JP5488394B2 - Semiconductor sealing resin composition and semiconductor device - Google Patents

Description

  The present invention relates to a semiconductor sealing resin composition and a semiconductor device using the same.

  In recent years, as electronic components such as integrated circuits (ICs), large scale integrated circuits (LSIs), and very large scale integrated circuits (VLSIs) and semiconductor devices have been increased in density and integration, their mounting methods have been changed from insertion mounting. It is changing to surface mounting. Along with this, lead pins are required to have a large number of pins and lead pitches are narrowed. Surface mount type QFP (Quad Flat Package), which is small and light, and can accommodate a large number of pins, is used in various semiconductor devices. It has been. And since the semiconductor device is excellent in the balance of productivity, cost, reliability and the like, it is mainly sealed with an epoxy resin composition.

  Conventionally, for the purpose of imparting flame retardancy, bromine-containing epoxy resins or antimony oxides have generally been used for epoxy resin compositions for semiconductor encapsulation. However, in recent years, there has been an increasing movement to regulate the use of halogen-containing compounds that are likely to generate dioxin-like compounds and highly toxic antimony compounds from the viewpoint of environmental protection. Under these circumstances, metal oxides such as aluminum hydroxide and magnesium hydroxide are used as flame retardants for replacing brominated epoxy resins and antimony compounds. However, these flame retardants may cause a decrease in fluidity due to an increase in molten resin viscosity, a decrease in continuous moldability due to a deterioration in mold release properties, and a decrease in solder resistance.

  From the above situation, an epoxy resin composition using a phenol aralkyl type epoxy resin having a biphenylene skeleton as an epoxy resin composition for encapsulating a semiconductor that can obtain good flame retardancy without adding a flame retardant imparting agent A thing is proposed (for example, refer patent documents 1 and 2). Although these epoxy resin compositions have the advantages of being able to obtain a highly reliable semiconductor device with low water absorption, low elastic modulus at heat, high adhesion, excellent flame retardancy, Manufacturing is costly. In addition, such a resin may not have sufficient fluidity to seal a thin semiconductor device.

JP 2004-203911 A Japanese Patent Application Laid-Open No. 2004-155841

  Therefore, the present invention has been made in view of such circumstances, and has good flame resistance and solder resistance, is excellent in fluidity, curability and continuous formability, and can be manufactured at a low cost. A resin composition is provided.

  The resin composition for semiconductor encapsulation of the present invention comprises structural units represented by the following general formula (1) and general formula (2), and at least one terminal has at least one alkyl group having 1 to 3 carbon atoms. A phenolic resin having an aromatic group having:

（一般式（１）において、Ｒ１およびＲ２は、互いに独立して、水素原子、または炭素数１〜６の炭化水素基であり、Ｒ３は、互いに独立して、炭素数１〜６の炭化水素基であり、ａは、０〜３の整数である）

(In General Formula (1), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is independently a hydrocarbon having 1 to 6 carbon atoms. A is an integer of 0 to 3)

（一般式（２）において、Ｒ５、Ｒ６、Ｒ８およびＲ９は、互いに独立して、水素原子、または炭素数１〜６の炭化水素基であり、Ｒ４およびＲ７は、互いに独立して、炭素数１〜６の炭化水素基であり、ｂは、０〜３の整数であり、ｃは０〜４の整数である）
エポキシ樹脂と、
無機充填剤と、
硬化促進剤と、
酸化ポリエチレンワックスと、
を含むことを特徴とする。

(In General Formula (2), R5, R6, R8 and R9 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R4 and R7 are independently of each other a carbon number. 1 to 6 hydrocarbon groups, b is an integer of 0 to 3, and c is an integer of 0 to 4)
Epoxy resin,
An inorganic filler;
A curing accelerator;
With oxidized polyethylene wax,
It is characterized by including.

  The resin composition for encapsulating a semiconductor according to the present invention is characterized in that the aromatic group having at least one alkyl group having 1 to 3 carbon atoms is a trimethylphenyl group.

  The resin composition for encapsulating a semiconductor according to the present invention is characterized in that the phenol resin contains a polymer represented by the following general formula (3).

（一般式（３）において、ｍ１は、平均値で、０．３以上、７以下の数であり、ｎ１は、平均値で、０．３以上、７以下の数である）。

(In general formula (3), m1 is an average value and is a number of 0.3 or more and 7 or less, and n1 is an average value and is a number of 0.3 or more and 7 or less).

  The resin composition for semiconductor encapsulation of the present invention is characterized in that the phenol resin contains a polymer represented by the following general formula (4).

（一般式（４）において、ｍ２は、平均値で、０．３以上、７以下の数であり、ｎ２は、平均値で、０．１以上、４以下の数である）。

(In the general formula (4), m2 is an average value and is a number of 0.3 or more and 7 or less, and n2 is an average value and is a number of 0.1 or more and 4 or less).

  In the resin composition for semiconductor encapsulation of the present invention, the curing accelerator is selected from a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. It contains at least one kind.

  The semiconductor device of the present invention is obtained by encapsulating a semiconductor element with the above-described resin composition for encapsulating a semiconductor of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, while having favorable flame resistance and solder resistance, it is excellent in fluidity | liquidity and curability, Furthermore, it is excellent in continuous moldability, and can be manufactured at low cost, and the resin composition for semiconductor sealing is provided. .

It is the figure which showed the cross-sectional structure about an example of the semiconductor device using the resin composition for semiconductor sealing which concerns on this invention. It is a GPC chart of the phenol resin 1 used in the Example. It is a FD-MS chart of the phenol resin 1 used in the Example. It is a GPC chart of the phenol resin 2 used in the Example. It is an FD-MS chart of the phenol resin 2 used in the Example.

  DESCRIPTION OF EMBODIMENTS Preferred embodiments of a semiconductor sealing resin composition and a semiconductor device according to the present invention will be described in detail with reference to the drawings. In the description of the drawings, the same reference numerals are assigned to the same elements, and duplicate descriptions are omitted.

  The resin composition for semiconductor encapsulation of the present invention comprises structural units represented by the following general formula (1) and general formula (2), and at least one terminal has at least one alkyl group having 1 to 3 carbon atoms. A phenolic resin having an aromatic group having:

（一般式（１）において、Ｒ１およびＲ２は、互いに独立して、水素原子、または炭素数１〜６の炭化水素基であり、Ｒ３は、互いに独立して、炭素数１〜６の炭化水素基であり、ａは、０〜３の整数である）

(In General Formula (1), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is independently a hydrocarbon having 1 to 6 carbon atoms. A is an integer of 0 to 3)

（一般式（２）において、Ｒ５、Ｒ６、Ｒ８およびＲ９は、互いに独立して、水素原子、または炭素数１〜６の炭化水素基であり、Ｒ４およびＲ７は、互いに独立して、炭素数１〜６の炭化水素基であり、ｂは、０〜３の整数であり、ｃは０〜４の整数である）
エポキシ樹脂と、無機充填剤と、硬化促進剤と、酸化ポリエチレンワックスと、を含むものである。

(In General Formula (2), R5, R6, R8 and R9 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R4 and R7 are independently of each other a carbon number. 1 to 6 hydrocarbon groups, b is an integer of 0 to 3, and c is an integer of 0 to 4)
An epoxy resin, an inorganic filler, a curing accelerator, and oxidized polyethylene wax are included.

  The phenol resin used in the present invention has an aromatic group having at least one alkyl group having 1 to 3 carbon atoms at at least one terminal. Such an aromatic group introduced at the terminal acts as a polymerization terminator in the polymerization reaction between the phenol resin and the epoxy resin. Since it becomes possible to suppress the molecular weight of the polymer obtained by this comparatively low, the obtained resin composition has high fluidity | liquidity. Therefore, the obtained resin composition has good operability. Furthermore, this phenol resin has hydrophobicity by the C1-C3 alkyl group couple | bonded with this aromatic group. As a result, the obtained resin composition has high solder resistance.

  The phenol resin used in the present invention preferably has a molecular weight of 200 or more and 1500 or less, more preferably 300 or more and 1400 or less, and further preferably 350 or more and 1200 or less, as measured by FD-MS analysis. When the molecular weight of the phenol resin is within the above range, a resin composition having a good balance between fluidity and curability can be obtained.

  In the above phenol resin, when the total of the structural units (1) and (2) in one molecule of the phenol resin is 100 mol%, the ratio of the structural unit (1) is k (mol%), the structural unit ( When the ratio of 2) is 1 (mol%), k is preferably 10 or more and 80 or less, more preferably 20 or more and 70 or less, and l is preferably 20 or more and 90 or less, more preferably. Is 30 or more and 80 or less. When each structural unit is in the above range, a resin composition having an excellent balance of curability, flame resistance, and moisture resistance can be obtained.

ここで、一般式（５）において、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９、およびｃは、上記一般式（２）における定義と同じであり、Ｒ１３およびＲ１４は、互いに独立して、炭素数１〜５の炭化水素基または水素原子であり、Ｘは、ハロゲン原子、水酸基または炭素数１〜６のアルコキシ基である。 Such a phenol resin can be obtained by copolymerizing an alkyl-substituted aromatic compound, a phenol compound, aldehydes, and a compound represented by the following general formula (5).

Here, in the general formula (5), R5, R6, R7, R8, R9, and c are the same as defined in the general formula (2), and R13 and R14 are independently of each other a carbon number of 1 -5 hydrocarbon group or hydrogen atom, and X is a halogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

The above alkyl-substituted aromatic compound used for the synthesis of the phenol resin has at least one alkyl group and at least one substitutable hydrogen atom in the aromatic ring. Such an alkyl-substituted aromatic compound has the following characteristics upon copolymerization by taking a structure that does not contain a polar group.
(I) Since it has no polar group, its reactivity with aldehydes is extremely low.
(Ii) Reaction with the compound (aromatic crosslinking group) represented by the general formula (5) is possible.
(Iii) Due to steric hindrance due to the relatively bulky alkyl group, the molecular chain is hardly extended in the reaction with the compound represented by the general formula (5).
Therefore, the alkyl-substituted aromatic compound binds to one end or both ends of the molecular chain to suppress the molecular chain extension / growth of the phenol resin. Thereby, it contributes to the improvement of the fluidity | liquidity of the phenol resin obtained.

  The alkyl-substituted aromatic compound used for the production of the phenol resin is particularly limited as long as it has a structure having at least one alkyl group and at least one substitutable hydrogen atom in the aromatic ring and does not contain a polar group. Is not to be done. Examples of such alkyl-substituted aromatic compounds include toluene, o-xylene, m-xylene, p-xylene, 1,3,5-trimethylbenzene, 1,2,3-trimethylbenzene, 1,2,4. -Trimethylbenzene, ethylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,3,5-triethylbenzene, 1,2,3-triethylbenzene, 1,2,4-triethylbenzene, cumene, o-cymene M-cymene, p-cymene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, pentylbenzene, dipentylbenzene and the like. Among these, trimethylbenzene is preferable from the viewpoint of introduction of a hydrophobic group, and 1,2,4-trimethylbenzene and 1,3,5-trimethylbenzene are preferable from the viewpoint of fluidity and raw material price. These may be used alone or in combination of two or more.

  Examples of the phenol compound used in the production of the phenol resin include phenol, o-cresol, p-cresol, m-cresol, phenylphenol, ethylphenol, n-propylphenol, isopropylphenol, tert-butylphenol, xylenol, and methylpropyl. Examples include, but are not limited to, phenol, methylbutylphenol, dipropylphenol, dibutylphenol, mesitol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, and the like. Among these, phenol and o-cresol are preferable, and phenol is more preferable from the viewpoint of reactivity with the epoxy resin. These may be used alone or in combination of two or more.

  Examples of the aldehydes used for producing the phenol resin include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. Among these, formaldehyde and paraformaldehyde are preferable from the viewpoints of curability of the resin composition and raw material costs.

  In the compound (aromatic crosslinking group) represented by the following general formula (5) used for the production of a phenol resin,

Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９、およびｃは、上記一般式（２）における定義と同じであり、Ｒ１３およびＲ１４は、互いに独立して、炭素数１〜５の炭化水素基または水素原子であり、Ｘは、ハロゲン原子、水酸基または炭素数１〜６のアルコキシ基である。

R5, R6, R7, R8, R9, and c are the same as defined in the general formula (2), and R13 and R14 are each independently a hydrocarbon group having 1 to 5 carbon atoms or a hydrogen atom. Yes, X is a halogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

  In R5, R6, R8 and R9 in the general formula (5), examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, tert-butyl. Group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 3,4-dimethylbutyl group, 4,4-dimethylbutyl group, 2 -Ethylbutyl group, 1-ethylbutyl group, cyclohexyl group, phenyl group and the like can be mentioned.

  In R7 in the general formula (5), the hydrocarbon group having 1 to 6 carbon atoms is a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, 2 -Methylbutyl group, 3-methylbutyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,2-dimethylbutyl group 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 3,4-dimethylbutyl group, 4,4-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group , A cyclohexyl group, and a phenyl group.

  = CR13R14 (alkylidene group) in the general formula (5) includes a methylidene group, an ethylidene group, a propylidene group, an n-butylidene group, an isobutylidene group, a tert-butylidene group, an n-pentylidene group, a 2-methylbutylidene group, 3-methylbutylidene group, tert-pentylidene group, n-hexylidene group, 1-methylpentylidene group, 2-methylpentylidene group, 3-methylpentylidene group, 4-methylpentylidene group, 2,2-dimethyl Butylidene group, 2,3-dimethylbutylidene group, 2,4-dimethylbutylidene group, 3,3-dimethylbutylidene group, 3,4-dimethylbutylidene group, 4,4-dimethylbutylidene group, 2 -Ethylbutylidene group, 1-ethylbutylidene group, cyclohexylidene group and the like.

  In X in the general formula (5), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, n-pentoxy group, 2-methylbutoxy group, 3-methylbutoxy group, tert-pentoxy group, n-hexoxy group, 1-methylpentoxy group, 2-methylpentoxy group, 3-methylpentoxy group, 4-methylpentoxy group, 2,2-dimethylbutoxy group, 2,3- Dimethylbutoxy group, 2,4-dimethylbutoxy group, 3,3-dimethylbutoxy group, 3,4-dimethylbutoxy group, 4,4-dimethylbutoxy group, 2-ethylbutoxy group, 1-ethylbutoxy group, etc. Can be mentioned.

  As the compound represented by the general formula (5), one kind may be used alone, or two or more kinds may be mixed and used. Among these, the m-form and p-form of xylylene glycol are preferable because they can be synthesized at a relatively low temperature and the reaction by-products can be easily distilled off and handled. When X is a halogen atom, hydrogen halide generated due to the presence of a small amount of moisture can be used as an acid catalyst.

  Although it does not specifically limit about the synthesis | combining method of the phenol resin used by this invention, For example, with respect to 1 mol of phenol compounds, the compound and aldehydes which are represented by General formula (5) are 0.2-0.8 in total. Mole, 0.05 to 0.25 mol of alkyl-substituted aromatic compound, 0.01 to 0.05 mol of acidic catalyst such as formic acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Lewis acid Is allowed to react for 2 to 20 hours while discharging the generated gas and moisture out of the system at a temperature of 50 to 200 ° C., and the remaining monomer is distilled off by a method such as vacuum distillation or steam distillation. Can be obtained. In addition, as a reaction operation, an alkyl-substituted aromatic compound is converted into a reaction system from the middle to the end of the reaction while a phenol compound, a compound represented by the general formula (5), and an aldehyde are subjected to a condensation reaction using an acidic catalyst. You may take the method of adding. In this case, the progress of the reaction is determined by gel permeation chromatography by sampling the generation of water, hydrogen halide, and alcohol gas by-produced by the reaction of the alkyl-substituted aromatic compound and phenol, or the product during the reaction. It can also be confirmed by molecular weight by the method.

Here, in order to obtain a phenol resin having a lower viscosity, the blending amount of the phenol compound is increased, the blending amount of the alkyl-substituted aromatic compound is increased, the alkyl-substituted aromatic compound is added at the initial stage of the reaction, and the acid catalyst is blended. If the amount of hydrogen halide gas generated is reduced, the method can be used to reduce the production of high molecular weight components by such means as quickly discharging the gas out of the system with a nitrogen stream or lowering the cocondensation temperature. . Moreover, the phenol resin with a low content of the structural unit of the formula (1) can be prepared by gradually adding aldehydes to the reaction system to reduce the blending amount of aldehydes.
In addition, the ratio of the structural unit of General formula (1) and General formula (2) in a phenol resin substantially reflects the ratio of the used raw material.

  In the synthesis of the phenol resin, when an alkyl-substituted aromatic compound is added or bound, there is a steric hindrance in the alkyl group of the alkyl-substituted aromatic compound, so that the phenol compound, the aldehyde or the general formula (5) Further addition of the compound is suppressed. Thereby, molecular chain extension does not occur, and as a result, an alkyl-substituted aromatic compound is introduced at the terminal. In addition, as the amount of the alkyl-substituted aromatic compound used in the synthesis is larger, a phenol resin containing more phenol resin having the alkyl-substituted aromatic compound bonded to both ends can be obtained. In addition, introduction | transduction of an alkyl substituted aromatic compound can be confirmed by measuring the obtained phenol resin by FD-MS method.

  The said phenol resin may contain the polymer represented by following General formula (3).

一般式（３）で表される化合物は、一分子当たり、ｍ１が０〜２０の整数であり、ｎ１が０〜２０の整数である化合物の混合物である。したがって、混合物におけるｍ１および
ｎ１は、平均値で記載すると、ｍ１は、平均値で、０．３〜７であり、より好ましくは０．５〜２であり、ｎ１は、平均値で、０．３〜７であり、より好ましくは０．５〜２である。ｍ１が上記下限値以上の場合、得られる樹脂組成物の硬化性が低下する恐れが少ない。また、ｍ１が上記上限値以下であると、フェノール樹脂自体の粘度により得られる樹脂組成物の流動性が低下する恐れが少ない。また、ｎ１が上記下限値以上の場合、得られる樹脂組成物の耐燃性および耐半田クラック性が低下する恐れが少ない。また、ｎ１が上記上限値以下であると、フェノール樹脂自体の粘度により得られる樹脂組成物の流動性が低下する恐れが少ない。
なお、ｍ１およびｎ１の値は、ＦＤ−ＭＳ分析法により求めることができる。一般式（３）の化合物のＦＤ−ＭＳ分析法により測定される分子量は、３５０以上、１２００以下であり、好ましくは４００以上、９００以下である。流動性、硬化性、耐燃性および耐半田性のバランスの観点から、一般式（３）の重合体の量は、一般式（１）および一般式（２）で表される構造単位を含み、少なくとも一方の末端に、少なくとも１つの炭素数１〜３のアルキル基を有する芳香族基を有する上記フェノール樹脂の全量を基準として、８０質量％以上、９５質量％以下であることが好ましい

The compound represented by the general formula (3) is a mixture of compounds in which m1 is an integer of 0 to 20 and n1 is an integer of 0 to 20 per molecule. Therefore, when m1 and n1 in the mixture are described as average values, m1 is an average value of 0.3 to 7, more preferably 0.5 to 2, and n1 is an average value of 0.00. It is 3-7, More preferably, it is 0.5-2. When m1 is not less than the above lower limit value, the curability of the resulting resin composition is less likely to decrease. Moreover, there is little possibility that the fluidity | liquidity of the resin composition obtained by the viscosity of phenol resin itself will fall that m1 is below the said upper limit. Moreover, when n1 is more than the said lower limit, there is little possibility that the flame resistance and solder crack resistance of the resin composition obtained will fall. Moreover, there is little possibility that the fluidity | liquidity of the resin composition obtained by the viscosity of phenol resin itself will fall that n1 is below the said upper limit.
In addition, the value of m1 and n1 can be calculated | required by the FD-MS analysis method. The molecular weight of the compound of the general formula (3) measured by the FD-MS analysis method is 350 or more and 1200 or less, preferably 400 or more and 900 or less. From the viewpoint of the balance between fluidity, curability, flame resistance and solder resistance, the amount of the polymer of the general formula (3) includes the structural units represented by the general formula (1) and the general formula (2), It is preferably 80% by mass or more and 95% by mass or less based on the total amount of the phenol resin having an aromatic group having at least one alkyl group having 1 to 3 carbon atoms at at least one terminal.

  Moreover, the said phenol resin may contain the polymer represented by following General formula (4).

一般式（４）で表される化合物もまた、一分子当たり、ｍ２が０〜２０の整数であり、ｎ２が０〜２０の整数である化合物の混合物である。したがって、混合物におけるｍ２およびｎ２は、平均値で記載すると、ｍ２は、平均値で、０．３〜７であり、より好ましくは１〜３であり、ｎ２は、平均値で、０．１〜４であり、より好ましくは０．５〜２である。ｍ２が上記下限値以上の場合、得られる樹脂組成物の硬化性が低下する恐れが少ない。また、ｍ２が上記上限値以下であると、フェノール樹脂自体の粘度により得られる樹脂組成物の流動性が低下する恐れが少ない。また、ｎ２が上記下限値以上の場合、得られる樹脂組成物の耐燃性および耐半田クラック性が低下する恐れが少ない。また、ｎ２が上記上限値以下であると、フェノール樹脂自体の粘度により得られる樹脂組成物の流動性が低下する恐れが少ない。
なお、ｍ２およびｎ２の値は、ＦＤ−ＭＳ分析法により求めることができる。一般式（４）の化合物のＦＤ−ＭＳ分析法により測定される分子量は、好ましくは５５０以上、１２００以下であり、より好ましくは６００以上、９００以下である。流動性、硬化性、耐燃性および耐半田性のバランスの観点から、一般式（４）の重合体の量は、一般式（１）および一般式（２）で表される構造単位を含み、少なくとも一方の末端に、少なくとも１つの炭素数１〜３のアルキル基を有する芳香族基を有する上記フェノール樹脂の全量を基準として、５質量％以上、２０質量％以下であることが好ましい。

The compound represented by the general formula (4) is also a mixture of compounds in which m2 is an integer of 0 to 20 and n2 is an integer of 0 to 20 per molecule. Accordingly, when m2 and n2 in the mixture are described as average values, m2 is an average value of 0.3 to 7, more preferably 1 to 3, and n2 is an average value of 0.1 to 4, more preferably 0.5-2. When m2 is not less than the above lower limit, there is little fear that the curability of the resulting resin composition will be lowered. Moreover, there is little possibility that the fluidity | liquidity of the resin composition obtained by the viscosity of phenol resin itself will fall that m2 is below the said upper limit. Moreover, when n2 is more than the said lower limit, there is little possibility that the flame resistance and solder crack resistance of the resin composition obtained will fall. Moreover, there is little possibility that the fluidity | liquidity of the resin composition obtained by the viscosity of phenol resin itself will fall that n2 is below the said upper limit.
Note that the values of m2 and n2 can be determined by FD-MS analysis. The molecular weight of the compound of the general formula (4) measured by the FD-MS analysis method is preferably 550 or more and 1200 or less, more preferably 600 or more and 900 or less. From the viewpoint of balance between fluidity, curability, flame resistance and solder resistance, the amount of the polymer of the general formula (4) includes the structural units represented by the general formula (1) and the general formula (2), It is preferably 5% by mass or more and 20% by mass or less based on the total amount of the phenol resin having an aromatic group having at least one alkyl group having 1 to 3 carbon atoms at at least one terminal.

  Examples of the polymer represented by the general formula (3) and the general formula (4) include phenol, p-xylylene glycol, formaldehyde and 1,3,5-trimethylbenzene or 1,2,4-trimethylbenzene. It can be obtained by reacting.

The phenol resin used in the present invention includes an aromatic group containing structural units represented by general formula (1) and general formula (2), and having at least one alkyl group having 1 to 3 carbon atoms at at least one terminal. Resin having a group, specifically, a resin in which one or both ends of a phenol aralkyl type resin are substituted with an alkyl-substituted aromatic compound, a piece of a phenol resin obtained by copolymerizing a phenol aralkyl type and a phenol novolac type It is not limited to those consisting of a resin in which the terminal or both-end phenol moieties are substituted with an alkyl-substituted aromatic compound, but is a by-product that will be generated simultaneously when the phenol resin is produced by the method described above. , Phenol aralkyl type resin, phenol novolac type resin, phenol aralkyl type and phenol novolac type It may contain copolymerized phenolic resin. By including the above-mentioned plurality of structures, it is excellent in flame resistance, is less viscous than phenol aralkyl resins, but is less likely to block, is excellent in handling, and can exhibit low water absorption. Further, such a phenolic resin can be manufactured at a lower cost because the total raw material cost is lower than that of the phenolaralkyl resin.

  When the phenol resin contains a phenol novolac resin, the content of the phenol novolac resin in the phenol resin is 5 to 20% by mass, more preferably 5 to 15% by mass, based on the total amount of the phenol resin used. By setting it as the above range, good curability and flame resistance can be obtained. The content of the phenol novolac type in the phenol resin can be determined by combining the FD-MS analysis method and the GPC area method.

  An aromatic group containing the structural unit represented by the general formula (1) and the general formula (2) in the resin composition for encapsulating a semiconductor and having at least one alkyl group having 1 to 3 carbon atoms at at least one terminal. The amount of the phenolic resin having an amount of preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass with respect to the total mass of the resin composition for semiconductor encapsulation. % Or more. When the lower limit is within the above range, the resulting resin composition has good fluidity. Moreover, the amount of the phenol resin in the resin composition for semiconductor encapsulation is preferably 10% by mass or less, more preferably 9% by mass or less, and further preferably based on the total mass of the resin composition for semiconductor encapsulation. Is 8 mass% or less. When the upper limit is within the above range, the resulting resin composition has good solder resistance.

  In the resin composition for semiconductor encapsulation of the present invention, other curing agents can be used in combination as long as the effects of using the phenol resin are not impaired. Examples of the curing agent that can be used in combination include a polyaddition type curing agent, a catalyst type curing agent, and a condensation type curing agent. Examples of polyaddition type curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylene diamine (MXDA), diaminodiphenylmethane (DDM), and m-phenylenediamine (MPDA). In addition to aromatic polyamines such as diaminodiphenylsulfone (DDS), polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide, and the like; alicyclics such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides, including acid anhydrides, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), aromatic acid anhydrides such as benzophenone tetracarboxylic acid (BTDA), etc .; Polyphenol compounds such as mer; polysulfide, thioester, polymercaptan compounds such as thioethers; isocyanate prepolymer, isocyanate compounds such as blocked isocyanate; and organic acids such as carboxylic acid-containing polyester resins.

Examples of the catalyst-type curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4 -Imidazole compounds such as methylimidazole (EMI24); Lewis acids such as BF ₃ complexes.

Examples of the condensation type curing agent include phenolic resin-based curing agents such as novolak type phenolic resin and resol type phenolic resin; urea resin such as methylol group-containing urea resin; melamine resin such as methylol group-containing melamine resin; Can be mentioned.

  Among these, a phenol resin-based curing agent is preferable from the viewpoint of balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like. The phenol resin-based curing agent is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak Resin, novolak resin such as naphthol novolak resin; polyfunctional phenol resin such as triphenolmethane phenol resin; modified phenol resin such as terpene modified phenol resin and dicyclopentadiene modified phenol resin; phenylene skeleton and / or biphenylene skeleton Aralkyl type resins such as phenol aralkyl resins having phenylene and / or naphthol aralkyl resins having a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F, etc. These may be used in combination of two or more be used one kind alone. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.

  When such other curing agents are used in combination, the structural unit represented by the general formula (1) and the general formula (2) is included, and at least one terminal has at least one alkyl group having 1 to 3 carbon atoms. The blending ratio of the phenolic resin having an aromatic group is preferably 15% by mass or more, more preferably 25% by mass or more, and more preferably 35% by mass or more with respect to the total curing agent. It is particularly preferred. When the blending ratio is within the above range, it is possible to obtain the effect of improving the flame resistance and solder resistance while maintaining good fluidity and curability.

  Although it does not specifically limit about the lower limit of the compounding ratio of the whole hardening | curing agent, It is preferable that it is 0.8 mass% or more in all the resin compositions, and it is more preferable that it is 1.5 mass% or more. When the lower limit value of the blending ratio is within the above range, sufficient fluidity can be obtained. Moreover, although it does not specifically limit about the upper limit of the mixture ratio of the whole hardening | curing agent, It is preferable that it is 10 mass% or less in all the epoxy resin compositions, and it is more preferable that it is 8 mass% or less. When the upper limit of the blending ratio is within the above range, good solder resistance can be obtained.

Examples of the epoxy resin used in the resin composition for semiconductor encapsulation of the present invention include crystalline epoxy resins such as biphenyl type epoxy resins, bisphenol type epoxy resins, and stilbene type epoxy resins; phenol novolac type epoxy resins and cresol novolak types. Novolac type epoxy resins such as epoxy resins; polyfunctional epoxy resins such as triphenolmethane type epoxy resins and alkyl-modified triphenolmethane type epoxy resins; phenol aralkyl type epoxy resins having a phenylene skeleton, phenol aralkyl type epoxy resins having a biphenylene skeleton Aralkyl-type epoxy resins such as dihydroxynaphthalene-type epoxy resins, naphthol-type epoxies such as epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimers Fats; Triazine core-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; Bridged cyclic hydrocarbon compound-modified phenolic epoxy resins such as dicyclopentadiene-modified phenolic epoxy resins, but are not limited thereto Not.
Aralkyl type epoxy resins such as phenol aralkyl type epoxy resins having a phenylene skeleton, phenol aralkyl type epoxy resins having a biphenylene skeleton, and these epoxy resins are preferable in terms of excellent balance of solder resistance, flame resistance and continuous moldability, A crystalline epoxy resin is preferable in that it has excellent fluidity. In addition, from the viewpoint of moisture resistance reliability of the obtained resin composition for semiconductor encapsulation, it is preferable not to contain Na ions and Cl ions as ionic impurities as much as possible, from the viewpoint of curability of the resin composition for semiconductor encapsulation. The epoxy equivalent of the epoxy resin is preferably 100 g / eq or more and 500 g / eq or less.

The amount of the epoxy resin in the resin composition for semiconductor encapsulation is preferably 2% by mass or more, more preferably 4% by mass or more, based on the total mass of the resin composition for semiconductor encapsulation. When the lower limit is within the above range, the resulting resin composition has good fluidity. Moreover, the amount of the epoxy resin in the resin composition for semiconductor encapsulation is preferably 15% by mass or less, more preferably 13% by mass or less, with respect to the total mass of the resin composition for semiconductor encapsulation. When the upper limit is within the above range, the resulting resin composition has good solder resistance.
The phenol resin and the epoxy resin have an equivalent ratio (EP) / (OH) between the number of epoxy groups (EP) of all epoxy resins and the number of phenolic hydroxyl groups (OH) of all phenol resins, of 0.8 or more, It is preferable to mix | blend so that it may become 1.3 or less. When the equivalent ratio is within the above range, sufficient curing characteristics can be obtained when the resulting resin composition is molded.

As the inorganic filler used in the resin composition for semiconductor encapsulation of the present invention, inorganic fillers generally used in the field can be used. Examples thereof include fused silica, spherical silica, crystalline silica, alumina, silicon nitride, and aluminum nitride. The particle size of the inorganic filler is desirably 0.01 μm or more and 150 μm or less from the viewpoint of filling properties in the mold cavity.
The amount of the inorganic filler in the resin composition for semiconductor encapsulation is preferably 80% by mass or more, more preferably 83% by mass or more, based on the total mass of the resin composition for semiconductor encapsulation. Preferably it is 86 mass% or more. When the lower limit value is within the above range, an increase in moisture absorption and a decrease in strength due to curing of the resulting resin composition can be reduced, and therefore a cured product having good solder crack resistance can be obtained.
Moreover, the amount of the inorganic filler in the resin composition for semiconductor encapsulation is preferably 93% by mass or less, more preferably 91% by mass or less, with respect to the total mass of the resin composition for semiconductor encapsulation. More preferably, it is 90 mass% or less. When the upper limit is within the above range, the resulting resin composition has good fluidity and good moldability.
In addition, when using inorganic flame retardants such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide, zinc borate, zinc molybdate and antimony trioxide described later, these inorganic flame retardants and the above It is desirable that the total amount of the inorganic filler is within the above range.

The curing accelerator used in the present invention only needs to promote the reaction between the epoxy group of the epoxy resin and the phenolic hydroxyl group of the compound containing two or more phenolic hydroxyl groups, and is a general epoxy resin composition for semiconductor encapsulation. You can use what is used for.
Specific examples include phosphorus-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; 1,8-diazabicyclo (5 , 4, 0) Undecene-7, benzyldimethylamine, nitrogen atom-containing compounds such as 2-methylimidazole. Among these, a phosphorus atom-containing compound is preferable from the viewpoint of curability, and from the viewpoint of balance between fluidity and curability, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, a phosphonium compound A catalyst having latency such as an adduct of silane compound and silane compound is more preferable. In view of fluidity, a tetra-substituted phosphonium compound is particularly preferred, and in view of the low modulus of heat of the cured resin composition, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound is particularly preferred. In view of the latent curing property, an adduct of a phosphonium compound and a silane compound is particularly preferable.
Examples of the organic phosphine that can be used in the resin composition for encapsulating a semiconductor of the present invention include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, and tributyl. Third phosphine such as phosphine and triphenylphosphine can be used.

Examples of the tetra-substituted phosphonium compound that can be used in the semiconductor sealing resin composition of the present invention include a compound represented by the following general formula (6).

一般式（６）において、Ｐはリン原子を表し、Ｒ１５、Ｒ１６、Ｒ１７およびＲ１８は、それぞれ独立して芳香族基またはアルキル基を表す。Ａはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸のアニオンを表し、ＡＨはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸を表す。ｘおよび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。

In the general formula (6), P represents a phosphorus atom, and R15, R16, R17 and R18 each independently represents an aromatic group or an alkyl group. A represents an anion of an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in an aromatic ring, and AH represents a functional group selected from a hydroxyl group, a carboxyl group, and a thiol group. Represents an aromatic organic acid having at least one of the following in the aromatic ring. x and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.

  Although the compound represented by General formula (6) is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (6) can be precipitated. In the compound represented by the general formula (6), R15, R16, R17, and R18 bonded to the phosphorus atom are phenyl groups and AH is bonded to the phosphorus atom from the viewpoint of excellent balance between the yield during synthesis and the curing acceleration effect. A compound having a hydroxyl group in an aromatic ring, that is, a phenol compound, and A is preferably an anion of the phenol compound.

  Examples of the phosphobetaine compound that can be used in the semiconductor sealing resin composition of the present invention include compounds represented by the following general formula (7).

一般式（７）において、Ｘ１は炭素数１〜３のアルキル基を表し、Ｙ１はヒドロキシル基を表し、ｆは０〜５の整数であり、ｇは０〜３の整数である。

In General formula (7), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group, f is an integer of 0-5, g is an integer of 0-3.

  The compound represented by the general formula (7) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt. However, the present invention is not limited to this.

  Examples of the adduct of a phosphine compound and a quinone compound that can be used in the semiconductor sealing resin composition of the present invention include compounds represented by the following general formula (8).

一般式（８）において、Ｐはリン原子を表し、Ｒ１９、Ｒ２０およびＲ２１は、互いに独立して、炭素数１〜１２のアルキル基または炭素数６〜１２のアリール基を表し、Ｒ２２、Ｒ２３およびＲ２４は、互いに独立して、水素原子または炭素数１〜１２の炭化水素基を表し、Ｒ２２とＲ２３は互いに結合して環を形成していてもよい。

In General Formula (8), P represents a phosphorus atom, R19, R20, and R21 each independently represent a C1-C12 alkyl group or a C6-C12 aryl group, and R22, R23, and R24 independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R22 and R23 may be bonded to each other to form a ring.

  Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent or a substituent such as an alkyl group and an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.

  In addition, examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone, and anthraquinones. 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, the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both organic tertiary phosphine and benzoquinone. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, the present invention is not limited to this.

  In the compound represented by the general formula (8), R19, R20 and R21 bonded to the phosphorus atom are phenyl groups, and R22, R23 and R24 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl A compound to which phosphine has been added is preferred in that it reduces the thermal elastic modulus of the cured product of the resin composition.

  Examples of the adduct of a phosphonium compound and a silane compound that can be used in the semiconductor sealing resin composition of the present invention include a compound represented by the following formula (9).

一般式（９）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ２５、Ｒ２６、Ｒ２７およびＲ２８は、互いに独立して、芳香環または複素環を有する有機基、あるいは脂肪族基を表し、Ｘ２は、基Ｙ２およびＹ３と結合する有機基である。Ｘ３は、基Ｙ４およびＹ５と結合する有機基である。Ｙ２およびＹ３は、プロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ２およびＹ３が珪素原子と結合してキレート構造を形成するものである。Ｙ４およびＹ５はプロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ４およびＹ５が珪素原子と結合してキレート構造を形成する
ものである。Ｘ２、およびＸ３は互いに同一であっても異なっていてもよく、Ｙ２、Ｙ３、Ｙ４、およびＹ５は互いに同一であっても異なっていてもよい。Ｚ１は芳香環または複素環を有する有機基、あるいは脂肪族基である。

In General formula (9), P represents a phosphorus atom and Si represents a silicon atom. R25, R26, R27 and R28 each independently represent an organic group having an aromatic ring or a heterocyclic ring or an aliphatic group, and X2 is an organic group bonded to the groups Y2 and Y3. X3 is an organic group bonded to the groups Y4 and Y5. Y2 and Y3 represent a group formed by releasing a proton from a proton donating group, and groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate structure. Y4 and Y5 each represent a group formed by releasing a proton from a proton donating group, and groups Y4 and Y5 in the same molecule are bonded to a silicon atom to form a chelate structure. X2 and X3 may be the same or different from each other, and Y2, Y3, Y4, and Y5 may be the same or different from each other. Z1 is an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group.

  In the general formula (9), as R25, R26, R27 and R28, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group, and the like. Among these, an aromatic group having a substituent such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, or the like. A substituted aromatic group is more preferred.

  Moreover, in General formula (9), X2 is an organic group couple | bonded with Y2 and Y3. Similarly, X3 is an organic group that binds to groups Y4 and Y5. Y2 and Y3 are groups formed by proton-donating groups releasing protons, and groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure. Similarly, Y4 and Y5 are groups formed by proton-donating groups releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. The groups X2 and X3 may be the same or different from each other, and the groups Y2, Y3, Y4, and Y5 may be the same or different from each other. The groups represented by -Y2-X2-Y3- and Y4-X3-Y5- in the general formula (9) are composed of groups in which a proton donor releases two protons. Examples of proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, salicylic acid, Examples include 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin. Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable from the viewpoint of easy availability of raw materials and a curing acceleration effect.

  Z1 in the general formula (9) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Reactions of aliphatic hydrocarbon groups such as octyl and octyl groups, aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl, glycidyloxypropyl, mercaptopropyl, aminopropyl and vinyl Among them, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable from the viewpoint of thermal stability.

  As a method for producing an adduct of a phosphonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved, and then room temperature. Sodium methoxide-methanol solution is added dropwise with stirring. Furthermore, when a solution prepared by dissolving a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide in methanol in methanol is added dropwise with stirring at room temperature, crystals are precipitated. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound. However, it is not limited to this.

  The lower limit of the blending ratio of the curing accelerator that can be used in the resin composition for semiconductor encapsulation of the present invention is preferably 0.1% by mass or more in the total resin composition. When the lower limit value of the blending ratio of the curing accelerator is within the above range, sufficient curability can be obtained. Moreover, it is preferable that the upper limit of the mixture ratio of a hardening accelerator is 1 mass% or less in all the resin compositions. When the upper limit of the blending ratio of the curing accelerator is within the above range, sufficient fluidity can be obtained.

  Since the oxidized polyethylene wax used in the present invention generally has a polar group composed of carboxylic acid and the like and a nonpolar group composed of a long carbon chain, the polar group is oriented to the resin cured product side during molding, In addition, the nonpolar group acts as a release agent by being oriented on the mold side. The oxidized polyethylene wax used in the present invention is not particularly limited. For example, an oxide of polyethylene wax produced by a low pressure polymerization method, an oxide of polyethylene wax produced by a high pressure polymerization method, and a high density Examples include oxides of polyethylene polymers. Among these, oxides of high density polyethylene polymers are more preferable. These oxidized polyethylene waxes may be used alone or in combination of two or more.

  The dropping point of the oxidized polyethylene wax used in the present invention is preferably 100 ° C. or higher and 140 ° C. or lower, more preferably 110 ° C. or higher and 130 ° C. or lower. The dropping point can be measured by a method based on ASTM D127. Specifically, using a metal nipple, it is measured as the temperature at which molten wax first drops from the metal nipple. In the following examples, it can be measured by the same method. When the dropping point of the oxidized polyethylene wax is within the above range, the oxidized polyethylene wax is excellent in thermal stability, and the oxidized polyethylene wax is hardly seized during continuous molding. Therefore, it is excellent in the mold release property of the resin cured material from a metal mold | die, and is excellent also in continuous moldability. Furthermore, when it is within the above range, the oxidized polyethylene wax is sufficiently melted when the resin composition is cured. Thereby, the oxidized polyethylene wax is dispersed substantially uniformly in the resin cured product. For this reason, segregation of the oxidized polyethylene wax on the surface of the cured resin is suppressed, and deterioration of mold stains and appearance of the cured resin can be reduced.

The acid value of the oxidized polyethylene wax used in the present invention is preferably 10 mgKOH / g or more and 50 mgKOH / g or less, more preferably 15 mgKOH / g or more and 40 mgKOH / g or less. The acid value affects the compatibility with the cured resin. Acid value is JIS K
It can be measured by a method based on 3504. Specifically, it is measured as the number of milligrams of potassium hydroxide required to neutralize free fatty acids contained in 1 g of waxes. In the following examples, it can be measured by the same method. When the acid value is within the above range, the oxidized polyethylene wax is in a compatible state with the epoxy resin matrix in the cured resin. Thereby, the oxidized polyethylene wax and the epoxy resin matrix do not cause phase separation. Therefore, segregation of the oxidized polyethylene wax on the surface of the cured resin product is suppressed, and deterioration of mold stains and appearance of the cured resin product can be reduced. Furthermore, since the oxidized polyethylene wax is present on the surface of the cured resin, the releasability of the cured resin from the mold is excellent. On the other hand, if the compatibility between the oxidized polyethylene wax and the epoxy resin matrix is too high, the oxidized polyethylene wax cannot ooze out on the surface of the cured resin, and sufficient releasability may not be ensured.

  The number average molecular weight of the oxidized polyethylene wax used in the present invention is preferably 500 or more and 5000 or less, more preferably 1000 or more and 4000 or less, from the viewpoint of the effect of reducing warpage. The number average molecular weight can be calculated by polystyrene conversion using a GPC apparatus such as HLC-8120 manufactured by Tosoh Corporation. In the following examples, it can be measured by the same method. When the number average molecular weight is within the above range, the oxidized polyethylene wax and the epoxy resin matrix are in a preferable compatible state. Therefore, the cured resin is excellent in releasability from the mold. On the other hand, if the compatibility between the oxidized polyethylene wax and the epoxy resin matrix is high, sufficient releasability may not be obtained. On the other hand, if the compatibility is low, phase separation occurs, which may cause mold stains and deterioration of the appearance of the cured resin.

The density of the oxidized polyethylene wax used in the present invention is 0.94 g / cm ³ or more, 1
. 03G / cm ³ or less, and more preferably 0.97 g / cm ³ or more and 0.99 g / cm ³ or less. The density can be calculated by density measurement at 20 ° C., for example, by a floating method based on ASTM D1505. In the following examples, it can be measured by the same method. When the density is within the above range, the oxidized polyethylene wax is excellent in thermal stability, and the oxidized polyethylene wax is difficult to seize during continuous molding. Therefore, it is excellent in the mold release property of the resin cured material from a metal mold | die, and is excellent also in continuous moldability. Furthermore, when it is within the above range, the oxidized polyethylene wax is sufficiently melted when the resin composition is cured. Thereby, the oxidized polyethylene wax is dispersed substantially uniformly in the resin cured product. Therefore, segregation of the oxidized polyethylene wax on the surface of the cured resin product is suppressed, and the deterioration of the appearance of the mold and the cured resin product can be reduced.

The average particle diameter of the oxidized polyethylene wax used in the present invention is preferably 20 μm or more and 70 μm or less, more preferably 30 μm or more and 60 μm or less. The average particle diameter can be measured by using a laser diffraction particle size distribution measuring device such as SALD-7000 manufactured by Shimadzu Corporation as a solvent and water, and a weight-based 50% particle diameter as an average particle diameter. it can. In the following examples, it can be measured by the same method. When the average particle size is within the above range, the oxidized polyethylene wax is in a compatible state with the epoxy resin matrix in the cured resin. Thereby, the oxidized polyethylene wax is present on the surface of the cured resin, and the release property of the cured resin from the mold is excellent. On the other hand, if the compatibility with the epoxy resin matrix is too high, it cannot be oozed out on the surface of the cured resin and sufficient releasability cannot be ensured. Furthermore, since the oxidized polyethylene wax and the epoxy resin matrix are in a favorable compatible state, segregation of the oxidized polyethylene wax on the surface of the cured resin is suppressed, and deterioration of the mold contamination and the appearance of the cured resin are reduced. Can do. Furthermore, when it is in the above range, the oxidized polyethylene wax is sufficiently melted when the resin composition is cured. Therefore, the resin composition is excellent in fluidity. The content ratio of particles having a particle size of 106 μm or more in the total oxidized polyethylene wax is preferably 0.1% by mass or less. This content ratio can be measured using, for example, a standard sieve having an opening of 105 μm according to JIS Z8801. In the following examples, it can be measured by the same method. If it is said content rate, an oxidized polyethylene wax will disperse | distribute substantially uniformly and it can suppress the deterioration of the external appearance of a mold | die stain | pollution | contamination and a resin cured material. In addition, when the resin composition is cured, the oxidized polyethylene wax is sufficiently melted, so that the fluidity is excellent.

  The blending ratio of the oxidized polyethylene wax used in the present invention is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.15% by mass or more and 0.5% by mass or less in the resin composition. is there. It is excellent in the mold release property of the resin cured material from a metal mold | die as it is said mixture ratio. Moreover, when it is within the above range, the adhesion between the cured resin and the lead frame member is not impaired, and the occurrence of peeling between the cured resin and the lead frame member during the soldering process can be suppressed. Furthermore, when it is within the above range, deterioration of mold stains and appearance of the cured resin can be suppressed.

  The production method of the oxidized polyethylene wax used in the present invention is not particularly limited. For example, polyethylene wax and high-density polyethylene polymer produced by a known method such as a low-pressure polymerization method or a high-pressure polymerization method are known oxidation. It can be oxidized and obtained according to the law. In addition, the polyethylene oxide wax used in the present invention is commercially available, and if necessary, pulverized by a rotating disk mill (pin mill), a screen mill (hammer mill), a centrifugal mill (turbo mill), a jet mill or the like. It can be used after pulverization and particle size adjustment using a machine.

Other release agents can be used in combination as long as the effects of using the oxidized polyethylene wax used in the present invention are not impaired. Examples of release agents that can be used in combination include natural waxes such as carnauba wax, and metal salts of higher fatty acids such as zinc stearate.

  In the present invention, a compound (F) (hereinafter referred to as compound (F)) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring can be used. The compound (F) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring is used as a curing accelerator for accelerating a crosslinking reaction between a phenol resin and an epoxy resin. Even in the case of using a phosphorus atom-containing curing accelerator that does not contain a resin, the reaction during melt-kneading of the resin composition can be suppressed, and the resin composition can be stably obtained. The compound (F) also has the effect of lowering the melt viscosity of the resin composition and improving the fluidity. As the compound (F), a monocyclic compound represented by the following general formula (10) or a polycyclic compound represented by the following general formula (11) can be used. You may have the substituent of.

一般式（１０）において、Ｒ２９およびＲ３３のいずれか一方が水酸基であり、一方が水酸基の場合、他方は水素原子、水酸基または水酸基以外の置換基であり、Ｒ３０、Ｒ３１およびＲ３２は、水素原子、水酸基または水酸基以外の置換基である。

In General Formula (10), when one of R29 and R33 is a hydroxyl group and one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group, and R30, R31, and R32 are a hydrogen atom, It is a hydroxyl group or a substituent other than a hydroxyl group.

一般式（１１）において、Ｒ３５およびＲ４１のいずれか一方が水酸基であり、一方が水酸基の場合、他方は水素原子、水酸基または水酸基以外の置換基であり、Ｒ３６、Ｒ３７、Ｒ３８、Ｒ３９およびＲ４０は、水素原子、水酸基または水酸基以外の置換基である。

In the general formula (11), when either one of R35 and R41 is a hydroxyl group and one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group, and R36, R37, R38, R39 and R40 are , A hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group.

  Specific examples of the monocyclic compound represented by the general formula (10) include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof. Specific examples of the polycyclic compound represented by the general formula (11) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Among these, a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring is preferable because of easy control of fluidity and curability. In consideration of volatilization in the kneading step, it is more preferable that the mother nucleus is a compound having a low volatility and a highly stable weighing naphthalene ring. In this case, specifically, the compound (F) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof. These compounds (F) may be used individually by 1 type, or may use 2 or more types together.

  The lower limit of the compounding ratio of the compound (F) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and particularly preferably 0.05% by mass or more in the total resin composition. It is. When the lower limit value of the compounding ratio of the compound (F) is within the above range, the resin composition can be sufficiently reduced in viscosity and improved in fluidity. In addition, the upper limit of the compounding ratio of the compound (F) is preferably 1% by mass or less, more preferably 0.8% by mass or less, and particularly preferably 0.5% by mass or less in the total resin composition. is there. When the upper limit of the compounding ratio of the compound (F) is within the above range, there is little possibility of causing a decrease in the curability of the resin composition and a decrease in the physical properties of the cured product.

  In the resin composition for semiconductor encapsulation of the present invention, an adhesion assistant such as a silane coupling agent can be added in order to improve the adhesion between the epoxy resin and the inorganic filler. Examples thereof include, but are not limited to, epoxy silane, amino silane, ureido silane, mercapto silane, etc., which react between the epoxy resin and the inorganic filler to improve the interfacial strength between the epoxy resin and the inorganic filler. If it is. Moreover, a silane coupling agent can also raise the effect of the compound (F) of reducing the melt viscosity of a resin composition and improving fluidity | liquidity by using together with the above-mentioned compound (F).

  Examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane. Etc. Examples of the aminosilane include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-aminopropyl. Methyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3 -Aminopropyltrimethoxysilane, etc. Examples of ureidosilane include γ-ureidopropyltriethoxysilane and hexamethyldisilazane. Examples of mercaptosilane include γ-mercaptopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

  The lower limit of the blending ratio of the adhesion assistant such as a silane coupling agent that can be used in the resin composition for semiconductor encapsulation of the present invention is preferably 0.01% by mass or more, more preferably in the total resin composition. It is 0.05 mass% or more, Most preferably, it is 0.1 mass% or more. If the lower limit of the mixing ratio of the adhesion assistant such as a silane coupling agent is within the above range, the interface strength between the epoxy resin and the inorganic filler does not decrease, and good solder crack resistance in the semiconductor device is achieved. Can be obtained. Moreover, as an upper limit of the mixture ratio of adhesion assistants, such as a silane coupling agent, 1 mass% or less is preferable in all the resin compositions, More preferably, it is 0.8 mass% or less, Most preferably, it is 0.6 mass%. It is as follows. If the upper limit of the blending ratio of the adhesion assistant such as a silane coupling agent is within the above range, the interface strength between the epoxy resin and the inorganic filler does not decrease, and good solder crack resistance in the semiconductor device is achieved. Can be obtained. Moreover, if the blending ratio of the adhesion assistant such as a silane coupling agent is within the above range, the water absorption of the cured product of the resin composition does not increase, and good solder crack resistance in a semiconductor device can be obtained. Can do.

In the semiconductor sealing resin composition of the present invention, in addition to the components described above, colorants such as carbon black, bengara and titanium oxide; natural waxes such as carnauba wax; synthetic waxes such as polyethylene wax; stearic acid and zinc stearate Release agents such as higher fatty acids and their metal salts or paraffins; low stress additives such as silicone oil and silicone rubber; inorganic ion exchangers such as bismuth oxide hydrate; metals such as aluminum hydroxide and magnesium hydroxide Additives such as hydroxides and flame retardants such as zinc borate, zinc molybdate, phosphazene, and antimony trioxide may be appropriately blended.

  The resin composition for semiconductor encapsulation of the present invention is prepared by uniformly mixing a phenol resin, an epoxy resin, an inorganic filler, and the other additives described above, for example, at room temperature using a mixer or the like. Accordingly, it is possible to adjust to a desired degree of dispersion, fluidity, and the like by melt-kneading using a kneader such as a heating roll, a kneader, or an extruder, and subsequently cooling and pulverizing as necessary.

  Next, the semiconductor device of the present invention will be described. As a method for producing a semiconductor device using the resin composition for semiconductor encapsulation of the present invention, for example, after a lead frame or a circuit board on which a semiconductor element is mounted is placed in a mold cavity, the resin for semiconductor encapsulation is used. The method of sealing this semiconductor element by shape | molding and hardening | curing a composition with shaping | molding methods, such as a transfer mold, a compression mold, and an injection mold, is mentioned.

  Examples of the semiconductor element to be sealed include, but are not limited to, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.

  As a form of the obtained semiconductor device, for example, dual in-line package (DIP), chip carrier with plastic lead (PLCC), quad flat package (QFP), low profile quad flat package ( LQFP), Small Outline Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package ( TCP), ball grid array (BGA), chip size package (CSP), etc., but are not limited to these.

  A semiconductor device in which a semiconductor element is encapsulated by a molding method such as transfer molding of a resin composition for encapsulating a semiconductor is used as it is or at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours. After completely curing the resin composition, it is mounted on an electronic device or the like.

  FIG. 1 is a view showing a cross-sectional structure of an example of a semiconductor device using the resin composition for encapsulating a semiconductor according to the present invention. The semiconductor element 1 is fixed on the die pad 3 via the die bond material cured body 2. The electrode pad of the semiconductor element 1 and the lead frame 5 are connected by a gold wire 4. The semiconductor element 1 is sealed with a cured body 6 of a semiconductor sealing resin composition.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to description of these Examples at all. Unless otherwise specified, the amount of each component described below is part by mass.

(Phenolic resin)
Phenol resin 1: phenol (Kanto Chemical special grade reagent, phenol, melting point 40.9 ° C., molecular weight 94, purity 99.3%) 100 parts by mass, p-xylylene glycol (Tokyo Chemical Industry p-xylylene glycol, melting point) 118 ° C., molecular weight 138, purity 98%) 34.5 parts by mass, and p-toluenesulfonic acid monohydrate (p-toluenesulfonic acid, molecular weight 190, purity 99%, manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 parts by mass Was weighed into a separable flask and heated while purging with nitrogen, and stirring was started at the start of melting. After confirming that the system reached 150 ° C., 13.5 parts by mass of 37% formaldehyde aqueous solution (formalin 37% manufactured by Wako Pure Chemical Industries, Ltd.) was added over 30 minutes. After reacting for 90 minutes while maintaining the temperature in the system in the range of 145 ° C. to 155 ° C., 1,3,5-trimethylbenzene (Tokyo Chemical Industry deer special reagent, boiling point 165 ° C., molecular weight 120, While adding 22.5 parts by mass (purity 99%) over 30 minutes, the temperature of the reaction system was lowered, and the reaction was further continued for 240 minutes while maintaining the range of 120 ° C to 130 ° C. From the start of addition of formaldehyde to the end of the reaction, water generated in the system by the reaction or mixed into the system with the addition of formalin was discharged out of the system by a nitrogen stream. After completion of the reaction, unreacted components were distilled off under reduced pressure conditions of 150 ° C. and 2 mmHg, and then 200 parts by mass of toluene was added and dissolved uniformly, then transferred to a separatory funnel and shaken with 150 parts by mass of distilled water. After repeating the operation of rinsing the water layer (washing) until the wash water becomes neutral, volatile components such as toluene and residual unreacted components are distilled off by subjecting the oil layer to 125 ° C. under reduced pressure, Phenol resin 1 (hydroxyl equivalent 159, softening point 67 ° C., ICI viscosity 0.65 dPa · s at 150 ° C.) which is a mixture of polymers represented by the following formula (12), formula (13) and formula (14) Obtained. As a result of GPC analysis and FD-MS analysis of the obtained phenol resin 1, the mass ratio of the polymers represented by the following formula (12), formula (13), and formula (14) was 63. 2 mass%, 34.6 mass%, and 2.2 mass%, and the average values of a1 to a3 and b1 to b3 in the following formulas (12), (13), and (14) are a1 = 1. 04, a2 = 0.94, a3 = 1.45, b1 = 0.92, b2 = 0.79, b3 = 0.60. The GPC chart of the phenol resin 1 is shown in FIG. 2, and the FD-MS chart is shown in FIG.

In addition, the measurement of the average value of a1-a3 and b1-b3 was calculated | required as follows. First, the mass ratio of each nucleus having the same number of aromatic rings was calculated by GPC analysis (area method) of the phenol resin 1. Subsequently, FD-MS analysis is performed, and the obtained molecular weight peak intensity is proportional to the mass ratio of each compound of formula (12), formula (13), and formula (14) in each nucleus, and the mass of each compound The ratio was calculated. Moreover, the average value of each a1-a3 and b1-b3 was calculated | required from the obtained molecular weight.
The GPC measurement of the phenol resin 1 was performed under the following conditions. 6 ml of the solvent tetrahydrofuran (THF) was added to 20 mg of the phenol resin 1 sample and sufficiently dissolved, and subjected to GPC measurement. The GPC system consists of WATERS module W2695 and Tosoh TSK.
GUARDCOLUMN HHR-L (diameter 6.0 mm, tube length 40 mm, guard column), two TSK-GEL GMHHR-L (diameter 7.8 mm, tube length 30 mm, polystyrene gel column) manufactured by Tosoh Corporation, differential refractive index manufactured by WATERS (RI) A detector W2414 connected in series was used. The flow rate of the pump was 0.5 ml / min, the temperature in the column and the differential refractometer was 40 ° C., and measurement was performed by injecting the measurement solution from a 100 μl injector.
The FD-MS measurement of the phenol resin 1 was performed under the following conditions. After adding 1 g of the solvent dimethyl sulfoxide (DMSO) to 10 mg of the phenol resin 1 sample and dissolving it sufficiently, it was applied to the FD emitter and subjected to measurement. The FD-MS system uses an MS-FD15A manufactured by JEOL Ltd. as the ionization unit and an MS-700 model name double-convergence mass spectrometer manufactured by JEOL Ltd. as the detector, and detects the detected mass. It measured in the range (m / z) 50-2000.

  Phenol resin 2: In the synthesis of phenol resin 1, 39.4 parts by weight of p-xylylene glycol (Tokyo Chemical Industry p-xylylene glycol, melting point 118 ° C., molecular weight 138, purity 98%), 37% formaldehyde aqueous solution (sum 12.5 parts by mass of formalin 37% manufactured by Kojun Pharmaceutical Co., Ltd., 1,2,4-trimethylbenzene instead of 1,3,5-trimethylbenzene (deer grade reagent manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 170 ° C., molecular weight 120, purity 99%), the other operations were the same as those of the phenol resin 1, and the phenol resin 2 (hydroxyl equivalent 166) which is a mixture of the polymers represented by the formulas (15), (16) and (17). And an ICI viscosity of 0.75 dPa · s at a softening point of 68 ° C. and 150 ° C.). As a result of GPC analysis and FD-MS analysis of the obtained phenol resin 2 in the same manner as the phenol resin 1, the mass of the polymer represented by the following formula (15), formula (16), and formula (17) The ratios are 61.4% by mass, 35.9% by mass, and 2.7% by mass, respectively, and the average of a4 to a6 and b4 to b6 in the following formulas (15), (16), and (17) The values were a4 = 0.98, a5 = 0.91, a6 = 1.40, b4 = 0.80, b5 = 0.68, b6 = 0.65. The GPC chart of the phenol resin 2 is shown in FIG. 4, and the FD-MS chart is shown in FIG.

Further, the results of FD-MS analysis and GPC analysis of phenol resin 1 and phenol resin 2 are shown in Table 1 below.

  Phenol resin 3: Phenol novolak resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-HF-3, hydroxyl group equivalent 104, softening point 80 ° C., ICI viscosity 1.08 dPa · s at 150 ° C.).

Phenol resin 4: Phenol aralkyl resin having a phenylene skeleton (Mitsui Chemicals, XLC-4L, hydroxyl equivalent 168, softening point 62 ° C., ICI viscosity 0.76 dPa · s at 150 ° C.).

  Phenol resin 5: In the synthesis of phenol resin 1, 29.4 parts by mass of p-xylylene glycol (p-xylylene glycol manufactured by Tokyo Chemical Industry Co., Ltd., melting point 118 ° C., molecular weight 138, purity 98%), 37% aqueous solution of formaldehyde Other operations are as follows: 11.5 parts by weight of formalin 37% manufactured by Kojun Pharmaceutical Co., Ltd., 1,3,5-trimethylbenzene (deer grade reagent by Tokyo Chemical Industry, boiling point 165 ° C., molecular weight 120, purity 99%) 0 parts by weight The same operation as the phenol resin 1 was performed, and the phenol resin 5 (hydroxyl equivalent 143, softening point 77 ° C., ICI viscosity 1.0 dPa · s at 150 ° C.) represented by the formula (18) was obtained. As a result of performing GPC analysis and FD-MS analysis of the obtained phenol resin 5 in the same manner as the phenol resin 1, the average values of a7 and b7 were a7 = 1.79 and b7 = 1.20.

  Phenol resin 6: Phenol (special grade reagent manufactured by Kanto Chemical, phenol, melting point 40.9 ° C., molecular weight 94, purity 99.3%) 100 parts by mass, xylene formaldehyde resin (manufactured by Fudou Co., Ltd., Nikanol LLL, average molecular weight molecular weight 340) 67.7 parts by mass, 0.03 parts by mass of p-toluenesulfonic acid monohydrate (p-toluenesulfonic acid, molecular weight 190, purity 99%, manufactured by Wako Pure Chemical Industries, Ltd.) were weighed into a separable flask and replaced with nitrogen. The mixture was heated while stirring was started at the start of melting. After making it react for 1 hour after confirming that the inside of the system reached 110 ° C., 48.8 parts by mass of 37% formaldehyde aqueous solution (37% formalin manufactured by Wako Pure Chemical Industries) and 0.5 part by mass of oxalic acid for 30 minutes Added over time. Subsequently, the reaction was carried out for 120 minutes while maintaining the temperature in the system in the range of 100 ° C to 110 ° C. Until the end of the reaction, water generated in the system by the reaction or mixed into the system with the addition of formalin was discharged out of the system by a nitrogen stream. After completion of the reaction, unreacted components were distilled off under reduced pressure conditions of 160 ° C. and 2 mmHg, and then 200 parts by mass of toluene was added and dissolved uniformly, then transferred to a separatory funnel, and 150 parts by mass of distilled water was added and shaken. After repeating the operation of rinsing the water layer (washing) until the wash water becomes neutral, volatile components such as toluene and residual unreacted components are distilled off by subjecting the oil layer to 125 ° C. under reduced pressure, A phenol resin 6 (hydroxyl equivalent 167, softening point 86 ° C., ICI viscosity 2.1 dPa · s at 150 ° C.) represented by the following formula (19) was obtained. As a result of conducting GPC analysis and FD-MS analysis of the obtained phenol resin 6 in the same manner as the phenol resin 1, the average values of a8 and b8 were a8 = 1.51 and b8 = 1.40.

  The softening points and ICI viscosities of the resulting phenolic resins 1-6 are summarized in Table 2 below. Furthermore, these phenolic resins were evaluated for blocking. The results are listed in Table 2 below.

In addition, blocking evaluation of the phenol resin was performed as follows.
In a cylindrical cylindrical container made of polypropylene having an inner diameter of 29 mm and a height of 10 cm, 20 g of granular phenol resin previously cooled to 5 ° C. was put, and a piston with an outer diameter of 29 mm and a mass of 200 g was inserted into the cylindrical container, and set to a predetermined temperature. When the phenolic resin was loaded in a standing condition in a thermostatic chamber for a certain period of time and then the cylindrical container was turned upside down, the phenolic resin was taken out of the container in its original granular form. ◎, ◯ when the internal shape of the piston is maintained but easily unraveled by hand, x when the internal shape of the piston is not unraveled by hand, and xx when the resin cannot be melted and taken out. The phenol resins 1 and 2 were the result of being excellent in blocking property, although being low viscosity compared with the phenol resin 4 (XLC-4L by Mitsui Chemicals, Inc.).

The following epoxy resins 1-5 were used for the epoxy resin.
Epoxy resin 1: phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC3000P, epoxy equivalent 275, softening point 60 ° C., ICI viscosity 1.1 dPa · s at 150 ° C.)
Epoxy resin 2: biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-4000HK, epoxy equivalent 191, melting point 105 ° C., ICI viscosity 0.1 dPa · s at 150 ° C.)
Epoxy resin 3: bisphenol F type epoxy resin (manufactured by Toto Kasei Co., Ltd., YSLV-80XY, epoxy equivalent 190, melting point 80 ° C., ICI viscosity 0.03 dPa · s at 150 ° C.)
Epoxy resin 4: A phenol aralkyl type epoxy resin having a phenylene skeleton (manufactured by Mitsui Chemicals, Inc., E-XLC-3L, epoxy equivalent 238, softening point 52 ° C., ICI viscosity 1.2 dPa · s at 150 ° C.).
Epoxy resin 5: bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YL6810)
, Epoxy equivalent 172, melting point 45 ° C., ICI viscosity at 150 ° C. 0.03 dPa · s)

  As the inorganic filler, 80 parts by mass of fused spherical silica FB560 (average particle size 30 μm) manufactured by Denki Kagaku Kogyo Co., Ltd., 10 parts by mass of synthetic spherical silica SO-C2 (average particle size 0.5 μm) manufactured by Admatechs Co., Ltd. A blend of 10 parts by mass of synthetic spherical silica SO-C5 (average particle size 1.5 μm) manufactured by Admatechs Co., Ltd. was used.

The following hardening accelerators 1-4 were used for the hardening accelerator.
Curing accelerator 1: Curing accelerator represented by the following formula (20)

  Curing accelerator 2: Curing accelerator represented by the following formula (21)

  Curing accelerator 3: Curing accelerator represented by the following formula (22)

  Curing accelerator 4: Curing accelerator represented by the following formula (23)

As the release agent, the following release agents 1 to 5 were used.
Release agent 1: Oxidized polyethylene wax (drop point 120 ° C., acid value 20 mg KOH / g, number average molecular weight 2000, density 0.98 g / cm ³ , average particle diameter 45 μm, content ratio of particles 106 μm or more in content ratio 0.0 Mass%, Ricowax PED191 manufactured by Clariant Japan Co., Ltd., which is an oxide of high-density polyethylene polymer, whose particle size is adjusted by a jet mill.) Release agent 2: Oxidized polyethylene wax (drop point 110) prepared by the method described above Jetting oxide of high density polyethylene polymer, acid content 12 mg KOH / g, number average molecular weight 1200, density 0.97 g / cm ³ , average particle size 50 μm, content ratio of particles 106 μm or larger (The particle size is adjusted by a mill.)
Release agent 3: Oxidized polyethylene wax (dropping point 120 ° C., acid value 20 mg KOH / g, number average molecular weight 2000, density 0.98 g / cm ³ , average particle size 30 μm, content ratio of particles having particle size 106 μm or more 0.0 Mass%, Rico wax PED191 manufactured by Clariant Japan Co., Ltd., which is an oxide of high-density polyethylene polymer, whose particle size is adjusted by a jet mill.)
Mold release agent 4: Carnauba wax (Nikko Fine Co., Ltd., Nikko Carnauba, melting point 83 ° C., acid value 7 mgKOH / g)

  As the compound (F), a compound represented by the following formula (24) (Tokyo Chemical Industry Co., Ltd., 2,3-naphthalenediol, purity 98%) was used.

The following silane coupling agents 1-2 were used for the silane coupling agent.
Silane coupling agent 1: γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)
Silane coupling agent 2: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)

  Carbon black (MA600) manufactured by Mitsubishi Chemical Corporation was used as the colorant.

Example 1
The following components were mixed at room temperature using a mixer, melted and kneaded with a heating roll at 80 ° C. to 100 ° C., then cooled, and then pulverized to obtain a semiconductor sealing resin composition.
Phenolic resin 2 4.89 parts by weight Epoxy resin 1 8.11 parts by weight Inorganic filler 86.00 parts by weight Curing accelerator 1 0.40 parts by weight Release agent 1 0.20 parts by weight Silane coupling agent 1 0.10 Part by mass Silane coupling agent 2 0.10 part by mass Colorant 0.20 part by mass The obtained resin composition for semiconductor encapsulation was evaluated for the following items. The evaluation results are shown in Table 3.

  Spiral flow: Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a spiral flow measurement mold according to EMMI-1-66 was applied at 175 ° C., injection pressure 6.9 MPa, holding pressure The epoxy resin composition was injected under the condition of time 120 seconds, and the flow length was measured. The spiral flow is a fluidity parameter, and the larger the value, the better the fluidity. The unit is cm.

  Flame resistance: Epoxy resin using a low pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) under conditions of a mold temperature of 175 ° C., an injection time of 15 seconds, a curing time of 120 seconds, and an injection pressure of 9.8 MPa. The composition was injection molded to produce a 3.2 mm thick flame proof test piece. About the obtained test piece, the flame resistance test was done according to the specification of UL94 vertical method. The table shows the flame resistance rank.

  Continuous moldability: epoxy resin composition using a low-pressure transfer automatic molding machine (Daiichi Seiko Co., Ltd., GP-ELF) under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 70 seconds. A silicon chip or the like is molded by sealing, and 80-pin QFP (preprating frame: nickel / palladium alloy gold-plated, package outer dimension: 14 mm × 20 mm × 2 mm thickness, pad size: 6.5 mm × 6.5 mm, Molding to obtain a chip size of 6.0 mm × 6.0 mm × 350 μm thickness was continuously performed up to 500 shots. Judgment criteria were ◎ for those that could be continuously molded up to 500 shots without any problems such as unfilling or mold release failure, ◯ for those that could be continuously molded up to 300 shots, and × otherwise.

  Package appearance and mold stain resistance: In the evaluation of the continuous moldability, the package and mold after 300 shots and after 500 shots were visually evaluated for stains. Judgment criteria for package appearance and mold dirtiness are indicated by x for those in which dirt has occurred up to 300 shots, ◯ for those that have not been soiled up to 300 shots, and ◎ that are not dirty up to 500 shots. Further, in the above-mentioned continuous formability, those that could not be formed without any problem up to 500 shots were judged based on the package appearance and mold contamination status when the continuous forming was abandoned.

  Solder resistance: The package formed in the above-described evaluation of continuous formability is post-cured at 175 ° C. for 8 hours, and the resulting package is humidified at 85 ° C. and 60% relative humidity for 168 hours, followed by IR reflow treatment at 260 ° C. Did. For 20 packages, the adhesion state of the interface between the semiconductor element and the cured product of the epoxy resin composition was observed with an ultrasonic flaw detector, and the peeling occurrence rate [(number of peeling occurrence packages) / (total number of packages) × 100] Calculated. Units%. The criteria for determining solder resistance were ◯ when no peeling occurred, Δ when the peeling rate was less than 20%, and x when the peeling rate was 20% or more.

Examples 2 to 13 and Comparative Examples 1 to 6
According to the composition of Table 3, an epoxy resin composition was produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Examples 1 to 13 include structural units represented by general formula (1) and general formula (2), and at least one terminal is an aromatic group having at least one alkyl group having 1 to 3 carbon atoms. It is a resin composition for semiconductor encapsulation containing a phenolic resin, an epoxy resin, an inorganic filler, a curing accelerator, and an oxidized polyethylene wax. What changed the kind, what changed the kind of epoxy resin, what changed the kind of hardening accelerator, or what mix | blended the compound (F) is included.
In any case, excellent results were obtained in the balance of fluidity (spiral flow), flame resistance, solder resistance, and continuous formability. On the other hand, a phenol resin comprising a structural unit represented by the general formula (1) and the general formula (2), and having an aromatic group having at least one alkyl group having 1 to 3 carbon atoms at at least one terminal; In Comparative Examples 1 to 6 containing no oxidized polyethylene wax, the flame resistance, solder resistance, and continuous moldability were also inferior.

  According to the present invention, it is possible to obtain a resin composition for semiconductor encapsulation that has good flame resistance and solder resistance, is excellent in fluidity and curability, is excellent in continuous moldability, and can be manufactured at low cost. Therefore, it is suitable for semiconductor device sealing.

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Die-bonding material hardening body 3 Die pad 4 Gold wire 5 Lead frame 6 Hardening body of resin composition for sealing

Claims (6)

A phenol resin comprising a structural unit represented by the following general formula (1) and general formula (2), and having an aromatic group having at least one alkyl group having 1 to 3 carbon atoms at at least one terminal;

(In General Formula (1), R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R 3 is independently a hydrocarbon having 1 to 6 carbon atoms. A is an integer of 0 to 3)

(In General Formula (2), R5, R6, R8 and R9 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R4 and R7 are independently of each other a carbon number. 1 to 6 hydrocarbon groups, b is an integer of 0 to 3, and c is an integer of 0 to 4)
Epoxy resin,
An inorganic filler;
A curing accelerator;
With oxidized polyethylene wax,
A resin composition for encapsulating a semiconductor, comprising:   2. The resin composition for semiconductor encapsulation according to claim 1, wherein the aromatic group having at least one alkyl group having 1 to 3 carbon atoms is a trimethylphenyl group. The said phenol resin contains the polymer represented by following General formula (3), The resin composition for semiconductor sealing of Claim 1 or 2 characterized by the above-mentioned.

(In the general formula (3), m1 is an average value and is a number of 0.3 or more and 7 or less, and n1 is an average value and is a number of 0.3 or more and 7 or less) The said phenol resin contains the polymer represented by following General formula (4), The resin composition for semiconductor sealing of any one of Claim 1 thru | or 3 characterized by the above-mentioned.

(In the general formula (4), m2 is an average value and is a number of 0.3 or more and 7 or less, and n2 is an average value and is a number of 0.1 or more and 4 or less) The curing accelerator includes at least one selected from a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound and an adduct of a phosphonium compound and a silane compound. The resin composition for semiconductor sealing of any one of Claim 1 thru | or 4.   A semiconductor device obtained by encapsulating a semiconductor element with the resin composition for encapsulating a semiconductor according to any one of claims 1 to 5.

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