JP5494137B2 - Semiconductor sealing resin composition and semiconductor device - Google Patents

Description

  The present invention relates to a resin composition for semiconductor encapsulation and a semiconductor device.

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 are becoming more dense and highly integrated, their mounting method is changed from insertion mounting. It is changing to surface mounting. In addition, semiconductor devices represented by surface mount type QFP (Quad Flat Package) and the like have been put into practical use because of demands for miniaturization, weight reduction, and lead pin multi-pinning of semiconductor devices. Since these semiconductor devices have an excellent balance of productivity, cost, reliability, etc., mold molding (sealing) using an epoxy resin composition has become the mainstream.
Conventionally, bromine-containing epoxy resins and antimony oxide have been generally used as flame retardants for the purpose of imparting flame retardancy to semiconductor devices in epoxy resin compositions for sealing. There is a growing movement to regulate the use of halogen-containing compounds that are likely to generate dioxin-like compounds and highly toxic antimony compounds.
Under these circumstances, metal hydroxides such as aluminum hydroxide and magnesium hydroxide have been proposed as flame retardants to replace brominated epoxy resins and antimony compounds. It is easy to cause deterioration of properties, and may not be sufficient in terms of moldability and reliability.
In addition, since lead contained in solder used for conventional mounting is harmful, replacement with lead-free solder is being promoted. The melting point of lead-free solder is higher than that of conventional lead / tin solder, and the temperature during solder mounting such as infrared reflow and solder immersion is increased from the conventional 220 ° C. to 240 ° C. to 240 ° C. to 260 ° C. Due to such an increase in mounting temperature, there is a high possibility that cracks will occur in the resin part during mounting.
Further, since it is necessary to lead the exterior solder plating for the lead frame, a lead frame preliminarily subjected to nickel / palladium plating is being used instead of the exterior solder plating. This nickel / palladium plating has a problem that a conventional sealing material cannot secure sufficient adhesion, and is easily peeled off from the lead frame during mounting.
Semiconductor devices are required to achieve both the above-mentioned environmental friendliness and reliability, especially thin surfaces such as TSOP (thin small outline package) and LQFP (low profile quad flat package). This is an important issue for mounting packages.

From the above situation, biphenylene skeleton-containing phenol aralkyl type epoxy resin, biphenylene skeleton-containing phenol aralkyl are used as epoxy resin compositions for semiconductor encapsulation that can obtain good flame retardancy without adding a flame retardant imparting agent. An epoxy resin composition using a mold curing agent has been proposed (see, for example, Patent Documents 1 and 2).
These epoxy resin compositions have the advantage of being able to obtain a highly reliable semiconductor device with low water absorption, low elastic modulus during heat, high adhesion, excellent flame retardancy, and molding after curing. Since the product is soft and has high lipophilicity, there may be a problem in continuous formability in the sealing process of the semiconductor device, and productivity may be reduced.
For such a problem, a method of adjusting the molecular weight distribution of the curing agent has been proposed (see, for example, Patent Document 3). However, adjustment of the molecular weight distribution described above requires, for example, a step of purifying monomer raw materials in advance of molecular weight classification using a distillation or fractionation column after synthesis or synthesis, after synthesizing a phenol resin. In addition to requiring a large-scale refining facility and a solvent treatment facility, there is a problem that the production cost increases due to a recovery loss.

JP-A-11-140277 Japanese Patent No. 362736 International Publication Number WO2005 / 087873

  Therefore, the present invention has been made in view of such circumstances, and provides a resin composition for semiconductor encapsulation that has good flame resistance and solder resistance, is excellent in continuous moldability, and can be manufactured at low cost. Is.

（一般式（１）において、Ｒ１およびＲ３は、互いに独立して、水素原子、または炭素数１〜１０の炭化水素基であり、Ｒ２は、互いに独立して、水素原子、炭素数１〜１０の炭化水素基、水酸基であり、ａは０〜３の整数、ｂおよびｃは０〜４の整数、mは０〜１０
の整数でありｍ≦１の成分を含み、ｎは０〜１０の整数である。）
で表される構造を含むフェノール樹脂と、
エポキシ樹脂と、
無機充填剤と、
を含むことを特徴とする。 The resin composition for semiconductor encapsulation of the present invention has the following general formula (1):

(In General Formula (1), R 1 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 2 is independently a hydrogen atom or carbon number 1 to 10. A is an integer of 0 to 3, b and c are integers of 0 to 4, and m is an integer of 0 to 10.
And an integer of m ≦ 1, and n is an integer of 0 to 10. )
A phenolic resin having a structure represented by:
Epoxy resin,
An inorganic filler;
It is characterized by including.

In the resin composition for semiconductor encapsulation of the present invention, the phenol resin including the structure represented by the general formula (1) includes a phenol resin of 1 ≦ m ≦ 10 and a phenol resin of m = 0. it can.
The resin composition for encapsulating a semiconductor of the present invention comprises a component (A) of the above general formula (1) obtained by measurement by a gel permeation chromatographic area method and a gel permeation chromatograph. The component ratio A / B with the component (B) of “m = 0” in the general formula (1) obtained by measurement by the area method can be 0.05 or more and 1.5 or less.
The resin composition for encapsulating a semiconductor of the present invention includes an “n = 0” component obtained by measurement by an area method of a gel permeation chromatograph of a phenol resin including the structure represented by the general formula (1). be able to.
The resin composition for encapsulating a semiconductor of the present invention comprises a component (a) of “1 ≦ m ≦ 10 and n = 1-3” of the above general formula (1) obtained by measurement by an area method of gel permeation chromatography. The ratio a / b with the component (b) of “m = 0 and n = 1-3” of the above general formula (1) obtained by measurement by the area method of gel permeation chromatograph is 0.05 or more and 0.55. It can be:
The resin composition for semiconductor encapsulation of the present invention may further contain a curing accelerator.
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 is possible to include 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.

  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. 2 is a GPC chart of phenol resin 1. 2 is an FD-MS chart of phenol resin 1. 2 is a GPC chart of phenol resin 2. 3 is a GPC chart of phenol resin 3. 3 is a GPC chart of phenol resin 4.

  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 this invention contains the phenol resin containing the structure represented by the said General formula (1), an epoxy resin, and an inorganic filler.
In the present invention, a phenol resin including a structure represented by the general formula (1) is used. The structural unit represented by the repeating number n of the phenol resin has an effect of improving the flame resistance, reducing the water absorption rate, and improving the solder resistance of the resin composition by having a biphenylene aralkyl skeleton. Furthermore, by having a structural unit represented by the number of repetitions m, it is possible to locally increase the density of the phenolic hydroxyl group and exhibit good reactivity with the epoxy group. As a result, the phenol resin is low in cost. It has the characteristics of having both flame resistance, solder resistance, reactivity and continuous formability.

R1 and R3 in the general formula (1) are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other, and are a hydrocarbon group containing an aromatic group. It is preferable. As a result, in addition to the biphenylene skeleton, there are more aromatic rings, and the flame resistance of the cured product of the resin composition using this can be made more excellent. R1 and R3 may be bonded to any position of the benzene ring. a is an integer of 0 to 3, and c is an integer of 0 to 4.
R2 in the general formula (1) is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a hydroxyl group, and may be the same or different. R2 may be bonded to any position of the benzene ring. b is an integer of 0-4.

Moreover, n in General formula (1) is an integer of 0-10, and it is desirable that the compound whose n = 1 and 2 are a main component from a fluid viewpoint. Although it does not specifically limit as a lower limit of the content rate of the component which is n = 1 and 2, It is preferable that it is 30 mass% or more with respect to the phenol resin whole quantity containing the structure represented by the said General formula (1). 40% by mass or more is more preferable. When the lower limit value of the content ratio of the components with n = 1 and 2 is within the above range, the resin composition can exhibit good fluidity. In order to make the content ratio of the components of n = 1 and 2 within the above-mentioned preferable range, it can be adjusted by the method [1] described later.

Further, m in the general formula (1) is an integer of 0 to 10, includes components of m ≦ 1, and is not particularly limited as long as the average value is larger than 0. In general formula (1), m = 0 is a phenol aralkyl resin containing a biphenylene skeleton, which is excellent in flame resistance, low water absorption, and solder crack resistance, but has insufficient reactivity and high lipophilicity. In some cases, the continuous formability is not sufficient. On the other hand, m ≧ 1 and n ≧ 1 have both a biphenylene skeleton and a high-density phenolic hydroxyl group, thereby maintaining good compatibility with the m = 0 component and good reactivity and curing with an epoxy resin. As a result, the resin composition is considered to exhibit good continuous moldability.
In the resin composition for semiconductor encapsulation of the present invention, the phenol resin including the structure represented by the general formula (1) preferably includes a phenol resin of 1 ≦ m ≦ 10 and a phenol resin of m = 0. .

Moreover, the phenol resin containing the structure represented by the general formula (1) has a higher viscosity of the phenol resin itself as the value of m is larger, that is, as the number of high-density phenolic hydroxyl groups is increased. Sexuality is impaired. The phenol resin including the structure represented by the general formula (1) preferably has components of m = 0 and 1 as main components from the viewpoint of achieving both continuous moldability and fluidity.
The content ratio of the “1 ≦ m ≦ 10” component contained in the total mass of the phenol resin including the structure represented by the general formula (1) is (A) mass%, and the content ratio of the “m = 0” component is ( When B)% by mass, the component ratio A / B is preferably 0.05 or more and 1.5 or less, and more preferably 0.1 or more and 1 or less. When the lower limit value of the component ratio A / B is within the above range, the resin composition can exhibit good curability and continuous moldability. When the upper limit value of the component ratio A / B is within the above range, the resin composition can exhibit good fluidity. In order to make the component ratio A / B within the above-mentioned preferable range, it can be adjusted by the method [2] described later.
Furthermore, what contains the "n = 0" component contained in the total mass of the phenol resin containing the structure represented by General formula (1) is preferable.
In particular, the content ratio of the components “1 ≦ m ≦ 10 and n = 1 to 3” contained in the total mass of the phenol resin including the structure represented by the general formula (1) is (a) mass%, “m = When the content ratio of the component “0 and n = 1 to 3” is (b) mass%, the component ratio a / b is preferably 0.05 or more and 0.55 or less, and 0.1 or more and 0.4 or less. It is more preferable that When the lower limit value of the component ratio a / b is within the above range, the resin composition can exhibit good curability and continuous moldability. When the upper limit value of the component ratio a / b is within the above range, the resin composition can exhibit good fluidity. In order to make the component ratio a / b within the above-mentioned preferable range, it can be adjusted by the method [2] described later.

  In the case of the above phenol resin synthesis reaction, the obtained phenol resin contains n = 0 component in the general formula (1) in addition to the phenol resin including the structure represented by the general formula (1). Although the content is not particularly limited, it is preferably 30% by mass, more preferably 25% by mass or less, based on the entire curing agent. When the upper limit is within the above range, the resulting resin composition has good solder resistance and flame resistance. In order to make the content rate of n = 0 component into the above-mentioned preferable range, it can adjust by the method [3] mentioned later.

The content ratio of m = 0 component and 1 ≦ m ≦ 10 component in the general formula (1) can be calculated as follows. Each component corresponding to the peak detected from the ratio of the detected peak area is obtained by performing gel permeation chromatography (GPC) measurement of the phenol resin to determine the polystyrene equivalent molecular weight of each component corresponding to the detected peak. The content ratio (mass%) of is calculated.
The gel permeation chromatography (GPC) measurement in the present invention is performed as follows. The GPC apparatus is composed of a pump, an injector, a guard column, a column, and a detector, and tetrahydrofuran (THF) is used as a solvent. The flow rate of the pump is measured at 0.5 ml / min. A flow rate higher than this is not preferable because the detection accuracy of the target molecular weight is lowered. In order to accurately measure at the above flow rate, it is necessary to use a pump with good flow rate accuracy, and the flow rate accuracy is preferably 0.10% or less. A commercially available guard column (for example, TSK GUARDCOLUMN HHR-L: diameter 6.0 mm, tube length 40 mm) manufactured by Tosoh Corporation, and a commercially available polystyrene gel column (TSK-GEL GMHHR- manufactured by Tosoh Corporation) are used for the guard column. L: diameter 7.8 mm, tube length 30 mm) are connected in series. A differential refractometer (RI detector, for example, a differential refractive index (RI) detector W2414 manufactured by WATERS) is used as the detector. Prior to measurement, the guard column, the column, and the inside of the detector are kept stable at 40 ° C. As a sample, a THF solution of the above phenol resin adjusted to a concentration of 3 to 4 mg / ml is prepared, and this is injected from about 50 to 150 μl of an injector for measurement. In analyzing the sample, a calibration curve prepared from a monodisperse polystyrene (hereinafter referred to as PS) standard sample is used. For the calibration curve, a logarithmic value of the molecular weight of PS and the peak detection time (retention time) of PS are plotted, and a regression of the cubic equation is used. As standard PS samples for preparing calibration curves, Shodex Standard SL-105 series product numbers S-1.0 (peak molecular weight 1060), S-1.3 (peak molecular weight 1310), S-2 manufactured by Showa Denko K.K. 0.0 (peak molecular weight 1990), S-3.0 (peak molecular weight 2970), S-4.5 (peak molecular weight 4490), S-5.0 (peak molecular weight 5030), S-6.9 (peak molecular weight 6930) ), S-11 (peak molecular weight 10700), S-20 (peak molecular weight 19900). For identifying the peak position of m = 0 component, a commercially available biphenylene skeleton-containing phenol aralkyl resin (for example, MEH-7851 manufactured by Meiwa Kasei Co., Ltd.) is used. For identifying the peak position of n = 0 component, commercially available A triphenylpropane type phenol resin (for example, MEH-7500, manufactured by Meiwa Kasei Co., Ltd.) is measured.

  The phenol resin may contain a structure other than the structure represented by the general formula (1), and is particularly limited as long as it is a structure in which a divalent hydrocarbon group is bonded to an aromatic hydrocarbon having a hydroxyl group. Is not to be done. For example, examples of the aromatic hydrocarbon having a hydroxyl group include structures such as phenol, dihydroxybenzene, trihydroxybenzene, hydroxynaphthalene, dihydroxynaphthalene, trihydroxynaphthalene, hydroxyanthracene, and dihydroxyanthracene. As methylene group, ethylidene group, isopropylidene group, benzylidene group, phenylethylidene group, phenylenebismethylene (xylylene) group, phenylenebisethylidene group, biphenylenebismethylene group, biphenylenebisethylidene group, naphthylenebismethylene group, naphthylene Examples thereof include a bisethylidene group.

  The phenol resin containing the structure represented by the general formula (1) used in the resin composition for encapsulating a semiconductor of the present invention includes, for example, a biphenylene compound represented by the following general formula (2), and the following general formula (3). It can obtain by reacting with the hydroxybenzaldehyde compound represented by these, a phenol compound, and an acidic catalyst.

（一般式（２）において、Ｘは、水酸基、ハロゲン原子、炭素数１〜４のアルコキシ基を示す。Ｒ３は、互いに独立して、水素原子、または炭素数１〜１０の炭化水素基であり、ｃは０〜４の整数である。）

(In General Formula (2), X represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms. R3 is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. And c is an integer of 0 to 4.)

（一般式（３）において、Ｒ２は、互いに独立して、水素原子、炭素数１〜１０の炭化水素基、水酸基であり、ｂは０〜４の整数である。）

(In general formula (3), R2 is a hydrogen atom, a C1-C10 hydrocarbon group, and a hydroxyl group independently of each other, and b is an integer of 0-4.)

The biphenylene compound used for the raw material of the phenol resin containing the structure represented by the general formula (1) is not particularly limited as long as it is a chemical structure represented by the general formula (2).
For example, 4,4′-bischloromethylbiphenyl, 4,4′-bisbromomethylbiphenyl, 4,4′-bisiodomethylbiphenyl, 4,4′-bishydroxymethylbiphenyl, 4,4′-bismethoxymethylbiphenyl 3,3 ′, 5,5′-tetramethyl-4,4′-bischloromethylbiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bisbromomethylbiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-bisiodomethylbiphenyl, 3,3', 5,5'-tetramethyl-4,4'-bishydroxymethylbiphenyl, 3,3 ', 5 5′-tetramethyl-4,4′-bismethoxymethylbiphenyl and the like can be mentioned.
When X is a halogen atom, hydrogen halide produced as a by-product during the reaction acts as an acidic catalyst, so there is no need to add an acidic catalyst in the reaction system, and a small amount of water can be added. The reaction can be started immediately. Among these, 4,4′-bismethoxymethylbiphenyl and 4,4′-bischloromethylbiphenyl can be obtained relatively inexpensively from the viewpoint of availability. These may be used alone or in combination of two or more.

  The hydroxybenzaldehyde used for the raw material of the phenol resin containing the structure represented by the general formula (1) is not particularly limited as long as it is a chemical structure represented by the general formula (3). Specifically, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 2 -Hydroxy-5-methylbenzaldehyde and the like. Among these, o-hydroxybenzaldehyde is preferable because it is easily available industrially. These may be used alone or in combination of two or more.

As a phenol compound used for manufacture of the phenol resin containing the structure represented by the general formula (1), for example, phenol, o-cresol, p-cresol, m-cresol, phenylphenol, ethylphenol, n-propylphenol , Iso-propylphenol, t-butylphenol, xylenol, methylpropylphenol, methylbutylphenol, dipropylphenol, dibutylphenol, nonylphenol, mesitol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, etc. However, it is not limited to these.
Among these, from the viewpoint of cost, 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.

  The method for synthesizing the phenol resin used in the present invention is not particularly limited. For example, the total amount of biphenylene compounds and hydroxybenzaldehydes is 0.1 to 0.8 mol per 1 mol of the phenol compound, and the biphenylene compound. / Hydroxybenzaldehyde ratio (weight ratio) 1 to 10, acidic catalyst such as formic acid, oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Lewis acid, etc. The reaction is carried out for 2 to 20 hours at a temperature of 180 ° C. while discharging the generated gas and moisture out of the system by nitrogen flow, and unreacted phenol, reaction byproducts (for example, hydrogen halide and methanol) remaining after the reaction, catalyst (For example, hydrochloric acid) can be obtained by distilling off by a method such as vacuum distillation or steam distillation.

Here, examples of a method for bringing the phenol resin into the above-described preferable range include the following methods.
[1] In order to make the content ratio of the components of n = 1 to 2 within the above-mentioned preferable range, the blending amount of the acid catalyst is decreased, the charging ratio of the phenol compound / biphenylene compound is increased, the reaction temperature is decreased, etc. By the method, the content ratio of the component of n = 1 to 2 can be increased.
[2] A method of increasing the biphenylene compound / hydroxybenzaldehyde ratio or adding a separately synthesized n = 0 component before and after the above synthesis in order to make the above component ratio A / B within the above preferred range. Thus, the component ratio A / B can be reduced.
[3] In order to make the content ratio of the n = 0 component within the above-mentioned preferable range, hydroxybenzaldehyde is gradually added to the reaction system from the middle to the end of the reaction while the phenol compound and the biphenylene compound are subjected to a condensation reaction using an acidic catalyst. You may take the method of adding to. In this case, the progress of the reaction is performed by sampling the water, hydrogen halide, and alcohol gas generated by the reaction of the biphenylene compound and phenol, or by sampling the product in the middle of the reaction and measuring the molecular weight by gel permeation chromatography. Can be confirmed.

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 the polyaddition type curing agent include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and metaxylylenediamine, aromatic polyamines such as diaminodiphenylmethane, m-phenylenediamine, and diaminodiphenylsulfone, dicyandiamide, organic Polyamine compounds including acid dihydralazide; alicyclic acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride; aromatic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic acid Acid anhydride containing; polyphenol compound such as novolac type phenol resin and phenol polymer; polymercaptan compound such as polysulfide, thioester and thioether; isocyanate prepolymer, Isocyanate compounds such as click 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 and 2,4,6-trisdimethylaminomethylphenol; imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole; Examples include Lewis acids such as BF ₃ complex.
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, and the like. Can be mentioned.

  Among these, a phenol resin-based curing agent is preferable from the viewpoint of balance between 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 The recited, they 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.

In the case of using such other curing agents in combination, the blending ratio of the phenol resin containing the structure represented by the general formula (1) is preferably 15% by mass or more based on the total curing agent, It is more preferably 25% by mass or more, and particularly preferably 35% by mass or more. 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. Further, the upper limit of the blending ratio of the entire curing agent is not particularly limited, but is preferably 10% by mass or less, and more preferably 8% by mass or less in the entire resin composition. 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 resin, bisphenol type epoxy resin, and stilbene type epoxy resin; phenol novolac type epoxy resin, cresol novolac type Novolak 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, naphthols such as epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimers Epoxy resins; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; and bridged cyclic hydrocarbon compound-modified phenol type epoxy resins such as dicyclopentadiene-modified phenol type epoxy resins. It is not limited.
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 to contain as few ionic impurities as Na ions and Cl ions, and from the viewpoint of curability of the semiconductor resin composition, an epoxy resin The epoxy equivalent of is preferably 100 g / eq or more and 500 g / eq or less.

The compounding 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 compounding quantity 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 lower limit is in 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.
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.

In the resin composition for encapsulating a semiconductor of the present invention, a curing accelerator can be further used. Any curing accelerator may be used as long as it has a function of accelerating the crosslinking reaction between the epoxy resin and the curing agent, and those used in general resin compositions for encapsulating semiconductors can be used.
Specific examples include phosphorus atom-containing curing accelerators 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 Nitrogen atom-containing curing accelerators such as (5,4,0) undecene-7, benzyldimethylamine, 2-methylimidazole and the like can be mentioned. Among these, phosphorus atom-containing curing accelerators can obtain preferable curability. . From the viewpoint of the balance between fluidity and curability, tetra-substituted phosphonium compound, phosphobetaine compound, adduct of phosphine compound and quinone compound, adduct of phosphonium compound and silane compound, etc., with phosphorus atom-containing curing acceleration An agent is more preferable. Tetra-substituted phosphonium compounds are particularly preferred when emphasizing the point of fluidity, and phosphobetaine compounds and phosphine compounds when emphasizing the low thermal modulus of the cured resin thermal composition of the semiconductor sealing resin composition. An adduct with a quinone compound is particularly preferred, and an adduct of a phosphonium compound and a silane compound is particularly preferred when importance is attached to latent curing properties.
Examples of the organic phosphine that can be used in the semiconductor sealing resin composition 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 mentioned.

（ただし、上記一般式（４）において、Ｐはリン原子を表す。Ｒ４、Ｒ５、Ｒ６およびＲ７は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す。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、ｙは１〜３の整数、ｚは０〜３の整数であり、かつｘ＝ｙである。）
一般式（４）で表される化合物は、例えば以下のようにして得られるがこれに限定されるものではない。まず、テトラ置換ホスホニウムハライドと芳香族有機酸と塩基を有機溶剤に混ぜ均一に混合し、その溶液系内に芳香族有機酸アニオンを発生させる。次いで水を加えると、一般式（４）で表される化合物を沈殿させることができる。一般式（４）で表される化合物において、リン原子に結合するＲ４、Ｒ５、Ｒ６およびＲ７がフェニル基であり、かつＡＨはヒドロキシル基を芳香環に有する化合物、すなわちフェノール類であり、かつＡは上記フェノール類のアニオンであるのが好ましい。 Examples of the tetra-substituted phosphonium compound that can be used in the semiconductor sealing resin composition of the present invention include compounds represented by the following general formula (4).

(In the general formula (4), P represents a phosphorus atom. R4, R5, R6 and R7 each represents an aromatic group or an alkyl group. A represents a functional group selected from a hydroxyl group, a carboxyl group and a thiol group.) Represents an anion of an aromatic organic acid having at least one of the following: AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group 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 (4) 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 (4) can be precipitated. In the compound represented by the general formula (4), R4, R5, R6 and R7 bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols, and A Is preferably an anion of the above phenols.

（ただし、上記一般式（５）において、Ｘ１は炭素数１〜３のアルキル基、Ｙ１はヒドロキシル基を表す。ｆは０〜５の整数であり、ｇは０〜４の整数である。）
一般式（５）で表される化合物は、例えば以下のようにして得られる。
まず、第三ホスフィンであるトリ芳香族置換ホスフィンとジアゾニウム塩とを接触させ、トリ芳香族置換ホスフィンとジアゾニウム塩が有するジアゾニウム基とを置換させる工程を経て得られる。しかしこれに限定されるものではない。 Examples of the phosphobetaine compound that can be used in the resin composition for semiconductor encapsulation of the present invention include compounds represented by the following general formula (5).

(However, in the said General formula (5), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group. F is an integer of 0-5, and g is an integer of 0-4.)
The compound represented by the general formula (5) 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.

（ただし、上記一般式（６）において、Ｐはリン原子を表す。Ｒ８、Ｒ９およびＲ１０は炭素数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、互いに同一であっても異なっていてもよい。Ｒ１１、Ｒ１２およびＲ１３は水素原子または炭素数１〜１２の炭化水素基を表し、互いに同一であっても異なっていてもよく、Ｒ１１とＲ１２が結合して環状構造となっていてもよい。） 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 (6).

(However, in the said General formula (6), P represents a phosphorus atom. R8, R9, and R10 represent a C1-C12 alkyl group or a C6-C12 aryl group, and even if it is mutually the same, R11, R12 and R13 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R11 and R12 are bonded to form a cyclic structure. May be.)

Examples of the phosphine compound used for the adduct of the phosphine compound and the quinone compound include aromatic compounds 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 or 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. As the solvent, ketones such as acetone and methyl ethyl ketone which have low solubility in the adduct are preferable. However, the present invention is not limited to this.
In the compound represented by the general formula (6), R8, R9 and R10 bonded to the phosphorus atom are phenyl groups, and R11, R12 and R13 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl A compound to which phosphine has been added is preferable in that it reduces the thermal elastic modulus of the cured product of the resin composition for semiconductor encapsulation.

（ただし、上記一般式（７）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ１４、Ｒ１５、Ｒ１６およびＲ１７は、それぞれ、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、互いに同一であっても異なっていてもよい。式中Ｘ２は、基Ｙ２およびＹ３と結合する有機基である。式中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。Ｙ
４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。）
一般式（７）において、Ｒ１４、Ｒ１５、Ｒ１６およびＲ１７としては、例えば、フェニル基、メチルフェニル基、メトキシフェニル基、ヒドロキシフェニル基、ナフチル基、ヒドロキシナフチル基、ベンジル基、メチル基、エチル基、ｎ−ブチル基、ｎ−オクチル基およびシクロヘキシル基などが挙げられ、これらの中でも、フェニル基、メチルフェニル基、メトキシフェニル基、ヒドロキシフェニル基、ヒドロキシナフチル基などの置換基を有する芳香族基もしくは無置換の芳香族基がより好ましい。 Examples of the adduct of a phosphonium compound and a silane compound that can be used in the resin composition for semiconductor encapsulation of the present invention include compounds represented by the following general formula (7).

(In the general formula (7), P represents a phosphorus atom and Si represents a silicon atom. R14, R15, R16 and R17 are each an organic group having an aromatic ring or a heterocyclic ring, or an aliphatic group. X2 is an organic group bonded to the groups Y2 and Y3, where X3 is an organic group bonded to the groups Y4 and Y5. Y3 represents 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.
4 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 (7), as R14, R15, R16 and R17, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, Examples thereof include n-butyl group, n-octyl group and cyclohexyl group. Among these, 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 (7), 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 general formula (7) 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, and salicylic acid. 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. Of these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable.
Z1 in the general formula (7) represents an organic group having an aromatic ring or a heterocyclic ring or an aliphatic group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. And aliphatic hydrocarbon groups such as octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxypropyl group, mercaptopropyl group, aminopropyl group and vinyl group 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 then dissolved. 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 prepared 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 blending ratio of the curing accelerator that can be used in the semiconductor sealing resin composition of the present invention is more preferably 0.1 wt% or more and 1 wt% or less in the total resin composition. When the blending amount of the curing accelerator is within the above range, sufficient curability can be obtained. Moreover, sufficient fluidity | liquidity can be acquired as the compounding quantity of a hardening accelerator is in the said range.

In the present invention, a compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring can be used. A compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring (hereinafter also referred to as “compound (E)”) is represented by the general formula (1). Even when a phosphorus atom-containing curing accelerator having no latent property is used as a curing accelerator that promotes the crosslinking reaction between the phenol resin containing the structure and the epoxy resin, the reaction during the melt-kneading of the resin compound The resin composition for semiconductor encapsulation can be obtained stably.
The compound (E) also has an effect of lowering the melt viscosity of the resin composition for semiconductor encapsulation and improving the fluidity. As the compound (E), a monocyclic compound represented by the following general formula (8) or a polycyclic compound represented by the following general formula (9) can be used. It may have a substituent.

（ただし、上記一般式（８）において、Ｒ１８、Ｒ２２はどちらか一方が水酸基であり、片方が水酸基のとき他方は水素原子、水酸基または水酸基以外の置換基である。Ｒ１９、Ｒ２０、およびＲ２１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 (8), one of R18 and R22 is a hydroxyl group, and when one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group. R19, R20, and R21 are It is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group.)

（ただし、上記一般式（９）において、Ｒ２３、Ｒ２９はどちらか一方が水酸基であり、片方が水酸基のとき他方は水素原子、水酸基または水酸基以外の置換基である。Ｒ２４、Ｒ２５、Ｒ２６、Ｒ２７およびＲ２８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 (9), one of R23 and R29 is a hydroxyl group, and when one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group. R24, R25, R26, R27) And R28 is 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 (8) include, for example, catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof. Specific examples of the polycyclic compound represented by the general formula (9) 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 (E) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof. These compounds (E) may be used individually by 1 type, or may use 2 or more types together.

  The compounding amount of the compound (E) is preferably 0.01% by weight or more and 1% by weight or less, more preferably 0.03% by weight or more and 0.8% by weight in the total semiconductor sealing resin composition. % Or less, particularly preferably 0.05% by weight or more and 0.5% by weight or less. When the lower limit value of the compounding amount of the compound (E) is within the above range, a sufficient viscosity reduction and fluidity improvement effect of the resin composition for semiconductor encapsulation can be obtained. Moreover, there exists little possibility of causing the fall of sclerosis | hardenability of a resin composition for semiconductor sealing, and the fall of physical property of hardened | cured material as the upper limit of the compounding quantity of a compound (E) is in the said range.

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 (E) of reducing the melt viscosity of a resin composition and improving fluidity | liquidity by using together with the above-mentioned compound (E).
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, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, etc. In addition, examples of ureidosilane include γ-ureidopropyltriethoxysilane, hexa And methyldisilazane.
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 coupling agent that can be used in the resin composition for encapsulating a semiconductor of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more in the total resin composition. Especially preferably, it is 0.1 mass% or more. When the lower limit of the blending ratio of the coupling agent is within the above range, the interface strength between the epoxy resin and the inorganic filler is not lowered, and good solder crack resistance in the semiconductor device can be obtained. Moreover, as an upper limit of a 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% or less. When the upper limit value of the mixing ratio of the 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 can be obtained. Moreover, if the blending ratio of the 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 the semiconductor device can be obtained.

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 Hydroxide, zinc borate, zinc molybdate, phosphazene,
You may mix | blend additives, such as flame retardants, such as antimony trioxide, suitably.

  The resin composition for encapsulating a semiconductor of the present invention is obtained by using, for example, a mixer, a phenol resin, an epoxy resin and an inorganic filler including the structure represented by the general formula (1), and other components described above. Mix uniformly at room temperature, and then melt-knead using a kneader such as a heating roll, kneader or extruder, if necessary, and then cool and pulverize as necessary. It can be adjusted to fluidity.

Next, the semiconductor device of the present invention will be described.
As a method of manufacturing 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 using 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.

The following phenol resins 1 and 2 were used for the phenol resin containing the structure represented by the general formula (1).
Phenol resin 1: phenol (special grade reagent manufactured by Kanto Chemical Co., Inc., phenol, melting point 40.9 ° C., molecular weight 94, purity 99.3%) 100 parts by mass, 4,4′-bischloromethylbiphenyl (Wako Pure Chemical Industries, Ltd.) Co., Ltd., bischloromethylbiphenyl, purity 96%, molecular weight 251) 44.69 parts by mass and pure water 0.5 parts by mass were weighed into a separable flask and heated while replacing with nitrogen to start melting. At the same time, stirring was started. After reacting for 1 hour while maintaining the temperature in the system in the range of 75 ° C. to 85 ° C., salicylaldehyde (salicylaldehyde, Tokyo Chemical Industry Co., Ltd., boiling point 196 ° C., molecular weight 122, purity 98%) 8.56 Mass parts were gradually added to the system over 2 hours, the temperature was further raised to 150 ° C., and the system was reacted for 1 hour while maintaining the system temperature in the range of 145 ° C. to 155 ° C. During the above reaction, hydrochloric acid and water generated in the system by the reaction were 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 phenol resin 1 having a structure represented by the following formula (10) (hydroxyl equivalent: 161, softening point: 85 ° C., ICI viscosity: 2 at 150 ° C. .1 dPa · s). A GPC chart is shown in FIG. 2, and an FD-MS chart is shown in FIG.
Phenol resin 2: In the synthesis of phenol resin 1, 14.37 parts by mass of 4,4′-bischloromethyl salicylaldehyde (salicylaldehyde manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 196 ° C., molecular weight 122, purity 98%) Biphenyl (bischloromethylbiphenyl manufactured by Wako Pure Chemical Industries, Ltd., purity 96%, molecular weight 251) was treated as 32.17 parts by mass, and the same operation as in phenol resin-1 was performed, and represented by the following formula (10) A phenol resin 2 containing a structure (hydroxyl equivalent 139, softening point 92 ° C., ICI viscosity 2.7 dPa · s at 150 ° C.) was obtained. A GPC chart is shown in FIG.

Phenol resins 3 and 4 were used as phenol resins other than the phenol resin including the structure represented by the general formula (1).
Phenol resin 3: phenol aralkyl resin having a biphenylene skeleton (Maywa Kasei Co., Ltd., MEH-7851SS. Hydroxyl equivalent 203, softening point 67 ° C., ICI viscosity 0.7 dPa · s at 150 ° C.) GPC chart is shown in FIG. .
Phenol resin 4: Triphenylpropane type phenol resin (Maywa Kasei Co., Ltd., MEH-7500. Hydroxyl equivalent 97, softening point 110 ° C., ICI viscosity 5.8 dPa · s at 150 ° C.) GPC chart is shown in FIG.

The GPC measurement of the phenol resins 1 to 4 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 includes WATERS module W2695, Tosoh Corporation TSK GUARDCOLUMN HHR-L (diameter 6.0 mm, tube length 40 mm, guard column), Tosoh TSK-GEL GMHHR-L (diameter 7. 8 mm, tube length 30 mm, two polystyrene gel columns), and a differential refractive index (RI) detector W2414 manufactured by WATERS, in series, were 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 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-focusing mass spectrometer manufactured by JEOL Ltd. as the detector. Measurement was performed at a detection mass range (m / z) of 50 to 2,000.

Component ratio A between “1 ≦ m ≦ 10” component (A) of the above general formula (1) and component (B) of “m = 0” of the above general formula (1) obtained by measurement by the GPC area method / B was calculated by the following procedure.
(1) GPC measurement of phenol resins 1 to 4 is performed.
(2) The peak position of m = 0 component is confirmed from the chart of the phenol resin 3 (FIG. 4).
(3) The peak position of the n = 0 component is confirmed from the chart of the phenol resin 4 (FIG. 5).
(4) On the GPC chart of the phenol resins 1 and 2, the peak or shoulder that cannot be attributed to the peak attributed to the phenol resin 3 or 4 is confirmed.
(5) By comparing the molecular weight (M / Z) obtained from the FD / MS analysis result of FIG. 2 with the polystyrene equivalent molecular weight of each peak or shoulder of (4), (n, m) is identified, and mass% is obtained from the area ratio of the chart.
The results of the component ratio A / B of the phenol resins 1 to 3 are shown in Table 1. In addition, about component ratio A / B of Example 3, 4, it calculated by proportional calculation from the compounding ratio and the mass% of the phenol resins 1 and 3 of a table | surface, and calculated | required. The component ratio A / B in Examples and Comparative Examples is shown in Table 2 and Table 3 together with the compounding ratio.
In addition, in the GPC measurement of the phenol resins 1 and 2, it was difficult to separate the peaks and analyze the details of components having a molecular weight (m / z) larger than 1108. Therefore, the component ratio is determined from the values of the component (a) “1 ≦ m ≦ 10 and n = 1 to 3” (a) and the component (b) of “m = 0 and n = 1 to 3” that can separate and identify peak areas. a / b was calculated and described as a / b ratio value in Tables 1-3.

The following epoxy resins 1-6 were used for the epoxy resin.
Epoxy resin 1: phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC3000, epoxy equivalent 276, softening point 58 ° C., ICI viscosity 1.11 dPa · s at 150 ° C.)
Epoxy resin 2: biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., YX4000K, epoxy equivalent 185, softening point 107 ° C., ICI viscosity at 150 ° C. 0.1 dPa · s)
Epoxy resin 3: bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., YL6810, epoxy equivalent 172, softening point 45 ° C., softening point 107 ° C., ICI viscosity 0.03 dPa · s at 150 ° C.)
Epoxy resin 4: bisphenol F type epoxy resin (manufactured by Toto Kasei Co., Ltd., YSLV-80XY, epoxy equivalent 190, softening point 80 ° C., ICI viscosity 0.03 dPa · s at 150 ° C.)
Epoxy resin 5: Phenol aralkyl type epoxy resin (Mitsui Chemicals, E-XLC-3L, epoxy equivalent 238, softening point 52 ° C., ICI viscosity 1.20 dPa · s at 150 ° C.)
Epoxy resin 6: Orthocresol novolac type epoxy resin (manufactured by DIC Corporation, N660. Epoxy equivalent 210, softening point 62 ° C., ICI viscosity 2.150 dPa · s at 150 ° C.)
As the inorganic filler, 100 parts by mass of fused spherical silica FB560 (average particle size 30 μm) manufactured by Denki Kagaku Kogyo Co., Ltd., synthetic spherical silica SO-C2 (average particle size 0.5 μm) manufactured by Admatechs Co., Ltd. 6.5. A blend of 7.5 parts by mass of part by mass, synthetic spherical silica SO-C5 (average particle size 30 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 (11)

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

Curing accelerator 3: Curing accelerator represented by the following formula (13)

Curing accelerator 4: Curing accelerator represented by the following formula (14)

As the compound (E), a compound represented by the following formula (15) (manufactured by Tokyo Chemical Industry Co., Ltd., 2,3-naphthalenediol, purity 98%) was used.

As the silane coupling agent, the following silane coupling agents 1 to 3 were used.
Silane coupling agent 1: γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803)
Silane coupling agent 2: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
Silane coupling agent 3: 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.
As the release agent, carnauba wax (Nikko carnauba, melting point 83 ° C.) manufactured by Nikko Fine Co., Ltd. was used.

Example 1
The following components were mixed at room temperature with a mixer, melted and kneaded with a heating roll at 80 ° C. to 100 ° C., then cooled, and then pulverized to obtain a resin composition for semiconductor encapsulation.
Phenolic resin 2 4.21 parts by weight Epoxy resin 1 8.79 parts by weight Inorganic filler 86.00 parts by weight Curing accelerator 1 0.40 parts by weight Silane coupling agent 1 0.10 parts by weight Silane coupling agent 2 05 parts by mass Silane coupling agent 3 0.05 parts by mass Colorant 0.30 parts by mass Release agent 0.10 parts by mass The obtained resin composition for semiconductor encapsulation was evaluated for the following items. The evaluation results are shown in Table 2 and 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 resin composition for semiconductor encapsulation obtained above 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: using a low-pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) under the 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. A stop resin composition was injection molded to produce a 3.2 mm thick flame resistant test piece. About the obtained test piece, the flame resistance test was done according to the specification of UL94 vertical method. The table shows Fmax, ΣF and the fire resistance rank after the determination. The resin composition for semiconductor encapsulation obtained above showed good flame resistance such as Fmax: 7 seconds, ΣF: 24 seconds, and fire resistance rank: V-0.

  Continuous moldability: The resin composition for semiconductor encapsulation obtained above was loaded into a tableting mold having a weight of 7.5 g and a size of φ16 mm using a rotary tableting machine, and tableted at a tableting pressure of 600 Pa. Got. The tablet was loaded into a tablet supply magazine and set inside the molding apparatus. Using a low-pressure transfer automatic molding machine (SY-COMP, manufactured by Cynex Co., Ltd.), under the conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa and a curing time of 60 seconds, 208 pin QFP (Cu lead frame, package outside dimensions: 28mm x 28mm x 3.2mm thickness, pad size: 15.5mm x 15.5mm, chip size 15.0mm x 15.0mm) Molding to obtain a semiconductor device with a thickness of × 0.35 mm was continuously performed up to 300 shots. At this time, the molding state (whether or not unfilled) of the semiconductor device was confirmed every 25 shots, and the number of shots in which unfilling could be confirmed first was listed in the table. As for molding, the resin composition for semiconductor encapsulation obtained above showed a good continuous moldability of 300 shots or more.

Solder resistance test 1: Using a low-pressure transfer molding machine (GP-ELF, manufactured by Daiichi Seiko Co., Ltd.) under conditions of a mold temperature of 180 ° C., an injection pressure of 7.4 MPa, and a curing time of 120 seconds. A lead frame on which a semiconductor element (silicon chip) is mounted is molded by injecting a resin composition for use, and 80 pQFP (Cu lead frame, size: 14 × 20 mm × thickness: 2.00 mm, semiconductor element: 7 A semiconductor device having a size of 7 mm × thickness 0.35 mm, and a semiconductor element and an inner lead portion of a lead frame are bonded with a gold wire having a diameter of 25 μm) was manufactured. Six semiconductor devices heat treated at 175 ° C. for 4 hours as post-cure were treated for 168 hours at 85 ° C. and 60% relative humidity, and then IR reflow treatment (260 ° C., in accordance with JEDEC Level 2 conditions) was performed. The presence or absence of peeling and cracks inside these semiconductor devices was observed with an ultrasonic flaw detector (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., mi-scope 10), and the occurrence of either peeling or cracking was regarded as defective. When the number of defective semiconductor devices is n, n / 6 is displayed. The semiconductor sealing resin composition obtained above showed a good reliability of 0/6.
Solder resistance test 2: A test was performed in the same manner as the solder resistance test 1 except that the post-cure processing conditions in the above-described solder resistance test 1 were set at 85 ° C. and a relative humidity of 85% for 168 hours. The semiconductor device produced using the resin composition for semiconductor encapsulation obtained above showed a good reliability of 0/6.

Examples 2-14, Comparative Examples 1-4
According to the formulations in Tables 2 and 3, a semiconductor sealing 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 Tables 2 and 3.

Examples 1-14 are the resin composition for semiconductor sealing containing the phenol resin containing the structure represented by General formula (1), an epoxy resin, and an inorganic filler, and are represented by General formula (1). It includes those in which the type and blending ratio of the phenol resin containing the structure to be changed, those in which the type of epoxy resin is changed, those in which the type of curing accelerator is changed, and those in which compound (E) is blended are 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, in Comparative Examples 1 to 4 that did not contain the phenol resin containing the structure represented by the general formula (1), the flame resistance, the solder resistance, and the continuous moldability were inferior.

According to the present invention, a resin composition for semiconductor encapsulation can be obtained which has good flame resistance and solder resistance, is excellent in fluidity and continuous moldability, and can be produced at low cost. Suitable for use.

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 semiconductor sealing

Claims (9)

The following general formula (1):

(In General Formula (1), R 1 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 2 is independently a hydrogen atom or carbon number 1 to 10. A is an integer of 0 to 3, b and c are integers of 0 to 4, m is an integer of 0 to 10 and includes a component of m ≦ 1, and n is 0 to 10. (It is an integer.)
A phenolic resin having a structure represented by:
Epoxy resin,
An inorganic filler;
Only including,
Obtained by the area method of the gel permeation chromatograph “1 ≦ m ≦ 10 and n = 1 to 3” of the general formula (1) obtained by the area method of the gel permeation chromatograph and the gel permeation chromatograph. The ratio a / b with the component (b) of “m = 0 and n = 1-3” of the general formula (1) is 0.05 or more and 0.55 or less.
A resin composition for encapsulating a semiconductor.   2. The resin for semiconductor encapsulation according to claim 1, wherein the phenol resin including the structure represented by the general formula (1) includes a phenol resin of 1 ≦ m ≦ 10 and a phenol resin of m = 0. Composition.   “1 ≦ m ≦ 10” component (A) of the general formula (1) obtained by measurement by the gel permeation chromatographic area method and the general formula (1) obtained by measurement by the gel permeation chromatographic area method 3) The resin composition for semiconductor encapsulation according to claim 1, wherein the component ratio A / B with the component (B) of “m = 0” is from 0.05 to 1.5.   The phenol resin including the structure represented by the general formula (1) includes an “n = 0” component obtained by measurement by an area method of a gel permeation chromatograph. The resin composition for semiconductor encapsulation as described in 2.   The content of the “n = 0” component obtained by measurement by the gel permeation chromatographic area method of the phenol resin containing the structure represented by the general formula (1) is 30% by mass with respect to the total curing agent. The resin composition for semiconductor sealing of any one of Claims 1-4 which is the following.   The total amount of the “n = 1” component and the “n = 2” component obtained by measurement by the gel permeation chromatograph area method of the phenol resin containing the structure represented by the general formula (1) is The resin composition for semiconductor sealing of any one of Claims 1-5 which is 30 mass% or more with respect to the phenol resin whole quantity containing the structure represented by Formula (1). The semiconductor sealing resin composition according to any one of claims 1 to 6 , further comprising a curing accelerator. The curing accelerator tetrasubstituted phosphonium compounds, phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and at least one selected from the adduct of a phosphonium compound and a silane compound, according to claim 7 A semiconductor sealing resin composition. A semiconductor device obtained by sealing a semiconductor element with the resin composition for sealing a semiconductor according to any one of claims 1 to 8 .

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