Kogyo Co., Ltd., serial number CV-1S). As the tablet-shaped epoxy resin composition, 100 mg of the epoxy resin composition was placed in a 25 mmφ mold and tableted for 3 t for 1 minute. Furthermore, the epoxy resin composition tested the sample immediately after tablet production, and tested the sample after storing at room temperature (25 degreeC) for 48 hours.
(2) Rectangular channel pressure measurement: The minimum melt viscosity was measured using a low pressure transfer molding machine (manufactured by NEC Corporation, 40t manual press) under the conditions of a mold temperature of 175 ° C. and an injection speed of 177 cm ³ / sec. The above epoxy resin composition was injected into a rectangular channel having a width of 13 mm and a length of 175 cm, and the time-dependent change in pressure was measured with a pressure sensor embedded 25 mm from the upstream end of the channel to measure the time course of the epoxy resin composition. The minimum pressure during flow was measured. Further, the sample after the epoxy resin composition was stored at room temperature (25 ° C.) for 48 hours was also measured.

(Spiral flow)
Using a low pressure transfer molding machine (KTS-15 manufactured by Kotaki Seiki Co., Ltd.), a spiral flow measuring mold conforming to ANSI / ASTM D 3123-72 was used, the mold temperature was 125 ° C., the injection amount was 6.9 MPa, and the temperature was maintained. The epoxy resin composition obtained above was injected under the condition of a pressure time of 15 minutes, and the flow length was measured.

(Bending strength, flexural modulus)
According to JIS K 6911, a transfer molding machine was used to mold an epoxy resin test piece of 80 mm × 10 mm × 4 mm (mold thickness) at a mold temperature of 125 ° C., an injection pressure of 6.9 MPa, and a curing time of 15 minutes, Flexural strength and flexural modulus were measured at 30 ° C and 260 ° C.

(Linear expansion coefficient: TMA analysis (thermomechanical analysis))
Using a transfer molding machine, in a mold for spiral flow measurement according to EMMI-1-66, mold temperature 125 ° C., injection pressure 6.9 MPa, curing time 15 minutes, 10 mm × 4 mm × 4 mm (thickness The cured product of the epoxy resin composition of 1) was molded, and TMA analysis (TMA-100, manufactured by Seiko Instruments Inc.) was performed at a temperature rising rate of 5 ° C / min. The coefficient of thermal expansion of the obtained TMA curve at 60 ° C and 260 ° C was read as α1, α2, and the temperature of the intersection of the TMA curve and the tangent line at 60 ° C and 260 ° C, respectively, and this temperature was taken as the glass transition temperature (Tg). did.

(Amount of package warp, amount of fluctuation)
Using a low pressure transfer molding machine (TOWA Co., Ltd., Y series), degassing molding (17 torr) at a mold temperature of 125 ° C., an injection pressure of 6.9 MPa, a curing time of 15 minutes, and an injection time of 15 seconds was performed at 50 mm. A panel having a size of × 55 mm × 350 μm (the maximum thickness of the cured resin for the sealing resin from the semiconductor element mounting surface of the substrate) was molded. The size of the substrate (core: CCL-HL832HS, 100 μm thick, Cu: 12 μm, core: manufactured by Mitsubishi Kazan Chemical Co., Ltd., PSR-AUS308, 12 μm thick, manufactured by Taiyo Ink Mfg. Co., Ltd.) used for molding. 55mm × 62mm, 3 × 3 = 9 pieces of flip chips (SIN surface, mounting solder bumps: φ100μm lead-free solder, 200μm pitch full grid) of 10mm × 10mm × 150μm thickness (excluding solder bumps) are mounted in advance. There is. After molding, 9 pieces were cut into a size of 14 × 14 mm to obtain a BGA package for testing. With respect to the nine obtained packages, the displacement in the height direction was measured using a shadow moire type warpage measuring device (PS-200 manufactured by Acrometrix Co.), and the displacement amount at room temperature was taken as the package warpage amount. Further, the displacement difference between the maximum displacement amount and the minimum displacement amount when the measurement temperature was raised from 25 ° C. to 260 ° C. and then lowered to 25 ° C. was defined as the package variation amount.

(Regarding Examples 1 and 3 and Comparative Example 1)
From the results of the DSC measurement, it was found that the addition amount of bisphenol phosphine can be suppressed more than the addition amount of TPP in order to exhibit the same curability as that of a general-purpose product TPP.
From the result of the curast measurement (90% torque saturation time), it was found that the low temperature fast curability of Examples 1 and 3 (bisphenol type phosphine) was superior to that of Comparative Example 1 (TPP). Further, from the result of the rising time, it was found that the latent properties of Examples 1 and 3 (bisphenol type phosphine) were superior to Comparative Example 1 (TPP). In addition, it was found that the latency of Example 3 can be enhanced more than that of Example 1.
From the result of the curast measurement after 48 hours, the change rate of the saturation torque value between 0 hour and 48 hours was smaller, so that the storability of Examples 1 and 3 (bisphenol type phosphine) was Comparative Example 1 (TPP). Turns out to be better than.
From the measurement result of the minimum melt viscosity, it was found that the fluidity and the storability of Examples 1 and 3 (bisphenol type phosphine) were superior to those of Comparative Example 1 (TPP). In this example, it can be said that a significant difference in the storability measurement result using the viscometer at the minimum melt viscosity is that the viscosity change amount is about 15 mPa · s or more.

(Example 2, Comparative Example 2)
From the results of the DSC measurement, it was found that the addition amount of bisphenol phosphine can be suppressed more than the addition amount of TPP in order to exhibit the same curability as that of a general-purpose product TPP.
From the result of the curast measurement (90% torque saturation time), it was found that the low-temperature fast-curing property of Example 2 (bisphenol type phosphine) was superior to that of Comparative Example 2 (TPP). Furthermore, from the result of the rise time, it was found that the latency of bisphenol type phosphine was superior to that of Comparative Example 2 (TPP).
From the result of the curast measurement after 48 hours, the change rate of the saturation torque value between 0 hour and 48 hours was smaller, and thus the storage stability of Example 2 (bisphenol type phosphine) was better than that of Comparative Example 2 (TPP). It turned out to be excellent.
From the measurement result of the minimum melt viscosity, it was found that the fluidity and the storability of Example 2 (bisphenol type phosphine) were superior to those of Comparative Example 2 (TPP).
From the measurement result of the warp amount (reflow temperature A: 175 ° C.), it was found that the initial warp amount of Example 2 (bisphenol type phosphine) was suppressed as compared with Comparative Example 2 (TPP). Further, from the measurement result of the warp amount (reflow temperature B: 260 ° C.), it was found that the fluctuation range of Example 2 (bisphenol type phosphine) was suppressed more than that of Comparative Example 2 (TPP). It can be said that about 10 μm or more is a significant difference in the measurement result of the amount of warpage in this example. Although the detailed mechanism is not clear, it is considered that the structure of the cured product incorporating the bisphenol type phosphine has a low elasticity because the bisphenol type phosphine has a high degree of freedom. In addition, since it can be cured at a low temperature, it is considered that the amount of warpage is suppressed.
From the measurement results of the physical property values, it was found that in Example 2 (bisphenol type phosphine), the spiral flow was longer than that of Comparative Example 2 (TPP) and the elasticity was excellent.

(Regarding Example 4 and Comparative Example 3)
From the result of the curast measurement (90% torque saturation time), it was found that the low temperature fast curability of Example 4 (bisphenol phosphine) was superior to that of Comparative Example 3 (TPP). Further, from the result of the rising time, it was found that the latent property (bisphenol type phosphine) of Example 4 was superior to those of Examples 1 and 3.
From the result of the curast measurement after 48 hours, the change rate of the saturation torque value between 0 hour and 48 hours was within the following allowable range, and thus the storage stability of Example 4 (bisphenol type phosphine) was evaluated as Comparative Example 3 (TPP). ) Is equivalent to. In the curast measurement of this example, it was determined that the storability was equivalent when the rate of change of the saturation torque value between 0 hours and 48 hours was within the allowable range of 100 to 130%.
From the measurement results of the minimum melt viscosity, it was found that the fluidity of Example 4 (bisphenol type phosphine) was superior to that of Comparative Example 3 (TPP), and the storability of Example 4 was equivalent to that of Comparative Example 4. .

(Regarding Example 5 and Comparative Example 4)
As a result of the curast measurement (90% torque saturation time), as shown by * 1 and 2 in Table 2, the 90% torque saturation time and the saturation torque value at 125 ° C. were too high to be measured. In this case, instead of the saturation torque value (* 2), the low temperature fast curability can be evaluated from the slope of the curast curve.
As shown in Table 3, in Example 5 (bisphenol-type phosphine), the curast curve has a larger inclination than Comparative Example 4 (TPP), and it was found that the low-temperature fast-curing property is excellent.
Instead of the saturation torque value (* 2) after 48 hours, the storability can be evaluated from the rate of change of the slope of the curast curve.
As shown in Table 3, the storability of Example 5 (bisphenol-type phosphine) was different from that of Comparative Example 4 (TPP) because the rate of change in the slope of the curast curve after 0 hour and 48 hours was within the following allowable range. It turned out to be equivalent. In the curast measurement of this example, if the change rate of the slope of the curast curve between 0 hours and 48 hours was within the allowable range of 100 to 130%, it was determined that the storability was the same.
From the measurement results of the physical property values, it was found that Example 5 (bisphenol type phosphine) was superior to Example 2 in high elasticity. In addition, the result of Example 5 has a higher glass transition temperature than that of Comparative Example 4. Therefore, it is considered that Example 5 is superior to Comparative Example 4 in elastic force at 260 ° C.

The above experimental results will be supplemented with the following assumptions.
The curing accelerators of Examples and Comparative Examples have different curing reaction mechanisms. That is,
In the examples, it is considered that two reactions of epoxy + phenol and epoxy + epoxy proceed in the comparative example. Therefore, it is difficult to make a simple comparison of the curing rates, but it is presumed as follows.
In Examples 1 to 3, since the addition amount (molar ratio) of the curing accelerator is smaller than that in Comparative Examples 1 and 2, the number of active species generated by ionic dissociation of biphenol phosphine is higher than that in Comparative Examples 1 and 2. Since the reaction start time is slower than that of Comparative Examples 1 and 2, since it is less, it is considered that once activated, the reaction proceeds at once. Therefore, it is considered that as a result of the slow rise of curast, the storability is improved and the fluidity in spiral flow is also improved.
On the other hand, in Comparative Examples 1 and 2, the reaction of epoxy + epoxy also proceeds, so it is considered that it takes more time to complete the curing.
In addition, in Examples 4 and 5, since the amount of the curing accelerator itself added was the same as that of Comparative Examples 3 and 4, curing was more likely to proceed at a lower temperature than Comparative Examples 3 and 4, and the rise of curast was suppressed. It is thought that the time will be faster.
In addition, in Comparative Examples 3 and 4, since the TPP + curing retarder 2,3-DON is contained, the curast rise time is also slower than that of Comparative Examples 1 and 2 having only TPP, but the fluidity is low. The spiral flow of the index is comparable to that of Comparative Example 2.

  Although the present invention has been described more specifically based on the embodiments, these are examples of the present invention, and various configurations other than the above can be adopted.

10 substrate 12 solder ball 20 semiconductor element 22 bump 30 sealing resin layer 32 underfill 100 semiconductor device 102 structure

Claims (14)

An epoxy resin composition comprising an epoxy resin (A), a phenol resin (B), and a curing accelerator (C),
A combination of the epoxy resin (A), which is a biphenylaralkyl-type epoxy resin, and the phenol resin (B), which is a biphenylaralkyl-type phenol resin, or the epoxy resin (A) and triphenylmethane, which are triphenylmethane-type epoxy resins. Including any of a combination with the phenol resin (B) which is a type phenol resin,
The curing accelerator (C) is an epoxy resin composition containing a biphenol type phosphine having a structure represented by the following general formula (1).

(In the general formula (1), R _{p1 to} R _p4 are each independently a hydrocarbon group having 1 to 6 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms. R _{a1 to} R _a16 each independently represent a hydrogen atom, a hydroxy group, a hydrocarbon group having 1 to 6 carbon atoms, or a hydrocarbon group having 6 to 14 carbon atoms. R _{a1 to} R _a4 , R _{a5 to} R _a8 , R _{a9 to} R _a12 , and R _{a13 to} R _a16 , which are aromatic hydrocarbon groups, may be the same or different from each other. May be bonded to each other to form a cyclic structure. X and Y are integers of 1 to 3, Z is an integer of 0 to 3, and X = Y.) The epoxy resin composition according to claim 1, wherein
An epoxy resin composition in which the curing accelerator (C) contains a biphenol type phosphine having a structure represented by the following general formula (2).

(In the general formula (2), R _{a17 to} R _a24 are each independently a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms. And may be the same or different from each other.) The epoxy resin composition according to claim 1 or 2, wherein
An epoxy resin composition in which the curing accelerator (C) contains a biphenol type phosphine having a structure represented by the following formula (3).

The epoxy resin composition according to any one of claims 1 to 3,
The epoxy resin composition in which the epoxy resin (A) that is a triphenylmethane type epoxy resin contains a structural unit represented by the following general formula (4) and / or the following general formula (5).

(In the general formulas (4) and (5), R ₁₀ , R ₁₁ , and R ₁₂ are a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and are the same as each other. A and c are integers of 0 to 3, b is an integer of 0 to 4 and may be the same or different from each other, X ₁ is a single bond or the following general formula. A group represented by any one of formulas (5A), (5B), and (5C): R ₁₃ , R ₁₄ , R ₁₅ and R in the following general formulas (5A), (5B) and (5C). ₁₆ is a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms and may be the same or different from each other, d is an integer of 0 to 2, and e, f and g are integers of 0 to 4 and may be the same or different from each other.)

The epoxy resin composition according to any one of claims 1 to 4,
The epoxy resin composition in which the epoxy resin (A) which is a biphenylaralkyl type epoxy resin contains a structural unit represented by the following general formula (6).

(X ₂ represents a hydrogen atom or a group represented by the following formula (6B).)

The epoxy resin composition according to any one of claims 1 to 5,
An epoxy resin composition in which the phenol resin (B) that is a triphenylmethane type phenol resin contains a structural unit represented by the following general formula (7) and / or the following general formula (8).

(In the general formulas (7) and (8), R ₁₇ , R ₁₈ , and R ₁₉ are a hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and are the same as each other. Y ₃ represents a hydroxyl group, h and j are integers of 0 to 3, i is an integer of 0 to 4, and they may be the same or different. ₁ represents a single bond or a group represented by any of the following general formulas (8A), (8B), or (8C): R ₂₀ , R ₂₁ , and R in the general formulas (8A) to (8C). ₂₂ and R ₂₃ are hydrocarbon groups having 1 to 6 carbon atoms or aromatic hydrocarbon groups having 6 to 14 carbon atoms and may be the same or different from each other, and k is an integer of 0 to 2. , L, m and n are integers of 0 to 4 and may be the same or different from each other.)

The epoxy resin composition according to any one of claims 1 to 6,
The epoxy resin composition in which the phenol resin (B), which is a biphenylaralkyl-type phenol resin, contains a structural unit represented by the following general formula (9).

(Y ₂ represents a hydrogen atom or a group represented by the following formula (9B).)

The epoxy resin composition according to any one of claims 1 to 7,
The epoxy resin composition, wherein the content of the epoxy resin (A) is 1% by weight or more and 90% by weight or less based on 100% by weight of the entire epoxy resin composition. The epoxy resin composition according to any one of claims 1 to 8, wherein
The content of the phenol resin (B), relative to the total 100% by weight of the epoxy resin composition is 60 wt% or less 1 wt% or more, Epoxy resin composition. The epoxy resin composition according to any one of claims 1 to 9,
The epoxy resin composition in which the content of the curing accelerator (C) is 0.05% by weight or more and 15% by weight or less based on 100% by weight of the entire epoxy resin composition. The epoxy resin composition according to any one of claims 1 to 10,
Furthermore, an epoxy resin composition containing an inorganic filler (D). The epoxy resin composition according to claim 11,
The content of the inorganic filler (D) is the relative total 100 wt% of the epoxy resin composition is 40 wt% to 99 wt% or less, the epoxy resin composition.   The epoxy resin composition according to any one of claims 1 to 12, which is used for sealing a semiconductor element. Semiconductor element,
A semiconductor device comprising a sealing member for sealing the semiconductor element,
A semiconductor device, wherein the sealing member is composed of a cured product of the epoxy resin composition according to any one of claims 1 to 13.

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