JP5234702B2 - Epoxy resin composition for sealing and semiconductor device - Google Patents

Description

  The present invention relates to an epoxy resin composition for sealing, and a semiconductor device using the same, and more particularly, has excellent room temperature storage stability and excellent fluidity, and particularly a sealing material for a thin semiconductor device. The present invention relates to a sealing epoxy resin composition suitable as a semiconductor device, and a semiconductor device using the same, with less occurrence of molding defects such as wire flow and voids.

  With recent high-density mounting of electronic components on printed wiring boards, semiconductor devices are mainly used in surface mount packages rather than pin insertion packages. Furthermore, surface-mounted ICs, LSIs, and the like are thin packages in order to increase the mounting density and reduce the mounting height, and at the same time, the occupied volume of the element in the package is increasing. In addition, the increase in the chip area and the increase in the number of pins have progressed due to the multi-functionality and large capacity of the elements, and further the increase in the number of pads has led to a reduction in pad pitch and a reduction in pad size, so-called narrow pad pitch. Progressing.

  In addition, in order to cope with further reduction in size and weight, CSP (Quad Flat Package), SOP (Small Outline Package), etc. are also available for CSPs that can easily accommodate higher pins and can be mounted at higher density. (Chip Size Package) and BGA (Ba1l Grid Array). In recent years, these packages have been developed with new structures such as a face-down type, a stacked (stacked) type, a flip chip type, and a wafer level type in order to realize high speed and multiple functions. Of these, the stacked type has a structure in which a plurality of chips are stacked inside the package and connected by wire bonding, and a plurality of chips having different functions can be mounted in one package, so that it can be multi-functional. It will be.

  Furthermore, the resin sealing process when manufacturing CSP and BGA is a so-called batch mold type sealing method in which a plurality of chips are sealed in one cavity instead of the conventional one-chip one-cavity sealing method. It has been developed to improve production efficiency and reduce costs.

  On the other hand, the encapsulant is required to satisfy a high level of reflow resistance, which is a problem when surface-mounting a semiconductor device on a printed circuit board, and temperature cycle characteristics required for reliability after mounting. In order to cope with this problem, the sealing material has been reduced in moisture absorption and expansion by reducing the resin viscosity and increasing the filling of the filler.

  However, conventional sealing materials frequently suffer from molding defects such as wire flow and voids, making it difficult to manufacture semiconductor devices that can cope with thinning, large chip area, multiple pins, narrow pad pitch, etc. . Further, in the case of a stacked type that is to be made into a long wire or a semiconductor device that is compatible with batch molding with a large cavity volume, more severe flow characteristics are required for the sealing material.

  Then, the epoxy resin molding material for semiconductor devices which uses the silane coupling agent or phosphate ester which has a secondary amino group as an essential component with respect to such a subject is proposed (for example, refer patent document 1). . Moreover, the sealing material composition which considered the resin fluidity | liquidity in a low shear area | region is proposed (for example, refer patent document 2, 3). However, satisfactory results have not yet been obtained.

In recent years, in order to increase the production efficiency of semiconductor devices and the like, shortening of the curing time of the sealing material has been demanded, and at the same time, there is little deterioration in curability even if left at room temperature for a long time due to workability requirements. Things are sought. And with respect to such a subject, use of a specific phosphorus compound and use of a specific clathrate type hardening accelerator are proposed (for example, refer to patent documents 4 and 5). However, satisfactory results have not been obtained from the viewpoint of storage stability at normal temperature and from the viewpoint of fluidity described above.
Japanese Patent No. 3511136 JP-A-10-176100 JP 2004-155857 A JP 2004-189781 A JP 2004-307545 A

  As described above, in recent years, semiconductor devices have been made thinner, larger chip areas, more pins, narrower pad pitches, etc., and a new structure such as a stacked type has been put into practical use. A sealing method having a large cavity volume, such as a batch mold, has been developed. And in order to respond | correspond to these, although the improvement by further reduction of a resin viscosity, a change of a filler composition, etc. is tried with respect to a sealing material, sufficient result has not been obtained yet.

  In addition, in order to increase the production efficiency of semiconductor devices and the like, it is required to shorten the curing time of the sealing material, and at the same time, from the requirement of workability, there is a demand for a material with little deterioration in curability even if left at room temperature for a long time. However, I haven't been able to get what I am satisfied with.

  The present invention has been made in response to such problems of the prior art, has excellent fluidity that can sufficiently cope with the thinning of semiconductor devices in recent years, and can be left at room temperature for a long time. To provide a sealing epoxy resin composition excellent in storage stability at room temperature with little deterioration such as curability, and a semiconductor device encapsulated using the same and less likely to cause molding defects such as wire flow and voids. With the goal.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have a specific sealing that uses an inorganic filler having a specific particle size distribution and a curing accelerator included by a specific compound as essential components. It has been found that the above object can be achieved by an epoxy resin composition for use and a semiconductor device using the same, and the present invention has been completed.

（式中、Ｒは水素原子、ハロゲン原子、アルキル基、置換もしくは非置換のフェニル基またはアルコキシ基であり、全てが同一であっても異なっていてもよい。Ｘは（ＣＨ_２）_ｎ基を表し、ｎは０〜２の整数である。）
（Ｉ）前記（Ｄ）無機充填剤のレーザー回折式粒度分布測定装置による粒度分布が、下記（ａ）および（ｂ）の条件を満たす
（ａ）（Ｄ）無機充填剤の総重量に対して、粒径３μｍ未満の成分が１５〜３０重
量％、粒径３μｍ以上１０μｍ以下の成分が２５〜３５重量％、粒径１０μｍを超
える成分が４０〜５０重量％である
（ｂ）粒径１μｍ以上の粒子の重量平均粒径（Ｄ１）と数平均粒径（Ｄ２）との比
（Ｄ１）／（Ｄ２）が５．０〜９．０である
（II）高化式フロー測定装置により測定した温度１７５℃、剪断応力１．２３×１０^５Ｐａにおける最低溶融粘度（η１）が３．５〜９．０Ｐａ・ｓ、温度１７５℃、剪断応力２．４５×１０^３Ｐａにおける最低溶融粘度（η２）が０．３〜０．７Ｐａ・ｓであって、前記各最低溶融粘度（η１）および（η２）が下記式を満足し、かつ、１７５℃におけるゲルタイムが３０〜６０秒である
１．０≦Ｌｏｇ［（η１）／（η２）］≦１．３ That is, the present invention relates to (A) biphenyl type epoxy resin, (B) aralkyl type phenol resin curing in which phenolic hydroxyl group is 0.5 to 1.6 mol per mol of epoxy group of component (A). (C) an inclusion curing accelerator comprising (C) 0.01 to 2% by weight of the total composition, wherein the curing accelerator is clathrated with a tetrakisphenol compound represented by the following general formula (1) Containing 50 to 95% by weight of an inorganic filler based on the whole resin composition ;
An epoxy resin composition for sealing, which satisfies the following conditions (I) and (II):

(In the formula, R is a hydrogen atom, a halogen atom, an alkyl group, a substituted or unsubstituted phenyl group or an alkoxy group, and all may be the same or different. X represents a (CH ₂ ) _n group. And n is an integer of 0 to 2.)
(I) The particle size distribution by the laser diffraction particle size distribution analyzer of the (D) inorganic filler satisfies the following conditions (a) and (b): (a) (D) with respect to the total weight of the inorganic filler The component having a particle size of less than 3 μm is 15 to 30% by weight, the component having a particle size of 3 to 10 μm is 25 to 35% by weight, and the component having a particle size exceeding 10 μm is 40 to 50% by weight. The ratio (D1) / (D2) of the weight average particle diameter (D1) and the number average particle diameter (D2) of the particles of 1 μm or more is 5.0 to 9.0. (II) By the Koka type flow measuring device Minimum melt viscosity (η1) at a measured temperature of 175 ° C. and shear stress of 1.23 × 10 ⁵ Pa is 3.5 to 9.0 Pa · s, minimum melt viscosity at a temperature of 175 ° C. and shear stress of 2.45 × 10 ³ Pa (Η2) is 0.3 to 0.7 Pa · s, and each of the minimum melt viscosities ( 1) and (.eta.2) satisfies the following equation, and gel time at 175 ° C. is 30 to 60 seconds 1.0 ≦ Log [(η1) / (η2)] ≦ 1.3

  Moreover, this invention is a semiconductor device by which a semiconductor element is sealed with the hardened | cured material of the said epoxy resin composition for sealing.

  According to the present invention, an epoxy resin composition for sealing having excellent fluidity and good storage stability at normal temperature, and no wire deformation and voids sealed with such an epoxy resin composition for sealing. A highly reliable semiconductor device can be obtained.

  Hereinafter, the present invention will be described in detail.

  First, each component used for the epoxy resin composition for sealing of this invention is demonstrated.

  As the epoxy resin (A) used in the present invention, as long as it has two or more epoxy groups in one molecule, it is generally used as a sealing material for electronic parts without being limited by molecular structure, molecular weight, etc. Can be widely used. Specifically, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, polyfunctional epoxy having naphthalene skeleton Resin, tri (hydroxyphenyl) alkane epoxy resin, tetra (hydroxyphenyl) alkane epoxy resin, alicyclic epoxy resin, brominated compounds thereof, and the like. These may be used alone or in combination. You may mix and use the above.

（式中、Ｒは水素原子またはアルキル基であり、全てが同一であっても異なっていてもよい。ｎは０以上の整数を表す。） In the present invention, among them, a biphenyl type epoxy resin is preferable, and a biphenyl type epoxy resin represented by the following general formula (1) is more preferable.

(In the formula, R is a hydrogen atom or an alkyl group, and all may be the same or different. N represents an integer of 0 or more.)

  Examples of the alkyl group represented by R in the general formula (2) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. As the epoxy resin of component (A), a biphenyl type epoxy resin in which R in the general formula (2) is a hydrogen atom or a methyl group and n is an integer of 0 to 2 is particularly preferable.

  When using a biphenyl type epoxy resin, it is preferable that the ratio with respect to the whole epoxy resin component is at least 30 weight%. A more desirable ratio is 50% by weight or more, and particularly preferably 70% by weight or more.

  From the viewpoint of ensuring reliability, the total chlorine content in the (A) epoxy resin used in the present invention is preferably 1500 ppm or less, and more preferably 1000 ppm or less. Moreover, it is preferable that the extraction water chlorine in 20 hours in the 50 weight% epoxy resin density | concentration at 120 degreeC is 5 ppm or less. That is, if the total chlorine content in the epoxy resin exceeds 1500 ppm or the extracted water chlorine exceeds 5 ppm, the moisture resistance reliability of the semiconductor device may be reduced.

  The (B) phenolic resin curing agent used in the present invention is not particularly limited as long as it has two or more phenolic hydroxyl groups in the molecule that can react with the epoxy group of the epoxy resin component. The Specifically, aralkyl type phenol resins such as phenol aralkyl resin and naphthol aralkyl resin, novolak type phenol resins such as phenol novolak resin and cresol novolak resin, and modified resins thereof such as epoxidized or butylated novolak type phenol. Resin, dicyclopentadiene modified phenolic resin, paraxylene modified phenolic resin, triphenolalkane type phenolic resin, polyfunctional type phenolic resin and the like. These may be used alone or in combination of two or more. You may mix and use.

（式中、Ｒは水素原子または炭素数１〜１０の置換もしくは非置換の一価の炭化水素基であり、ｎは０以上の整数を表す） In the present invention, among them, an aralkyl type phenol resin is preferable, and a phenol aralkyl resin represented by the following general formula (2) is more preferable.

(In the formula, R is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 or more)

  As the hydrocarbon group represented by R in the general formula (3), an alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, methoxy group, C1-C10 alkoxyl groups, such as an ethoxy group, a propoxy group, and a butoxy group, C6-C10 aryl groups, such as a phenyl group, a tolyl group, and a xylyl group, C6-C10, such as a benzyl group and a phenethyl group And an aralkyl group. As the phenol resin curing agent (B), a phenol aralkyl resin in which R in the general formula (3) is a hydrogen atom or a methyl group and n is an integer of 0 to 10 is particularly preferable.

  When using a phenol aralkyl resin, it is preferable that the ratio with respect to the whole phenol resin hardening | curing agent component is at least 30 weight%. A more desirable ratio is 50% by weight or more, and particularly preferably 70% by weight or more.

  From the viewpoint of ensuring reliability, the phenolic resin curing agent of component (B) is also preferably 10 ppm or less, and preferably 5 ppm or less, both for chlorine ions and sodium ions extracted at a temperature of 120 ° C. More preferred.

  The mixing ratio of the (A) epoxy resin and the (B) phenolic resin curing agent is preferably in the range of 0.5 to 1.6 mol of phenolic hydroxyl group per mol of epoxy group, and 0.6 to 1.4 mol. The range which becomes is more preferable. If it is less than 0.5 mol, the phenolic hydroxyl group is insufficient, the proportion of homopolymerization of the epoxy group increases, and the glass transition temperature may be lowered. On the other hand, when the amount exceeds 1.6 mol, the ratio of phenolic hydroxyl groups increases, the reactivity decreases, and the crosslinking density is low and sufficient strength may not be obtained.

  The inclusion curing accelerator (C) used in the present invention is an inclusion compound in which the curing accelerator serves as a guest and the tetrakisphenol compound represented by the general formula (1) is used as a host. Such an clathrate compound has the effect | action which provides the thermal stability excellent in the composition with the hardening acceleration | stimulation effect | action with respect to (A) epoxy resin. That is, this clathrate compound has good moisture resistance during storage and does not decompose or sublime. Moreover, the composition which mix | blended this is excellent in heat stability, ie, stability at normal temperature (one-component stability), stability at the time of heating from normal temperature to curing temperature, and stability at curing temperature. Therefore, although the obtained composition is extremely stable at room temperature, it is rapidly cured when heated to a certain temperature (curing temperature) equal to or higher than a certain temperature to give a desired cured product.

  In this (C) inclusion curing accelerator, the curing accelerator to be a guest can be used without particular limitation as long as it is conventionally used as a curing accelerator for epoxy resins, Of these, imidazole curing accelerators and amine curing accelerators are preferable, and imidazole curing accelerators are more preferable.

  Specific examples of the imidazole curing accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole. 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2 Ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'- Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 -[2'-ethyl-4-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-di Droxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3 -Benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate and the like.

  Specific examples of the amine curing accelerator include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, dimethylaminopropylamine, diethylaminopropylamine. , Trimethylhexamethylenediamine, pentanediamine, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, alkyl-t-monoamine, 1,4-diazabicyclo (2,2,2) octane (triethylenediamine), N, N , N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylethylenediamine, , N-dimethylcyclohexylamine, dimethylaminoethoxyethoxyethanol, dimethylaminohexanol, and other aliphatic amines; piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N, N ′, N ″ -tris (diamino) Propyl) hexahydro-s-triazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, Alicyclic and heterocyclic amines such as bis (4-aminocyclohexyl) methane, N, N′-dimethylpiperazine, 1,8-diazabicyclo (4,5,0) undecene-7; o-phenylenediamine, m -Phenylenediamine, p- Aromatic amines such as enylenediamine, diaminodiphenylmethane, m-xylenediamine, pyridine, picoline; modified polyamines such as epoxy compound-added polyamine, Michael-added polyamine, Mannich-added polyamine, thiourea-added polyamine, ketone-capped polyamine; dicyandiamide; guanidine Organic acid hydrazide; diaminomaleonitrile; amine imide; boron trifluoride-piperidine complex; boron trifluoride-monoethylamine complex;

  These curing accelerators may be used alone or in combination of two or more. Among them, 2-ethyl-4-methylimidazole, 2-methylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferable as the imidazole curing accelerator, and as the amine curing accelerator, However, ethylenediamine, trimethylenediamine, and tetramethylenediamine are preferable. As the curing accelerator used in the present invention, 2-ethyl-4-methylimidazole, 2-methylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole are particularly preferable.

  Specific examples of the tetrakisphenol compound represented by the general formula (1) of the host include 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis ( 3-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-4- Hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-4-hydroxyphenyl) ethane, 1 1,1,2,2-tetrakis (3,5-dibromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-4-hydroxyphenyl) ethane 1,1,2,2-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-4-hydroxyphenyl) ethane, 1,1,2, 2-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2- Tetrakis (3-bromo-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2 Tetrakis (3-t-butyl-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-bromo-4-hydroxyphenyl) ethane, 1,1,2, 2-tetrakis (3-chloro-5-phenyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis [(4-hydroxy-3-phenyl) phenyl] ethane, 1,1,3,3- Tetrakis (4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ) Propane, 1,1,3,3-tetrakis (3-chloro-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dichloro-4-hydro Xylphenyl) propane, 1,1,3,3-tetrakis (3-bromo-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dibromo-4-hydroxyphenyl) propane, 1, 1,3,3-tetrakis (3-phenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-diphenyl-4-hydroxyphenyl) propane, 1,1,3,3- Tetrakis (3-methoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-t- Butyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 1,1, , 4-Tetrakis (4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dimethyl-4 -Hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-chloro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dichloro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-methoxy-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) butane, 1,1,4, 4-tetrakis (3-bromo-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dibromo-4-hydroxyphenyl) butane, 1,1,4 4- tetrakis (3-t-butyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-di -t- butyl-4-hydroxyphenyl) butane, and the like. These may be used individually by 1 type, and may mix and use 2 or more types. Among the tetrakisphenol compounds, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane, 1, 1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane is preferred.

  (C) The clathrate accelerator is obtained by directly adding a tetrakisphenol compound to a reaction when the guest accelerator is a liquid, and when the accelerator is a solid, By adding a tetrakisphenol compound to a liquid containing a curing accelerator and reacting it, or by directly causing a solid curing reaction between a solid curing accelerator and a powdered tetrakisphenol compound, high selectivity and high Produced in yield. The resulting clathrate accelerator has a structure in which the molecules of the guest curing accelerator enter the crystal lattice vacancies formed by the molecules of the host tetrakisphenol compound. The inclusion ratio of the compound and the curing accelerator included in the compound varies depending on the molecular size, structure, polarity, solubility and the like of the curing accelerator. This clathrate accelerator is a crystalline solid.

  The blending amount of the (C) clathrate accelerator is preferably in the range of 0.01 to 2% by weight based on the entire resin composition in order to obtain the effects of the present invention.

  Examples of the inorganic filler (D) used in the present invention include fused silica pulverized by a ball mill, spherical silica obtained by flame melting, spherical silica produced by a sol-gel method, crystalline silica, alumina, boron nitride , Aluminum nitride, silicon nitride, magnesia, magnesium silicate and the like. These inorganic fillers can be used alone or in combination of two or more. When the semiconductor element to be sealed is an element that generates a large amount of heat, it is preferable to use alumina, boron nitride, aluminum nitride, silicon nitride, or the like that has as high a thermal conductivity as possible and a low thermal expansion coefficient. These may be blended with fused silica or the like.

  The shape of the inorganic filler is not particularly limited, and flaky, dendritic, spherical and other inorganic fillers can be used alone or in combination. A spherical shape is preferred for reducing the viscosity and increasing the filling.

In the present invention, the (D) inorganic filler needs to satisfy the following conditions (a) and (b) in the particle size distribution measured by a laser diffraction particle size distribution measuring device.
(A) (D) 15 to 30% by weight of a component having a particle size of less than 3 μm, 25 to 35% by weight of a component having a particle size of 3 to 10 μm, and a component having a particle size exceeding 10 μm based on the total weight of the inorganic filler (B), the ratio (D1) / (D2) of the weight average particle diameter (D1) and the number average particle diameter (D2) of the particles having a particle diameter of 1 μm or more is 5.0 to 9 .0

  If the particle size distribution does not satisfy the above conditions, desired viscosity characteristics and flow characteristics cannot be achieved.

In the present invention, it is preferable that the particle size distribution measured by a laser diffraction type particle size distribution analyzer further satisfies the following conditions (c) and (d), and achieves desired viscosity characteristics and flow characteristics. It becomes easier.
(C) having at least one peak in each of a particle size range of less than 3 μm, a particle size range of 3 μm or more and 10 μm or less, and a particle size range of more than 10 μm in a particle size distribution diagram showing frequency values at each particle size (d) The ratio (P1) / (P2) of the maximum frequency value (P1) in the particle size range of less than 3 μm and the maximum frequency value (P2) in the particle size range of more than 10 μm in the particle size distribution diagram showing the frequency value in the particle size is 0 .3 to 1.0

  (D) The amount of the inorganic filler is preferably 50 to 95% by weight of the total resin composition, more preferably 75 to 95% by weight, and even more preferably 85 to 92% by weight. preferable. If it is less than 50% by weight, the expansion coefficient cannot be sufficiently lowered, the water absorption rate increases, and the package may crack at the temperature during solder reflow. Moreover, when it exceeds 95 weight%, there exists a possibility that a viscosity may become high and a filling property may fall.

  In the present invention, from the viewpoint of filling properties, it is preferable to further blend (E) a silane coupling agent having an amino group, and it is particularly preferable to use a silane coupling agent having a secondary amino group.

  Examples of the silane coupling agent having a secondary amino group include γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane, and γ-anilinopropylmethyldiethoxy. Silane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ- Anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropyltrimethoxysilane, N- (p-methoxy) Phenyl) -γ-aminopropylto Liethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldimethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylmethyldiethoxysilane, N- (p-methoxyphenyl) -γ- Aminopropylethyldiethoxysilane, N- (p-methoxyphenyl) -γ-aminopropylethyldimethoxysilane, γ- (N-methyl) aminopropyltrimethoxysilane, γ- (N-ethyl) aminopropyltrimethoxysilane, γ- (N-butyl) aminopropyltrimethoxysilane, γ- (N-benzyl) aminopropyltrimethoxysilane, γ- (N-methyl) aminopropyltriethoxysilane, γ- (N-ethyl) aminopropyltriethoxy Silane, γ- (N-butyl) aminopropyltriethoxysilane, γ (N-benzyl) aminopropyltriethoxysilane, γ- (N-methyl) aminopropylmethyldimethoxysilane, γ- (N-ethyl) aminopropylmethyldimethoxysilane, γ- (N-butyl) aminopropylmethyldimethoxysilane, γ- (N-benzyl) aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyltrimethoxysilane, N-β- (N -Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and the like.

  Examples of the silane coupling agent having an amino group other than the secondary amino group include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropylmethyl. Diethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxysilane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ -(N-methyl) anilinopropyltrimethoxysilane, γ- (N-ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) ) Aminopropyltriethoxysilane, γ- (N, N-dibutyl) aminopropyl Riethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- ( N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropylmethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilino Examples include propylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, and N- (dimethoxymethylsilylisopropyl) ethylenediamine. These silane coupling agents may be used alone or in combination of two or more.

  In addition, silane coupling such as epoxy silane, mercapto silane, alkyl silane, phenyl silane, ureido silane, vinyl silane and the like generally used for this kind of sealing epoxy resin composition within a range not impairing the effect of the present invention. A coupling agent such as an agent, a titanium coupling agent, an aluminum chelate, or an aluminum / zirconium-based compound can be used in combination with the silane coupling agent having an amino group.

  (E) As for the compounding quantity of the silane coupling agent which has an amino group, the range used as 0.03-5.0 weight% of the whole resin composition is preferable, and the range used as 0.10-2.5 weight% is more. preferable. If it is less than 0.03% by weight, the adhesiveness to the printed wiring board tends to decrease. If it exceeds 5.0% by weight, the volatile matter increases, and voids and other molding defects are likely to occur. At the same time, the formability of the package tends to decrease.

  In the sealing epoxy resin composition of the present invention, in addition to the above components, powders such as silicone rubber and silicone gel, which are generally blended in this kind of composition within a range not inhibiting the effects of the present invention, Stress-reducing agents such as silicone-modified epoxy resins and phenolic resins, thermoplastic resins made of methyl methacrylate-butadiene-styrene, flame retardants and flame retardants such as brominated epoxy resins and antimony oxide, and colorants such as carbon black , Nonionic surfactants, fluorosurfactants, wetting improvers such as silicone oil, antifoaming agents, and the like can be optionally added. For the purpose of reducing the viscosity, conventionally known diluents such as n-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, t-butylphenyl glycidyl ether, dicyclopentadiene diepoxide, phenol, cresol, and t-butylphenol are used. Can be blended.

  In preparing the sealing epoxy resin composition of the present invention as a molding material, (A) an epoxy resin, (B) a phenol resin curing agent, (C) an inclusion curing accelerator, (D) inorganic After the filler and various components blended as necessary are uniformly mixed using a high-speed mixer or the like, it is melted at a temperature of, for example, 50 to 110 ° C. with a two-roll, continuous kneader or the like. After kneading and forming into a thin sheet, it may be cooled and ground to an appropriate size. In addition, when blending (E) an amino group-containing silane coupling agent and other coupling agents that can be used in combination with this, (D) the inorganic filler is previously treated with these coupling agents, Then, you may make it mix with another component.

The epoxy resin composition for sealing of the present invention prevents the occurrence of molding defects such as wire flow and voids in a semiconductor device, and also from the viewpoint of preventing the occurrence of defects during reflow, an elevated flow measurement device The minimum melt viscosity (η1) at a temperature of 175 ° C. and a shear stress of 1.23 × 10 ⁵ Pa measured at 175 ° C. is 3.5 to 9.0 Pa · s, the temperature is 175 ° C., and the minimum melt viscosity is 2.45 × 10 ³ Pa. The viscosity (η2) is 0.3 to 0.7 Pa · s, the minimum melt viscosities (η1) and (η2) satisfy the following formula, and the curing time at 175 ° C. is 30 to 60 seconds. It is preferable.
1.0 ≦ Log [(η1) / (η2)] ≦ 1.3

  The sealing epoxy resin composition of the present invention can also be used as a general molding material, but it is a sealing material for semiconductor devices, in particular, thin, multi-pin, long wire, narrow pad pitch, or organic substrate or organic It is suitably used as a sealing material for a semiconductor device in which a semiconductor chip is disposed on a mounting substrate such as a film. In this case, the molding can be performed by a transfer molding method or the like, and the molding conditions may be a temperature of 165 to 185 ° C. and a time of 1 to 5 minutes.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all. In the following description, “%” means “% by weight”.

[Manufacture of inorganic filler preparations]
Various kinds of spherical fused silica powders having different particle size distributions are appropriately mixed, and particles having a particle size of less than 3 μm, particles having a particle size of 3 μm or more and 10 μm or less, and particles having a particle size of more than 10 μm are shown in Table 1. Inorganic filler preparations (I) to (VI) were obtained. Among these inorganic fillers (I) to (VI), the inorganic filler preparation (VI) has three peaks (maximum frequency at a particle size of 1.73 μm) in a particle size distribution diagram showing frequency values at each particle size. Value (P1) 3.43 wt%, particle size 7.70 μm with maximum frequency value 3.91 wt%, particle size 26.1 μm with maximum frequency value (P2) 5.60 wt%). The ratio P1 / P2 between the maximum frequency value (P1) at 73 μm and the maximum frequency value (P2) at a particle size of 26.1 μm was 0.6. In addition, the other inorganic filler preparations (I) to (V) had one peak in the entire particle size range.

  Measure the particle size distribution of the inorganic filler preparations (I) to (VI) (for particles having a particle size of 1 μm or more) using a laser diffraction particle size distribution analyzer (SALD-2200 manufactured by Shimadzu Corporation). Then, when the weight average particle diameter (D1), the number average particle diameter (D2) and the ratio (D1 / D2) thereof were obtained for particles having a particle diameter of 1 μm or more, the results shown in Table 1 were obtained. It was.

Examples 1-7 , Reference Examples , Comparative Examples 1-5
Using the inorganic filler preparations (I) to (VI), the components shown in Tables 2 and 3 were mixed (dry blended) at room temperature, then heated and kneaded at 80 to 110 ° C., and then cooled. Then, an epoxy resin composition for sealing was produced by pulverization.

The materials other than the inorganic filler preparations (I) to (VI) shown in Tables 2 and 3 are as follows.
o-Cresol novolac epoxy resin:
Product name ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.
(Epoxy equivalent 195, softening point 65 ° C.)
Biphenyl type epoxy resin:
Product name YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.
(Epoxy equivalent 196, melting point 106 ° C.)
Brominated epoxy resin:
Product name YDB-400 manufactured by Tohto Kasei Co., Ltd.
(Epoxy equivalent 375, softening point 80 ° C., bromine content 48% by weight)
Phenol novolac resin: Product name H-1 manufactured by Meiwa Kasei Co., Ltd.
(Hydroxyl equivalent 106, softening point 80 ° C.)
Phenol aralkyl resin: product name XL-225 manufactured by Mitsui Chemicals, Inc.
(Hydroxyl equivalent 175, softening point 70 ° C.)
Inclusion hardening accelerator (I): 2-ethyl-4-methylimidazole with a content of 30% clathrated with 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (TEP) Product name TEP-2E4MZ
Inclusion curing accelerator (II): 10% ethylenediamine clathrated by TEP, manufactured by Nippon Soda Co., Ltd. Product name TEP-ED
Inclusion hardening accelerator (III): 2-phenyl-4-methyl-5-hydroxymethylimidazole with 42% content included by TEP Nippon Soda Co., Ltd. Product name TEP-2P4MHZ
Curing accelerator: 2-ethyl-4-methylimidazole Silane coupling agent (I): γ-glycidoxypropyltrimethoxysilane Silane coupling agent (II): γ-anilinopropyltrimethoxysilane Colorant: Carbon black Product name MA-600 manufactured by Mitsubishi Chemical Corporation
Mold release agent: Carnauba wax Product name: Purified carnauba wax No. 1
Flame retardant aid: Antimony trioxide manufactured by Toko Sangyo Co., Ltd. Trade name HTT-200

  About the epoxy resin composition for sealing obtained by each said Example and each comparative example, various characteristics were evaluated by the method shown below.

[Spiral flow]
Transfer molding was performed under conditions of a temperature of 175 ° C. and a pressure of 9.8 MPa, and the spiral flow was measured.
[Geltime]
A predetermined amount of the epoxy resin composition for sealing was spread in a circular shape having a diameter of 4 to 5 cm on a hot plate kept at 175 ° C. and kneaded at a constant speed, and the time until the sample became a gel was measured.
[Minimum melt viscosity]
Minimum melt viscosity at a shear stress of 1.23 × 10 ⁵ Pa at a temperature of 175 ° C. using a Koka-type flow measuring device (CFT-500C manufactured by Shimadzu Corporation) under a pressure of 10 kg and using a nozzle with a diameter of 1 mm. The minimum melt viscosity (η2) at (η1) and the shear stress of 2.45 × 10 ³ Pa was measured, and the logarithmic ratio Log (η1 / η2) was calculated.
[Storage stability]
For the sealing epoxy resin composition stored at 25 ° C. for 168 hours, the spiral flow was measured in the same manner as described above, and the residual ratio (%) relative to the initial spiral flow was calculated.
[Deformation of wire and generation of voids]
Using a double QFP matrix frame (10 samples), transfer molding was performed using a multi-plunger device under conditions of a temperature of 175 ° C. and a pressure of 6.9 MPa, and voids generated inside and outside of the obtained QFP package The number (total number of voids generated in each sample) was counted. Internal voids were counted using an ultrasonic flaw detector, while external voids were counted by visual observation. Moreover, the presence or absence of the deformation | transformation of the wire in the vent part and corner part of a QFP package was investigated using the soft X-ray apparatus, and the deformation | transformation incidence rate was computed. The generation of voids was measured for the initial epoxy resin composition for sealing and the epoxy resin composition for sealing after storage at 25 ° C. for 168 hours.
[Reflow resistance]
A silicon chip (6 mm × 6 mm) with zigzag wiring made of aluminum is bonded to a lead frame made of 42 alloy, and transfer molding is performed using a sealing epoxy resin composition at a temperature of 175 ° C. and a pressure of 6.9 MPa. After sealing, the aluminum electrode on the chip surface and the lead frame are wire-bonded with a gold wire having a diameter of 30 μm, and further post-cured at a temperature of 180 ° C. for 10 hours to obtain a semiconductor device (20 mm × 14 mm × 2. 0 mm). The semiconductor device was subjected to moisture absorption treatment at 85 ° C. and 85% RH for 72 hours, and then heated in an infrared reflow furnace at 240 ° C. for 90 seconds to investigate the occurrence of cracks in the semiconductor package, and the rate of occurrence was calculated. (Sample number 20).
[Moisture resistance reliability]
Using an epoxy resin composition for sealing, transfer molding was performed under the conditions of 175 ° C. and 6.9 MPa, and then post-curing was performed at a temperature of 180 ° C. for 10 hours to obtain a surface mount type QFP-1H (tab 6.7 mm × 6.7 mm) package, and the package was subjected to moisture absorption treatment at 85 ° C. and 85% RH for 72 hours and reflow treatment at 240 ° C. for 90 seconds, and then at 65 ° C. and 95% RH for 500 hours. A moisture resistance test (PCT) was performed to examine the corrosion rate of the aluminum electrode on the chip (number of samples: 20).
[High temperature storage reliability]
After placing the semiconductor package produced in the same manner as the evaluation test of the moisture resistance reliability in a constant temperature bath at 180 ° C. for 1000 hours, the presence or absence of a defective joint between the gold wire and the aluminum wiring was examined, and the rate of occurrence was determined. Determined (20 samples).

These results are shown in Table 2 and Table 3 together with the composition.

  As is apparent from Tables 2 and 3, the sealing epoxy resin compositions of the examples have significantly improved storage stability at room temperature compared to the comparative examples, and also have reflow resistance and moisture resistance reliability. Also, it had good characteristics in terms of high temperature storage.

Claims (7)

(A) Biphenyl type epoxy resin, (B) Aralkyl type phenol resin curing agent in an amount such that phenolic hydroxyl group is 0.5 to 1.6 mol per mol of epoxy group of component (A) , (C) Composition 0.01 to 2% by weight of the whole product, a clathrate accelerator obtained by clathrating a curing accelerator with a tetrakisphenol compound represented by the following general formula (1), and (D) 50 of the total resin composition Containing ~ 95 wt% inorganic filler,
An epoxy resin composition for sealing, which satisfies the following conditions (I) and (II):

(In the formula, R is a hydrogen atom, a halogen atom, an alkyl group, a substituted or unsubstituted phenyl group or an alkoxy group, and all may be the same or different. X represents a (CH ₂ ) _n group. And n is an integer of 0 to 2.)
(I) The particle size distribution by the laser diffraction particle size distribution analyzer of the (D) inorganic filler satisfies the following conditions (a) and (b): (a) (D) with respect to the total weight of the inorganic filler The component having a particle size of less than 3 μm is 15 to 30% by weight, the component having a particle size of 3 to 10 μm is 25 to 35% by weight, and the component having a particle size exceeding 10 μm is 40 to 50% by weight. The ratio (D1) / (D2) of the weight average particle diameter (D1) and the number average particle diameter (D2) of the particles of 1 μm or more is 5.0 to 9.0. (II) By the Koka type flow measuring device Minimum melt viscosity (η1) at a measured temperature of 175 ° C. and shear stress of 1.23 × 10 ⁵ Pa is 3.5 to 9.0 Pa · s, minimum melt viscosity at a temperature of 175 ° C. and shear stress of 2.45 × 10 ³ Pa (Η2) is 0.3 to 0.7 Pa · s, and each of the minimum melt viscosities ( 1) and (.eta.2) satisfies the following equation, and gel time at 175 ° C. is 30 to 60 seconds 1.0 ≦ Log [(η1) / (η2)] ≦ 1.3 2. The epoxy resin composition for sealing according to claim 1, wherein the particle size distribution of the (D) inorganic filler measured by a laser diffraction particle size distribution analyzer further satisfies the following conditions (c) and (d): .
(C) The particle size distribution diagram showing the frequency value for each particle size has at least one peak in each of a particle size range of less than 3 μm, a particle size range of 3 μm to 10 μm, and a particle size range of more than 10 μm. d) Ratio of the maximum frequency value (P1) in the particle size range of less than 3 μm to the maximum frequency value (P2) in the particle size range of more than 10 μm in the particle size distribution diagram showing the frequency value at each particle size (P
1) / (P2) is 0.3 to 1.0   The epoxy resin composition for sealing according to claim 1 or 2, wherein the curing accelerator in the (C) inclusion curing accelerator contains at least one of an imidazole curing accelerator and an amine curing accelerator. object.   The curing accelerator in the inclusion curing accelerator (C) is at least one selected from the group consisting of 2-ethyl-4-methylimidazole, 2-methylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. The epoxy resin composition for sealing according to claim 1 or 2, which is a seed.   The tetrakisphenol compound in the (C) inclusion curing accelerator is 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxy). 5) At least one member selected from the group consisting of (phenyl) ethane and 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane. The epoxy resin composition for sealing according to 1. (E) The epoxy resin composition for sealing according to any one of claims 1 to 5 , further comprising a silane coupling agent having an amino group. A semiconductor device, wherein a semiconductor element is sealed with a cured product of the epoxy resin composition for sealing according to any one of claims 1 to 6 .