JP2009227742A - Epoxy resin composition, epoxy resin composition for sealing semiconductor, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition giving a cured material reduced in an elastic modulus and increased in a glass transition temperature, and to provide an epoxy resin composition using the epoxy resin composition for sealing a semiconductor, and a semiconductor device exhibiting excellent solder resistance in moistening and reduced in a warp. <P>SOLUTION: The epoxy resin composition comprises an epoxy resin (A), a curing agent (B), and a monofunctional phenol compound (C) having one substituent represented by general formula (1). In the formula, X represents a 2-12C aromatic group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

  Many attempts have been made to lower the elastic modulus of the epoxy resin composition for semiconductor encapsulation for the purpose of improving the reliability of the semiconductor package. An epoxy resin composition for semiconductor encapsulation is a metal frame or a base material in a semiconductor package when an extreme temperature change such as solder reflow is given to the sealed semiconductor element during the manufacturing process of the semiconductor package. It is known that peeling occurs due to a difference in linear expansion coefficient between a base material such as a metal and a cured product of a resin composition at an interface with another resin substrate, thereby causing a semiconductor defect. As a countermeasure, by lowering the elastic modulus of the cured product of the epoxy resin composition for semiconductor encapsulation, the method of relaxing the stress generated in the interface and the molded product, and the ratio of the filler are improved. A technique for reducing a difference in linear expansion coefficient from the above-described base material is known.

  As a technique for reducing the elastic modulus of the cured product of the epoxy resin composition for semiconductor encapsulation, it is common to use a low stress agent in the epoxy resin composition for semiconductor encapsulation. As a low-stress agent, a technique of adding a high molecular weight silane component, a thermoplastic oligomer, or the like (see, for example, Patent Documents 1 and 2) is known, but a cured product of an epoxy resin composition for semiconductor encapsulation is known. Problems such as a decrease in the glass transition temperature, the stress-reducing agent itself oozes out of the cured product and causes mold contamination, and a moldability problem due to an increase in the melt viscosity of the resin composition in the molding operation. there were.

  Moreover, the technique of obtaining the hardened | cured material of low elasticity modulus by making low the sclerosis | hardenability degree of the epoxy resin composition for semiconductor sealing by utilizing a specific hardening accelerator is also known. As such a curing accelerator, an adduct of triarylphosphine and quinones is typical, but a cured product obtained by using these curing accelerators has many unreacted functional groups in the epoxy resin. In addition, the water absorption rate of the cured product may be adversely affected. Moreover, it is very difficult to achieve both the control of the elastic modulus of the cured product and the control of the curability, which is the original role of the curing accelerator, and the desired elastic modulus may not be obtained.

  Furthermore, a technique for forming a sea-island structure having low-elasticity islands by phase separation in the system after curing using a curable resin component having liquid crystallinity (see, for example, Patent Document 3) is also disclosed. However, there is a problem that the degree of freedom in selecting the resin and the mixing ratio of the composition components is low, and it is not always possible to obtain a desired elastic modulus, and it is necessary to use an expensive raw material in terms of cost.

In recent years, many semiconductor structures having a ball grid array (hereinafter sometimes referred to as BGA) structure have been designed. In the BGA structure, a semiconductor element is mounted on a substrate having ball-shaped electrodes on the lower surface, the substrate and the semiconductor element are connected with a metal wire, and the semiconductor element and the wire bonded portion are collectively sealed with a sealing resin. To do. In such a structure, the substrate may be deformed as “warping” due to the difference in the coefficient of linear expansion between the substrate material and the sealing resin or the curing shrinkage of the sealing resin. It is a problem.
As countermeasures for warping, reduction of linear expansion coefficient, reduction of elastic modulus, improvement of glass transition temperature, etc. in a cured product of sealing resin are generally used.

  As a method for preventing the warpage, a technique for improving the glass transition temperature and improving heat resistance by introducing a maleimide compound into a sealing resin is well known, and sealing a reactive maleimide group. There are a technique for trimerization in a resin for use (for example, see Patent Document 4) and a technique for reacting a maleimide compound and an allyl group present in a sealing resin (for example, see Patent Document 5). In these techniques, a double bond possessed by a maleimide group and one other functional group, a total of bifunctional maleimide compounds, are used, but the above functional group is excellent in heat resistance as a cured product. Since the cured product has a high elastic modulus due to the increase in cross-linking due to, the effect of improving the warp was not observed.

  A technique for introducing a monofunctional epoxy compound having an imide skeleton into an epoxy resin composition has been reported as a technique for simultaneously achieving a low elasticity and an improved glass transition temperature in a cured resin for sealing (for example, patents) Reference 6). By making these monofunctional groups, the crosslink density in the cured product is reduced, and at the same time, the polar bond of the polymer network is increased by the imide skeleton, and the perturbation of the network molecule is suppressed, thereby improving the glass transition temperature. Can be achieved.

  However, it is known that the imide compound undergoes a hydrolysis reaction under specific conditions (see, for example, Patent Document 7). For example, the hydrolysis reaction is performed under acidic conditions or basic conditions. It is promoted by heating with. On the other hand, a general epoxy resin curing accelerator represented by an adduct of triarylphosphine and quinones has basicity in a sealing resin system, and these curing accelerator and the imide compound are When coexisting in a hygroscopic resin system, the hydrolysis reaction of the imide compound is promoted.

  The amic acid produced by the hydrolysis reaction of the imide compound has a very high acidity, and when a large amount of the amic acid is mixed in the epoxy resin composition, the curing accelerating action of the curing accelerator is significantly inhibited. Such deterioration of curability is not preferable from the viewpoint of fast curability for the purpose of improving production efficiency.

As described above, no technique has been found that can simultaneously improve the glass transition temperature of the epoxy resin composition and reduce the elastic modulus while maintaining fast curability even under moisture absorption conditions.
JP 2001-288336 A (page 1-3) JP 2001-207021 (page 1-3) JP-A-9-194687 (page 1-2) Japanese Patent Laid-Open No. 10-7770 (2 pages) JP-A-3-237126 (page 1-3) Special table 2006-225544 (page 1-2) Special table 2006-512445 (pages 21-22)

  The present invention relates to an epoxy resin composition capable of reducing the elastic modulus as a cured product and improving the glass transition temperature, an epoxy resin composition for semiconductor encapsulation using the same, and solder resistance at the time of moisture absorption Provided is a semiconductor device having excellent properties and reduced warpage.

That is, the present invention
1. An epoxy resin composition comprising an epoxy resin (A), a curing agent (B), and a monofunctional phenol compound (C) having one substituent represented by the following general formula (1);

［式中、Ｘは、炭素数２以上１２以下の芳香族基を示す］

[Wherein X represents an aromatic group having 2 to 12 carbon atoms]

2. The epoxy resin composition according to claim 1, wherein the aromatic group as X in the formula (1) is a phenyl group or a naphthalenyl group,
3. An epoxy resin composition for semiconductor encapsulation, comprising the epoxy resin composition according to item 1 or 2, and an inorganic filler (D),
4). The said epoxy resin composition is 50-95 wt% of inorganic fillers (D) with respect to the total amount of an epoxy resin (A), a hardening | curing agent (B), a monofunctional phenol compound (C), and an inorganic filler (D). The epoxy resin composition for semiconductor encapsulation according to claim 3, which is contained at a ratio of
5. The epoxy resin composition for semiconductor encapsulation according to claim 4, wherein the epoxy resin composition for semiconductor encapsulation is a ball grid array sealing material,
6). A semiconductor device in which an electronic component is sealed with a cured product of the epoxy resin composition for semiconductor sealing according to item 4 or 5,
7). The semiconductor device according to claim 6, wherein the semiconductor device has a ball grid array structure,
It is.

  The epoxy resin composition of the present invention can reduce the elastic modulus of a cured product and improve the glass transition temperature of the cured product. The semiconductor device obtained using the epoxy resin composition for semiconductor encapsulation containing the epoxy resin composition of the present invention has excellent reliability such as solder resistance at the time of moisture absorption. In particular, in a semiconductor device in which warpage is a problem, such as a BGA type semiconductor device, warpage of the semiconductor element mounting substrate after curing of the epoxy resin composition for semiconductor encapsulation of the present invention is reduced.

  Hereinafter, preferred embodiments of the epoxy resin composition, the epoxy resin composition for semiconductor encapsulation, and the semiconductor device of the present invention will be described.

  The epoxy resin composition of the present invention comprises an epoxy resin (A), a curing agent (B), and a monofunctional phenol compound (C) having one group represented by the general formula (1). Thus, the epoxy resin composition can reduce the elastic modulus of the cured product, and at the same time, can improve the glass transition temperature of the cured product.

  Furthermore, the present invention is an epoxy resin composition for semiconductor encapsulation containing the epoxy resin composition and an inorganic filler, and the present invention provides an electronic component using a cured product of the epoxy resin composition for semiconductor encapsulation. It is a semiconductor device obtained by sealing. The semiconductor device thus obtained has excellent solder resistance when absorbing moisture. In addition, the semiconductor device is less warped due to the sealing resin, and is particularly effective when the semiconductor device to be sealed has a BGA structure.

  The epoxy resin (A) used in the present invention is a monomer, oligomer, or polymer in general having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak Type epoxy resin, cresol novolac type epoxy resin, hydroquinone type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type Epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified phenol type epoxy resin, phenol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton, naphthol type epoxy resin, naphth Copolymers of phenols and phenols, naphthalene epoxy resins, bisnaphthol epoxy resins, naphthol aralkyl epoxy resins having a phenylene and / or biphenylene skeleton, sulfur atom-containing epoxy resins, salicylaldehyde epoxy Examples thereof include resins, and these may be used alone or in combination. Among these, a phenol aralkyl type epoxy resin having a phenylene and / or biphenylene skeleton and a naphthol having a phenylene and / or a biphenylene skeleton are used to maximize the characteristics obtained from the monofunctional phenol compound (C) used in the present invention. It is preferable to use an aralkyl type epoxy resin or the like.

  The curing agent (B) used in the present invention functions as a curing agent for the epoxy resin (A), and is a monomer, oligomer or polymer in general having two or more phenolic hydroxyl groups in one molecule. Although the structure is not particularly limited, for example, phenol novolak resin, cresol novolak resin, triphenolmethane type phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, aralkyl type phenol resin, phenylene and / or biphenylene skeleton Phenol aralkyl resin having phenylene, and / or naphthol aralkyl resin having biphenylene skeleton, salicylaldehyde type phenol resin, copolymer resin of benzaldehyde type phenol resin and aralkyl type phenol resin, bisphenol Nord compounds include dihydroxynaphthalene compounds and the like, these are no problem be used singly or in admixture. Among these, the phenylene and / or biphenylene skeleton is used to maximize the characteristics obtained by using the monofunctional phenol compound (C) having one group represented by the general formula (1) used in the present invention. It is preferable to use a phenol aralkyl resin having a phenylene, and / or a naphthol aralkyl resin having a biphenylene skeleton.

  The epoxy resin (A) used in the present invention has two or more epoxy groups as a reactive group in one molecule, and the curing agent (B) has one molecule of a phenolic hydroxyl group as a reactive group. Although it has what has 2 or more in it, Preferably, it is preferable that each compound contains what has 3 or more reactive groups. As a combination of an epoxy resin (A) and a hardening | curing agent (B), any one may contain what has a 3 or more reactive group. As such a specific example, it is preferable that at least one of the epoxy resin (A) and the curing agent (B) contains 30 wt% or more of those having 3 or more reactive groups. (A) includes a mixture of 70 wt% of a compound having two epoxy groups in one molecule and 30 wt% of a compound having three or more epoxy groups in one molecule. Furthermore, it is more preferable that at least one of the epoxy resin (A) and the curing agent (B) contains 40 wt% or more of those having 3 or more reactive groups. A plurality of kinds of these compounds containing three or more reactive groups may be mixed. That is, in the case of the epoxy resin (A), it may be a single compound having three epoxy groups or a mixture of compounds having three, four, five or more epoxy groups.

  In the present invention, the epoxy resin (A) or the curing agent (B) can be used without having 3 or more reactive groups, but those having 3 or more reactive groups are within the above range. If it is outside, the crosslink density of the cured resin may be low, and the inclusion of the monofunctional phenol compound (C) may further reduce the crosslink density, resulting in insufficient curing.

The monofunctional phenol compound (C) having one group represented by the general formula (1) used in the present invention is a phenol compound having substantially no group other than one phenolic hydroxyl group as a reactive group. That is.
The reactive group in the monofunctional phenolic compound (C) is a chemical reaction with the epoxy resin (A) and the curing agent (B) in the curing reaction of the epoxy resin composition of the present invention and the temperature history of the production process. It is a substituent that can be chemically reacted with each other when the monofunctional phenol compound (C) has the substituent. Specifically, a substituent containing an oxirane ring such as an epoxy group and an oxetane group; reacts with an epoxy group or a phenolic hydroxyl group such as a group having an active hydrogen atom such as a phenolic hydroxyl group, a thiol group, a carboxyl group, and an amino group. Group; groups capable of reacting with each other by substituents such as vinyl group, allyl group and maleimide group. These substituents are not suitable for the purpose of the present invention because the reaction cannot improve the crosslink density of the epoxy resin and reduce the elastic modulus.

  The monofunctional phenol compound (C) having one group represented by the general formula (1) used in the present invention has no reactive group other than one phenolic hydroxyl group, thereby efficiently The crosslink density of the cured product can be reduced and the elastic modulus can be reduced. Furthermore, in the structure represented by the general formula (1), the two carbonyl groups bonded to the nitrogen atom form a hydrogen bond with the main chain skeleton of the epoxy resin to create a pseudo cross-linked state. Thereby, the glass transition temperature of hardened | cured material can be improved by suppressing the perturbation property of the network molecule | numerator of hardened | cured material. At this time, when the main chain skeleton of the epoxy resin contains a phenylene group, a biphenylene group or a naphthalenyl group, the hydrogen bond becomes strong and the monofunctional phenol having one group represented by the general formula (1) in the present invention. Since the effect of compound (C) is expressed to the maximum, it is preferable.

［式中、Ｘは、炭素数２以上１２以下の芳香族基を示す。］ The structure represented by the general formula (1) will be described.

[Wherein, X represents an aromatic group having 2 to 12 carbon atoms. ]

In the structure represented by the general formula (1), X represents an aromatic group having 2 to 12 carbon atoms. This aromatic group may be either a heteroaromatic group or an aromatic hydrocarbon group, specifically, a heteroaromatic group such as a pyrrolyl group, a furanyl group, a pyridinyl group, a pyranyl group, an imidazolyl group, a thiophenyl group, Aromatic hydrocarbon groups such as phenyl group and naphthalenyl group can be mentioned.
Among these aromatic groups, when a phenyl group or a naphthalenyl group is used, the monofunctional phenol compound (C) having one group represented by the general formula (1) used in the present invention has an increased hydrogen bond. And since the effect which improves the glass transition temperature in the hardened | cured material of an epoxy resin composition becomes large, it is preferable.

  Further, the fact that the aromatic group X has a substituent impairs the characteristics expressed by using the monofunctional phenol compound (C) having one group represented by the general formula (1) used in the present invention. However, as before, this substituent must be non-reactive. Examples of the substituent include an alkyl group and a halogen group. Examples of the alkyl group include straight chain alkyl groups such as methyl group, ethyl group, propylene group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group, and branched groups. And a cyclic alkyl group such as a cycloalkyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the halogen group include a fluoro group, a chloro group, a bromo group, and an iodo group. These substituents are used as necessary in the selection of the compound (C), such as simplification of the production method and adjustment of physical property values such as the melting point.

  In the monofunctional phenol compound (C) having one group represented by the general formula (1), the structure of the portion other than the group represented by the general formula (1) is a phenol compound having one phenolic hydroxyl group. This is the structure. Examples of compounds having such a phenol structure include phenol, 1-naphthol, 2-naphthol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 2-benzylphenol, 3-benzylphenol, and 4-benzylphenol. 4-cumylphenol and the like. Among these, when the structure of phenol, 1-naphthol or 2-naphthol is used, the monofunctional phenol compound (C) is excellent in reactivity with the epoxy resin (A) and is easily introduced into the skeleton structure of the cured product. In addition to being easy to exhibit its characteristics, it is preferable because it has properties that are difficult to hydrolyze.

  When the imide group in the imide compound in the conventional invention is hydrolyzed, the amic acid that is a hydrolysis product may cause a decrease in curability and the moldability of the resin composition may deteriorate. However, although the monofunctional phenol compound (C) in the present invention has a structure in which the amide bond of the substituent represented by the general formula (1) constituting this can be hydrolyzed, its hydrolyzability is as described above. Compared with an imide compound, it is much lower and the possibility of such a defect is extremely low, and the elastic modulus of the cured product can be reduced.

The easiness of hydrolysis (hydrolyzability) is that of the amic acid generated by subjecting a compound corresponding to the monofunctional phenol compound (C) to a hydrolysis reaction with a sufficient amount of water under a hydrochloric acid catalyst. It can be measured by measuring the amount of substance, and can be quantified as a hydrolysis rate.
For example, 400 mg of monofunctional phenol is treated in a mixed solution of 20 mL of a 1.2 mol / L pyridine hydrochloride solution and 20 mL of ion-exchanged water at a temperature of 140 ° C. for 1 hour to carry out a hydrolysis reaction. Generate acid. The solution after this reaction was titrated using a potentiometric automatic titrator with a 0.1 mol / L sodium hydroxide solution set, and the monofunctional phenol was hydrolyzed from the amount of sodium hydroxide solution dropped at the equivalence point. The measurement can be performed by quantifying the amount of the carboxylic acid generated by the decomposition of the compound (C).
The ratio (%) of the amount of the generated carboxylic acid to the amount of the compound (C) contained in 400 mg is defined as the hydrolysis rate. The hydrolysis rate is preferably 50% or less, and more preferably 10% or less because the possibility of the above-described failure is extremely reduced.

  The epoxy resin composition of the present invention is not particularly limited with respect to the content (blending) ratio of the epoxy resin (A) and the curing agent (B), but with respect to 1 mol of the epoxy group of the epoxy resin (A). The phenolic hydroxyl group of the curing agent (B) is preferably used in an amount of about 0.5 to 2 mol, more preferably about 0.7 to 1.5 mol. Thereby, various characteristics improve more, maintaining the balance of the various characteristics of an epoxy resin composition to a suitable thing.

  Moreover, the suitable usage-amount of the monofunctional phenol compound (C) which has one group represented by General formula (1) is the equivalent ratio of an epoxy resin (A) and a hardening | curing agent (B), and target hardening. Although it differs depending on the degree of reduction in the elastic modulus of the product, in the combination of generally used epoxy resin (A) and curing agent (B), specifically for the sum of epoxy resin (A) and curing agent (B) , Preferably between 0.5 and 15% by weight. The degree of decrease in elastic modulus in the case of a cured product tends to be proportional to the amount added, and can be arbitrarily adjusted during use. Although the added amount can be used outside the above range, if it exceeds the above range, the crosslinking density necessary and sufficient for gelation cannot be obtained, and resin curing failure may occur. Moreover, when less than said range, the reduction effect of the elasticity modulus of hardened | cured material may not fully be acquired, or a glass transition temperature may not improve.

  In addition to the above components, an inorganic filler (D) can be used in the epoxy resin composition of the present invention as necessary. In particular, inorganic fillers are effective for use in fields requiring high heat resistance, such as epoxy resin compositions for semiconductor encapsulation. There is no restriction | limiting in particular about the kind of inorganic filler (D), and what is generally used as a resin additive can be used.

  As this inorganic filler (D), what is generally used for the epoxy resin composition for semiconductor sealing can be used. For example, fused spherical silica, fused crushed silica, crystalline silica, talc, alumina, titanium white, silicon nitride, and the like can be mentioned, and those most preferably used for semiconductor encapsulation are spherical fused silica and crushed fused. Silica. These inorganic fillers may be used alone or in combination. Moreover, these may be surface-treated with a coupling agent. The shape of the inorganic filler is preferably as spherical as possible and the particle size distribution is broad in order to improve fluidity.

  Although content of an inorganic filler (D) is not specifically limited, 50 to 95 weight% is preferable in all the epoxy resin compositions. Although it can be used outside the above range, if it falls below the lower limit, sufficient solder resistance may not be obtained, and if it exceeds the upper limit, sufficient fluidity may not be obtained.

  The content of the inorganic filler (D) is such that the epoxy resin (A), the curing agent (B) and the monofunctional phenolic compound (C) having one group represented by the general formula (1) or inorganic Considering the specific gravity of the filler (D), the weight% may be converted to volume% and handled.

  In the present invention, a curing accelerator can be arbitrarily used. As the curing accelerator, a monofunctional compound having one group represented by the epoxy resin (A), the curing agent (B), and the general formula (1). If it has a function which accelerates | stimulates hardening reaction of a phenolic compound (C), there will be no restriction | limiting. Specifically, organic phosphine compounds such as triphenylphosphine and tritertiary butylphosphine; amine compounds such as tributylamine and benzyldimethylamine; imidazole compounds such as 2-methylimidazole and 2-phenylimidazole; tetraphenylphosphonium tetra Phosphonium salts such as phenylborate, tetraphenylphosphonium bromide, and tetraphenylphosphonium tetranaphthoic acid borate; molecular compounds of tetraphenylphosphonium and bisphenol A, molecular compounds of tetraphenylphosphonium and bisphenol F, tetraphenylphosphonium and 2,3 -Phosphonium molecular compounds, such as molecular compounds of dihydroxynaphthalene; 2- (triphenylphosphonio) phen Acrylate, phosphonium inner salt compounds such as the adduct of triphenylphosphine with benzoquinone; 1,8-diazabicyclo (5,4,0) -7-curing accelerators such diazabicycloalkene compounds such as undecene available. These curing accelerators can also be used after being finely divided, microcapsuled (core shell), mechano-fusion treated, or the like.

  Of these, when the phosphonium molecular compound and the phosphonium inner salt compound are used, the monofunctional phenol having one group represented by the epoxy resin (A), the curing agent (B) and the general formula (1) It is preferable because the reaction of the compound (C) is well accelerated and sufficient crosslinking is formed. Such preferable curing accelerators include molecular compounds of tetraphenylphosphonium and 2,3-dihydroxynaphthalene, molecular compounds of tetraphenylphosphonium and bisphenol F, 2- (triphenylphosphonio) phenolate, triphenylphosphine and benzoquinone. Examples include adducts.

  In the epoxy resin composition of the present invention, the amount of the curing accelerator used is not particularly limited, but the monofunctional group having one group represented by the epoxy resin (A), the curing agent (B) and the general formula (1). The amount is preferably about 0.01 to 10% by weight, more preferably about 0.1 to 5% by weight, based on the resin component composed of the phenol compound (C). Thereby, the sclerosis | hardenability, fluidity | liquidity, and hardened | cured material characteristic of an epoxy resin composition are expressed with sufficient balance.

  The epoxy resin composition of the present invention is necessary in addition to the epoxy resin (A), the curing agent (B), and the monofunctional phenol compound (C) having one group represented by the general formula (1). Depending on the silane coupling agent such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane and vinyl silane, titanate coupling agent, aluminum coupling agent, coupling agent such as aluminum / zirconium coupling agent; Colorants such as carbon black and bengara; natural waxes such as carnauba wax; synthetic waxes such as polyethylene wax; mold release agents such as higher fatty acids such as stearic acid and zinc stearate and metal salts thereof or paraffin; silicone oil and Low stress components such as silicone rubber; Brominated epoxy Various additives such as resin, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate and phosphazene; inorganic ion exchangers such as bismuth oxide hydrate; There is no problem.

  The epoxy resin composition of the present invention comprises an epoxy resin (A), a curing agent (B), a monofunctional phenol compound (C) having one group represented by the general formula (1), and if necessary, inorganic filling The material (D), other additives and the like are sufficiently uniformly mixed using a mixer, then melt-kneaded with a kneader, cooled and pulverized. The mixer is not particularly limited, and examples thereof include blenders such as a ball mill, a Henschel mixer, a V blender, a double cone blender, a concrete mixer, and a ribbon blender. The kneader is not particularly limited, but a hot roll, a heating kneader, a uniaxial or biaxial screw type kneader, or the like is preferably used.

  The epoxy resin composition for semiconductor encapsulation of the present invention is a monofunctional phenol having one group represented by the epoxy resin (A), the curing agent (B) and the general formula (1) in the epoxy resin composition of the present invention. The compound (C), the inorganic filler (D), and, if necessary, other additives can be used by the same method as the above epoxy resin composition.

  The epoxy resin composition of the present invention can be used to obtain a semiconductor device in which various electronic components such as semiconductor elements are sealed with the cured product. To manufacture such a semiconductor device, a transfer mold is used. The molding may be performed by a conventionally used molding method such as a compression mold or an injection mold.

The form of the semiconductor device of the present invention is not particularly limited. For example, SIP (Single Inline Package), HSIP (SIP with Heatsink), ZIP (Zig-zag Inline Package), DIP (Dual Inline Package), SDIP (Shrink) Dual Inline Package), SOP (Small Outline Package), SSOP (Shrink Small Outline Package), TSOP (Thin Small Outline Package), SOJ (Small Outline J-leaded Package), QFP (Quad Flat Package), QFP (FP) ( QFP Fine Pitch), TQFP (Thin Quad Flat Package), QFJ (PLCC) (Quad Flat J-leaded Package), BGA (Ball Grid Array), and the like.
The semiconductor device of the present invention thus obtained is excellent in solder resistance during moisture absorption.

  The epoxy resin composition for semiconductor encapsulation of the present invention is preferable because it is particularly effective for reducing warpage when used in a semiconductor device having a ball grid array (BGA) structure as a sealing material for ball grid array.

A typical example of a semiconductor device having a ball grid array structure will be described with reference to the drawings (FIG. 1).
As an example of sealing a semiconductor device having a ball grid array structure using the epoxy resin composition for semiconductor sealing obtained above, a semiconductor element (a) is mounted on a semiconductor element mounting substrate (b) having a through hole. In the semiconductor element mounting substrate in which the solder ball (c) is disposed in the through hole and the terminal formed on the through hole on the surface opposite to the surface on which the solder ball (c) is disposed And a semiconductor element mounting substrate in which electrodes formed on the semiconductor element (a) are electrically connected by wire bonding (d), and a semiconductor on the surface of the semiconductor element mounting substrate on which the semiconductor element is mounted Using an epoxy resin composition for semiconductor encapsulation so as to cover the element (a), the terminals of the solder balls (c), and the wire bonds (d), a composition such as a tarance fur mold is formed. The method, sealed with a cured product (e), it is possible to obtain a semiconductor device of ball grid array structure.

  In the semiconductor device having the ball grid array structure, the difference in the linear expansion coefficient between the substrate (b) and the cured product (e) of the semiconductor sealing epoxy resin composition causes the substrate (b) to face upward or downward. May be warped. When the epoxy resin composition for semiconductor encapsulation of the present invention is used, since the cured resin product has a low elastic modulus and a high glass transition temperature, the difference in linear expansion coefficient from the substrate is alleviated. , Warpage defects are less likely to occur.

  In the present embodiment, the case where the epoxy resin composition of the present invention is used as a sealing material for a semiconductor device has been described. However, the use of the epoxy resin composition of the present invention is not limited thereto. .

  Next, specific examples of the present invention will be described, but the present invention is not limited thereto.

  In the practice of the present invention, a commercially available reagent was used as it was for 1-naphthol, which is a monofunctional phenol for comparison. Monofunctional phenol components C1 to C10, monofunctional phenol components C11 to 12 for comparison, and curing accelerators E1 to E3 in the present invention were prepared by the methods described below.

(Synthesis of Compound C1)
A beaker with a capacity of 100 mL was charged with 5.45 g (0.050 mol) of 4-aminophenol and 20 mL of dimethylformamide, stirred, and 7.05 g (0.050 mol) of benzoic acid chloride was added to dimethyl chloride while cooling the beaker with ice. A solution dissolved in 15 mL of formamide was added dropwise over 15 minutes. After the dropwise addition, 50 mL (0.050 mol) of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction solution obtained by continuing stirring at room temperature for 2 hours, and neutralized so that the pH of the system was 7. This solution was added dropwise to 5 times the weight of ion-exchanged water, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 9.90 g of a white powder.
This compound was designated C1. As a result of analyzing the compound C1 by ¹ H-NMR and mass spectrum, it was confirmed to be a compound represented by the following formula (2). The yield of the obtained compound C1 was 93%.

(Synthesis of Compound C2)
A beaker with a capacity of 100 mL was charged with 5.45 g (0.050 mol) of 3-aminophenol, 20 mL of diethyl ether, and 5 mL of pyridine. The mixture was stirred and the beaker was cooled with ice while cooling 11.30 g (0.3. (050 mol) in 15 mL of diethyl ether was added dropwise over 15 minutes. After dropping, the reaction solution obtained by continuing stirring at room temperature for 2 hours was concentrated about 10 times with an evaporator, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 9.69 g of a white powder.
This compound was designated C2. As a result of analyzing the compound C2 by ¹ H-NMR and mass spectrum, it was confirmed to be a compound represented by the following formula (3). The yield of the obtained compound C2 was 91%.

(Synthesis of Compound C3)
A beaker with a capacity of 100 mL was charged with 5.45 g (0.050 mol) of 4-aminophenol and 20 mL of dimethylformamide, stirred, and 9.55 g (0.050 mol) of 2-naphthoic acid chloride while the beaker was ice-cooled. Was dissolved dropwise in 15 mL of dimethylformamide over 15 minutes. After the dropwise addition, 50 mL (0.050 mol) of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction solution obtained by continuing stirring at room temperature for 2 hours, and neutralized so that the pH of the system was 7. This solution was added dropwise to 5 times the weight of ion-exchanged water, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 11.70 g of a white powder.
This compound was designated as C3. As a result of analyzing the compound C3 by ¹ H-NMR and mass spectrum, it was confirmed to be a compound represented by the following formula (4). The yield of the obtained compound C3 was 89%.

(Synthesis of Compound C4)
A beaker with a capacity of 100 mL was charged with 5.45 g (0.050 mol) of 3-aminophenol and 20 mL of dimethylformamide, stirred, and 9.55 g (0.050 mol) of 2-naphthoic acid chloride while the beaker was ice-cooled. Was dissolved dropwise in 15 mL of dimethylformamide over 15 minutes. After the dropwise addition, 50 mL (0.050 mol) of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction solution obtained by continuing stirring at room temperature for 2 hours, and neutralized so that the pH of the system was 7. This solution was added dropwise to 5 times the weight of ion-exchanged water, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 11.57 g of a white powder.
This compound was designated as C4. As a result of analyzing the compound C4 by ¹ H-NMR and mass spectrum, it was confirmed to be a compound represented by the following formula (5). The yield of the obtained compound C4 was 88%.

(Synthesis of Compound C5)
A beaker with a capacity of 100 mL was charged with 5.45 g (0.050 mol) of 4-aminophenol and 20 mL of dimethylformamide, stirred, and 9.55 g (0.050 mol) of 1-naphthoic acid chloride while the beaker was ice-cooled. Was dissolved dropwise in 15 mL of dimethylformamide over 15 minutes. After the dropwise addition, 50 mL (0.050 mol) of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction solution obtained by continuing stirring at room temperature for 2 hours, and neutralized so that the pH of the system was 7. This solution was added dropwise to 5 times the weight of ion-exchanged water, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 11.97 g of a white powder.
This compound was designated as C5. As a result of analyzing the compound C5 by ¹ H-NMR and mass spectrum, it was confirmed to be a compound represented by the following formula (6). The yield of the obtained compound C5 was 91%.

(Synthesis of Compound C6)
A beaker with a capacity of 100 mL was charged with 5.45 g (0.050 mol) of 3-aminophenol and 20 mL of dimethylformamide, stirred, and 11.75 g (0.050 mol) of 1-naphthoic acid bromide while cooling the beaker with ice. Was dissolved dropwise in 15 mL of dimethylformamide over 15 minutes. After the dropwise addition, 50 mL (0.050 mol) of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction solution obtained by continuing stirring at room temperature for 2 hours, and neutralized so that the pH of the system was 7. This solution was added dropwise to 5 times the weight of ion-exchanged water, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 11.70 g of a white powder.
This compound was designated as C6. As a result of analyzing the compound C6 by ¹ H-NMR and mass spectrum, it was confirmed to be a compound represented by the following formula (7). The yield of the obtained compound C6 was 89%.

(Synthesis of Compound C7)
A beaker with a capacity of 100 mL was charged with 7.95 g (0.050 mol) of 5-amino-1-naphthol and 20 mL of dimethylformamide, stirred, and 11.18 g (0.050 mol) of benzoic acid chloride while the beaker was ice-cooled. ) In 15 mL of dimethylformamide was added dropwise over 15 minutes. After the dropwise addition, 50 mL (0.050 mol) of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction solution obtained by continuing stirring at room temperature for 2 hours, and neutralized so that the pH of the system was 7. This solution was added dropwise to 5 times the weight of ion-exchanged water, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 11.18 g of a white powder.
This compound was designated as C7. Compound C7 was analyzed by ¹ H-NMR and mass spectrum, and as a result, it was confirmed that it was a compound represented by the following formula (8). The yield of the obtained compound C7 was 85%.

(Synthesis of Compound C8)
A beaker with a capacity of 100 mL was charged with 5.45 g (0.050 mol) of 4-aminophenol and 20 mL of dimethylformamide, stirred, and 10.85 g (0.050 mol) of 4-phenylbenzoic acid chloride while the beaker was ice-cooled. ) In 15 mL of dimethylformamide was added dropwise over 15 minutes. After the dropwise addition, 50 mL (0.050 mol) of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction solution obtained by continuing stirring at room temperature for 2 hours, and neutralized so that the pH of the system was 7. This solution was added dropwise to 5 times the weight of ion-exchanged water, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 13.15 g of a white powder.
This compound was designated as C8. Compound C8 was analyzed by ¹ H-NMR and mass spectrum, and as a result, it was confirmed that it was a compound represented by the following formula (9). The yield of the obtained compound C8 was 91%.

(Synthesis of Compound C9)
A beaker with a capacity of 100 mL was charged with 5.45 g (0.050 mol) of 4-aminophenol and 20 mL of dimethylformamide, stirred, and while cooling the beaker with ice, 9.10 g (0.050 mol) of 4-propylbenzoic acid chloride. ) In 15 mL of dimethylformamide was added dropwise over 15 minutes. After the dropwise addition, 50 mL (0.050 mol) of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction solution obtained by continuing stirring at room temperature for 2 hours, and neutralized so that the pH of the system was 7. This solution was added dropwise to 5 times the weight of ion-exchanged water, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 10.29 g of a white powder.
This compound was designated as C9. As a result of analyzing Compound C9 by ¹ H-NMR and mass spectrum, it was confirmed to be a compound represented by the following formula (10). The yield of the obtained compound C9 was 81%.

(Synthesis of Compound C10)
Into a beaker with a capacity of 100 mL, 6.90 g (0.050 mol) of 3,5-dimethyl-4-aminophenol and 20 mL of dimethylformamide were added, stirred, and 2-naphthoic acid chloride was added while cooling the beaker with ice. A solution of 55 g (0.050 mol) dissolved in 15 mL of dimethylformamide was added dropwise over 15 minutes. After the dropwise addition, 50 mL (0.050 mol) of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction solution obtained by continuing stirring at room temperature for 2 hours, and neutralized so that the pH of the system was 7. This solution was added dropwise to 5 times the weight of ion-exchanged water, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 13.14 g of a white powder.
This compound was designated as C10. As a result of analyzing the compound C10 by ¹ H-NMR and mass spectrum, it was confirmed to be a compound represented by the following formula (11). The yield of the obtained compound C10 was 90%.

(Synthesis of Compound C11)
A beaker with a capacity of 100 mL was charged with 5.46 g (0.050 mol) of 4-aminophenol and 20 mL of dimethylformamide, stirred, and 7.40 g (0.050 mol) of phthalic anhydride was added to dimethyl while the beaker was ice-cooled. A solution dissolved in 15 mL of formamide was added dropwise over 15 minutes. A solution obtained by dissolving 0.95 g (0.005 mol) of paratoluenesulfonic acid in 30 mL of toluene was added to a reaction solution obtained by continuing stirring at room temperature for 2 hours after the dropping, and this solution was added to a Dean-Stark tube. It put into the equipped flask, 140 degreeC was returned for 4 hours, and spin-dry | dehydrated and closed. The obtained reaction solution was dropped into 500 mL of water, and the precipitated powder was collected by suction filtration. This powder was vacuum-dried with a vacuum dryer at 120 ° C. for 2 hours to obtain 10.63 g of a white powder.
This compound was designated as C11. As a result of analyzing the compound C11 by ¹ H-NMR and mass spectrum, it was confirmed to be a compound represented by the following formula (12). The yield of the obtained compound C11 was 89%.

(Synthesis of Compound C12)
A beaker with a capacity of 100 mL was charged with 7.65 g (0.050 mol) of 5-aminosalicylic acid and 20 mL of dimethylformamide, stirred, and 7.05 g (0.050 mol) of benzoic acid chloride was added to dimethyl chloride while cooling the beaker with ice. A solution dissolved in 15 mL of formamide was added dropwise over 15 minutes. After the dropwise addition, 50 mL (0.050 mol) of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction solution obtained by continuing stirring at room temperature for 2 hours, and neutralized so that the pH of the system was 7. This solution was added dropwise to 5 times the weight of ion-exchanged water, and the precipitated powder was collected by suction filtration. This powder was dried in a vacuum dryer at 140 ° C. for 2 hours to obtain 10.79 g of a white powder.
This compound was designated as C12. As a result of analyzing the compound C12 by ¹ H-NMR and mass spectrum, it was confirmed to be a compound represented by the following formula (13). The yield of the obtained compound C12 was 84%.

(Synthesis of curing accelerator E1)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 10.4 g (0.060 mol) of 2-bromophenol, 17.3 g (0.066 mol) of triphenylphosphine, 0.65 g (5 mmol) of nickel chloride In addition, 40 mL of ethylene glycol was charged, and the reaction was performed at 160 ° C. with stirring. After cooling the reaction solution, 40 mL of pure water was added dropwise, and the precipitated powder was washed with toluene, filtered and dried to obtain a white powder.
Next, the obtained powder was dissolved in 100 ml of methanol, and 60 ml of 1 mol / L sodium hydroxide aqueous solution and 500 ml of pure water were sequentially added. The obtained crystals were filtered and washed to obtain 12.7 g of pale yellow crystals.
This compound was designated E1. Compound C1 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed to be the target triphenyl (2-hydroxyphenyl) phosphonium. The yield of the obtained curing accelerator E1 was 83%.

(Synthesis of curing accelerator E2)
A separable flask (volume: 200 mL) equipped with a condenser and a stirrer was charged with 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 mL of acetone, and reacted at room temperature with stirring. . The precipitated crystals were washed with acetone, filtered and dried to obtain 20.0 g of brown crystals.
This compound was designated E2. Compound E2 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed to be an adduct of the target triphenylphosphine and benzoquinone. The yield of the obtained curing accelerator E2 was 84%.

(Synthesis of curing accelerator E3)
A beaker with a stirrer (capacity: 1000 mL) is charged with 25.2 g (0.060 mol) of tetraphenylphosphonium bromide, 17.28 g (0.120 mol) of 2,3-dihydroxynaphthalene, and 200 mL of methanol, and may be stirred. After dissolution, 60 ml of 1 mol / L sodium hydroxide aqueous solution and 600 mL of pure water were sequentially added. The precipitated powder was washed with pure water, filtered and dried to obtain a white powder.
This compound was designated as E3. Compound E3 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed to be a molecular compound of target tetraphenylphosphonium and 2,3-dihydroxynaphthalene. The yield of the obtained compound E3 was 83%.

[Preparation of epoxy resin composition and manufacture of semiconductor device]
As described below, an epoxy resin composition containing the compounds C1 to C10, the comparative compounds C11 to C12, the curing accelerators E1 to E3, and other phenol compounds was prepared, and a semiconductor device was manufactured.

Example 1
First, as epoxy resin (A) (component (A)), biphenyl type epoxy resin (Japan Epoxy Resin Co., Ltd. YX-4000HK, melting point: 105 ° C., epoxy equivalent: 193, ICI melt viscosity at 150 ° C .: 0. 15 poise), as a curing agent (B) (component (B)), phenol aralkyl resin (XLC-LL manufactured by Mitsui Chemicals, Inc., softening point: 77 ° C., hydroxyl group equivalent: 172, ICI melt viscosity at 150 ° C .: 3. 6poise), monofunctional phenolic compound (C) (component (C)), compound C1 obtained by the above synthesis, curing accelerator E1 obtained by the above synthesis, inorganic filler (D) (component ( D)) as fused spherical silica (average particle size 15 μm), as other additives, carbon black, brominated bisphenol A type epoxy resin and carna The wax, were prepared, respectively.

  Next, the biphenyl type epoxy resin: 55 parts by weight, the phenol aralkyl resin: 45 parts by weight, the curing accelerator E1: 1.8 parts by weight, the monofunctional phenolic compound C1: 4.3 parts by weight, and the fused spherical silica: 700 Parts by weight, carbon black: 2 parts by weight, brominated bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight were first mixed at room temperature and then kneaded at 95 ° C. for 8 minutes using a hot roll. Then, it cooled and grind | pulverized and the epoxy resin composition was obtained.

  Next, using the epoxy resin composition obtained above as an epoxy resin composition for semiconductor encapsulation, eight 100-pin TQFP packages (semiconductor devices) and 15 16-pin DIP packages (semiconductor devices) , Each manufactured.

  The 100-pin TQFP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 7.4 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.

  The package size of the 100-pin TQFP was 14 × 14 mm, the thickness was 1.4 mm, the silicon chip (semiconductor element) size was 8.0 × 8.0 mm, and the lead frame was 42 alloy.

  The 16-pin DIP was manufactured by transfer molding at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa and a curing time of 2 minutes, and post-cured at 175 ° C. for 8 hours.

  The package size of the 16-pin DIP is 6.4 × 19.8 mm, the thickness is 3.5 mm, the silicon chip (semiconductor element) size is 3.5 × 3.5 mm, and the lead frame is made of 42 alloy. .

(Example 2)
In Example 1, instead of the curing accelerator E1: 1.8 parts by weight, the curing accelerator E2: 1.9 parts by weight and the compound C1: 4.3 parts by weight are used instead of the compound C2: 4.3 parts by weight. Except for the above, an epoxy resin composition (epoxy resin composition for semiconductor encapsulation) was obtained in the same manner as in Example 1, and a package (semiconductor) was obtained in the same manner as in Example 1 using this epoxy resin composition. Device).

(Example 3)
In Example 1, instead of curing accelerator E1: 1.8 parts by weight, curing accelerator E3: 3.3 parts by weight, compound C1: instead of 4.3 parts by weight, compound C3: 6.6 parts by weight, YX Epoxy resin composition in the same manner as in Example 1 except that YX-4000HK: 57 parts by weight instead of -4000HK: 55 parts by weight and XLC-LL: 43 parts by weight instead of 45 parts by weight of XLC-LL were used. A product (epoxy resin composition for semiconductor encapsulation) was obtained, and a package (semiconductor device) was produced using this epoxy resin composition in the same manner as in Example 1.

Example 4
In Example 1, instead of the curing accelerator E1: 1.8 parts by weight, 1,8-diazabicyclo- (5,4,0) -7-undecene (manufactured by San Apro Co., Ltd., trade name: DBU): 0. 8 parts by weight, compound C1: Epoxy resin composition (epoxy resin composition for semiconductor encapsulation) in the same manner as in Example 1, except that 3.2 parts by weight of compound C4 was used instead of 4.3 parts by weight. And using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 5)
In Example 1, an epoxy resin composition (epoxy resin for semiconductor encapsulation) was used in the same manner as in Example 1 except that Compound C5: 10.5 parts by weight was used instead of Compound C1: 4.3 parts by weight. And a package (semiconductor device) was produced in the same manner as in Example 1 using this epoxy resin composition.

(Example 6)
First, as component (A), biphenyl aralkyl type epoxy resin (Nippon Kayaku Co., Ltd. NC-3000, softening point: 60 ° C., epoxy equivalent: 272, ICI melt viscosity at 150 ° C .: 1.3 poise), component ( B), biphenyl aralkyl type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., Ltd., softening point: 68 ° C., hydroxyl equivalent: 199, ICI melt viscosity at 150 ° C .: 0.9 poise), monofunctional phenol compound (C) Compound C6, curing accelerator E2 as curing accelerator, fused spherical silica (average particle size 15 μm) as component (D), carbon black, brominated bisphenol A type epoxy resin and carnauba wax as other additives Were prepared.

  Next, the biphenyl aralkyl type epoxy resin: 60 parts by weight, the biphenyl aralkyl type phenol resin: 40 parts by weight, the curing accelerator E2: 1.9 parts by weight, the compound C6: 5.3 parts by weight, and the fused spherical silica: 700 Parts by weight, carbon black: 2 parts by weight, brominated bisphenol A type epoxy resin: 2 parts by weight, carnauba wax: 2 parts by weight were first mixed at room temperature and then kneaded at 105 ° C. for 8 minutes using a hot roll. Thereafter, the mixture was cooled and pulverized to obtain an epoxy resin composition.

  Next, a package (semiconductor device) was manufactured in the same manner as in Example 1 using the epoxy resin composition obtained above as an epoxy resin composition for semiconductor encapsulation.

(Example 7)
In Example 6, instead of curing accelerator E2: 1.9 parts by weight, curing accelerator E3: 3.3 parts by weight, compound C6: instead of 5.3 parts by weight, compound C7: 5.3 parts by weight, NC -3000: 60 parts by weight, NC-3000: 62 parts by weight, MEH-7851SS: 40 parts by weight, MEH-7851SS: 38 parts by weight A resin composition (epoxy resin composition for semiconductor encapsulation) was obtained, and a package (semiconductor device) was produced in the same manner as in Example 1 using this epoxy resin composition.

(Example 8)
In Example 6, in place of the curing accelerator E2: 1.9 parts by weight, DBU: 0.8 parts by weight, Compound C6: 5.3 parts by weight, instead of Compound C8: 7.2 parts by weight In the same manner as in Example 6, an epoxy resin composition (epoxy resin composition for semiconductor encapsulation) was obtained, and using this epoxy resin composition, a package (semiconductor device) was obtained in the same manner as in Example 1. Manufactured.

Example 9
In Example 6, instead of curing accelerator E2: 1.9 parts by weight, curing accelerator E1: 1.8 parts by weight, compound C6: instead of 5.3 parts by weight, compound C9: 3.8 parts by weight were used. Except for the above, an epoxy resin composition (epoxy resin composition for semiconductor encapsulation) was obtained in the same manner as in Example 6, and the package (semiconductor) was obtained in the same manner as in Example 1 by using this epoxy resin composition. Device).

(Example 10)
In Example 6, an epoxy resin composition (epoxy resin for semiconductor encapsulation) was used in the same manner as in Example 6 except that compound C10: 11.7 parts by weight was used instead of compound C6: 5.3 parts by weight. And a package (semiconductor device) was produced in the same manner as in Example 1 using this epoxy resin composition.

(Comparative Example 1)
In Example 6, instead of NC-3000: 60 parts by weight, instead of NC-3000: 62 parts by weight, MEH-7851SS: 40 parts by weight, MEH-7851SS: 38 parts by weight, Compound C6: 5.3 parts by weight Instead, an epoxy was prepared in the same manner as in Example 6 except that the compound C11: 4.8 parts by weight and the curing accelerator E2: 1.9 parts by weight were used instead of the curing accelerator E3: 3.3 parts by weight. A resin composition was obtained, and using this epoxy resin composition, a package (semiconductor device) was produced in the same manner as in Example 1.

(Comparative Example 2)
In Example 1, an epoxy resin composition was obtained in the same manner as in Example 1 except that Compound C12: 5.1 parts by weight was used instead of Compound C1: 4.3 parts by weight. Using the product, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Comparative Example 3)
In Example 6, in place of hardening accelerator E2: 1.9 parts by weight, DBU: 0.8 parts by weight, compound C6: 5.3 parts by weight, 1-naphthol: 2.9 parts by weight was used. Obtained an epoxy resin composition in the same manner as in Example 6, and a package (semiconductor device) was produced in the same manner as in Example 1 by using this epoxy resin composition.

(Comparative Example 4)
In Example 1, the component corresponding to the component (C) was not used and the curing accelerator E1: 1.8 parts by weight was used instead of the curing accelerator E3: 3.3 parts by weight. In the same manner as in Example 1, an epoxy resin composition was obtained, and using this epoxy resin composition, a package (semiconductor device) was produced in the same manner as in Example 1.

(Comparative Example 5)
In Example 6, the component corresponding to the component (C) was not used, but the curing accelerator E2 was changed to 1.9 parts by weight, and the curing accelerator E3 was used except that 3.3 parts by weight was used. In the same manner as in Example 6, an epoxy resin composition was obtained, and using this epoxy resin composition, a package (semiconductor device) was produced in the same manner as in Example 1.

[Characteristic evaluation]
Characteristic evaluation (1) to (4) of the epoxy resin composition (epoxy resin composition for semiconductor encapsulation) obtained in each example and each comparative example, and the semiconductor obtained in each example and each comparative example The characteristic evaluation (5) of the apparatus was performed as follows.

(1) Spiral flow Using a mold for spiral flow measurement according to EMMI-I-66, measurement was performed at a mold temperature of 175 ° C, an injection pressure of 6.8 MPa, and a curing time of 2 minutes.

  This spiral flow is a parameter of fluidity, and the larger the value, the better the fluidity.

(2) Curing torque Using a curast meter (Orientec Co., Ltd., JSR curast meter IV PS type), the torque after 175 ° C. and 300 seconds was measured and evaluated as a curing torque. Further, assuming that the curing torque was 100%, the ratio (%) of the torque after 90 seconds to the curing torque was defined as 90-second torque saturation.
This hardening torque shows that curability is so favorable that a numerical value is large.

(3) 90 seconds torque saturation at the time of moisture absorption After the resin composition for molding same as the above-mentioned curing torque is compressed into a tablet, it is stored for 24 hours in an environment with a temperature of 30 ° C. and a relative humidity of 60% to absorb moisture. As a sample, a curast meter (manufactured by Orientec Co., Ltd., JSR curast meter IV PS type) was used, and the torque after 175 ° C. for 300 seconds (curing torque during moisture absorption) was measured. This moisture curing torque was taken as 100%, and the ratio (%) of the torque 90 seconds after the start of measurement to the moisture cured torque was defined as the 90 second torque saturation at moisture absorption.
The higher the 90-second torque saturation at the time of moisture absorption, the less the deterioration of curability due to moisture.

(4) Hydrolysis rate When a compound corresponding to the monofunctional phenol compound (C) was used, the hydrolysis rate of the corresponding compound (C) alone was evaluated. 400 mg of the compound corresponding to the compound (C) obtained above was treated in a mixed solution of 20 mL of 1.2 mol / L pyridine hydrochloride solution and 20 mL of ion-exchanged water at a temperature of 140 ° C. for 1 hour. The solution was titrated using an automatic potentiometric titrator set with 0.1 mol / L sodium hydroxide solution, and the amount of carboxylic acid generated by decomposition from the equivalence point was quantified. The ratio (%) of the amount of the generated carboxylic acid to the amount of the compound (C) contained in 400 mg was defined as the hydrolysis rate.
A compound having a high hydrolysis rate generates a large amount of amic acid as a hydrolysis product in the molding process, and the curability is remarkably deteriorated.

(5) Glass transition temperature Using a mold capable of obtaining a molded product of 500 × 10 × 3 mm, a test piece formed by molding at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa, and a curing time of 5 minutes is 175 ° C. After storing in a hot air dryer for 4 hours, using a rheometer Rheopolymer, manufactured by Jusco International Co., Ltd., measured to 300 ° C in an oscillation strain control measurement mode, frequency 1 Hz, strain 0.03, and the phase angle was The temperature showing the first peak was measured as the glass transition temperature. The glass transition temperature affects the solder crack resistance when the semiconductor is sealed with resin, and the higher the value, the better the solder crack resistance.

(6) Storage elastic modulus at 260 ° C. (thermal elastic modulus)
Using a mold from which a molded product of 500 × 10 × 3 mm can be obtained, a test piece formed by molding at a mold temperature of 175 ° C., an injection pressure of 6.8 MPa, and a curing time of 5 minutes was obtained using a hot air dryer at 175 ° C. After storage for a period of time, a storage elastic modulus at 260 ° C. was measured using a rheometer Rheopolymer manufactured by Jusco International Co., Ltd. in an oscillation strain control measurement mode, a frequency of 1 Hz, and a strain of 0.03. The elastic modulus at high temperature affects the solder crack resistance when the semiconductor is sealed with resin, and the lower the value, the better the solder crack resistance.

(7) Solder resistance The 100-pin TQFP was left in an environment of 85 ° C. and 85% relative humidity for 168 hours, and then immersed in a solder bath at 260 ° C. for 10 seconds.

  Then, the presence or absence of the occurrence of external cracks was observed under a microscope, and displayed as a percentage (%) as crack generation rate = (number of packages in which cracks occurred) / (total number of packages) × 100.

  Further, the ratio of the peeled area between the silicon chip and the cured epoxy resin composition was measured using an ultrasonic flaw detector, and the peel rate = (peeled area) / (silicon chip area) × 100. The average value of the package was obtained and expressed as a percentage (%).

  These crack generation rate and peeling rate indicate that the smaller the numerical value, the better the solder resistance at the time of moisture absorption, and the higher the reliability of the obtained package.

(8) Package warpage 225-pin BGA package (substrate is a BT resin substrate with a thickness of 0.36 mm, package size is 24 × 24 mm, thickness 1.17 mm, silicon chip is size 9 × 9 mm, thickness 0.35 mm, chip and circuit The substrate bonding pad was bonded with a gold wire having a diameter of 25 μm.) Was transfer molded at a mold temperature of 180 ° C. and an injection pressure of 7.8 MPa for 2 minutes, and further post-cured at 175 ° C. for 4 hours. After cooling to room temperature, the displacement in the height direction was measured using a surface roughness meter in the diagonal direction from the gate of the package, and the value with the largest variation difference was taken as the warpage before soldering. Furthermore, after IR reflow treatment was performed at a peak temperature of 260 ° C under JEDEC conditions, the displacement in the height direction was measured using a surface roughness meter in the diagonal direction from the gate of the package, and the value with the largest variation difference was soldered. The amount of warpage before the treatment was used. The number of tests was set to n = 10, the measurement unit was measured in μm, and the warp amount was 80 μm or less for all (pass).

  As shown in Table 1, the epoxy resin compositions obtained in Examples 1 to 10 (the epoxy resin composition of the present invention and the epoxy resin composition for semiconductor encapsulation) all impair the curability and fluidity. Instead, the value of 260 ° C. storage modulus is reduced while maintaining the glass transition temperature. Furthermore, since the epoxy resin composition of the present invention uses the compound (C) having a low hydrolysis rate, the package (semiconductor device of the present invention) sealed with this cured product has moisture absorption. Sometimes the curability does not decrease. Also, these have good solder resistance and excellent reliability, and showed good warpage characteristics when used in BGA packages.

  On the other hand, the epoxy resin composition obtained in Comparative Example 1 was a monofunctional phenol compound having a structure different from that of the monofunctional phenol compound (C) used in the present invention and having a high hydrolysis rate. The curability at the time of moisture absorption was insufficient. Since the epoxy resin composition obtained in Comparative Example 2 used a phenol compound that was not monofunctional, the 260 ° C. storage modulus could not be reduced, and defects occurred due to solder resistance and package warpage. The epoxy resin composition obtained in Comparative Example 3 is a monofunctional phenol having no specific substituent in the above compound (C) and has a 260 ° C. storage elastic modulus reduction, but also has a marked glass transition temperature. The soldering resistance was poor, and the warpage characteristics were insufficient. None of the epoxy resin compositions obtained in Comparative Examples 4 and 5 contains a monofunctional phenol compound (C), and has a high storage elastic modulus at 260 ° C. The packages obtained in these Comparative Examples are Both of them were inferior in solder resistance and warpage characteristics.

It is sectional drawing for demonstrating the typical example of the semiconductor device which has the ball grid array structure of this invention.

Explanation of symbols

a Semiconductor element b Substrate c Solder ball d Wire bond e Hardened material

Claims (7)

An epoxy resin composition comprising an epoxy resin (A), a curing agent (B), and a monofunctional phenol compound (C) having one group represented by the following general formula (1).

[Wherein, X represents an aromatic group having 2 to 12 carbon atoms. ]   The epoxy resin composition according to claim 1, wherein the aromatic group as X in the formula (1) is a phenyl group or a naphthalenyl group.   The epoxy resin composition for semiconductor sealing containing the epoxy resin composition of Claim 1 or 2, and an inorganic filler (D).   The said epoxy resin composition is 50-95 wt% of inorganic fillers (D) with respect to the total amount of an epoxy resin (A), a hardening | curing agent (B), a monofunctional phenol compound (C), and an inorganic filler (D). The epoxy resin composition for semiconductor encapsulation according to claim 3, which is contained at a ratio of   The epoxy resin composition for semiconductor encapsulation according to claim 4, wherein the epoxy resin composition for semiconductor encapsulation is a ball grid array sealing material.   A semiconductor device in which an electronic component is sealed with a cured product of the epoxy resin composition for sealing a semiconductor according to claim 4 or 5.   The semiconductor device according to claim 6, wherein the semiconductor device has a ball grid array structure.

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