JP2011046866A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition and a semiconductor device having excellent soldering characteristics. <P>SOLUTION: The epoxy resin used for sealing a semiconductor includes: (A) an epoxy resin; (B) a curing agent; (C) an inorganic filler; and (D) an organic compound having a phenolic hydroxide group and carboxylic compound. Also, the semiconductor device is a cured product of the epoxy resin composition and seals a semiconductor element inside. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  As a sealing method for semiconductor elements such as IC and LSI, transfer molding of an epoxy resin composition is suitable for mass production at low cost and has been adopted for a long time, and a phenol resin that is an epoxy resin or a curing agent in terms of reliability. Improvements have been made to improve the characteristics. However, due to the recent trend of downsizing, weight reduction, and higher performance of electronic devices, semiconductor devices have been increasingly integrated and the surface mounting of semiconductor devices has been promoted. The demand for resin compositions has become increasingly severe. For this reason, the problem which cannot be solved with the conventional epoxy resin composition has also come out.

  The biggest problem is that the semiconductor device is exposed to a high temperature of 200 ° C. or higher in the solder dipping or reflow process due to the use of surface mounting, and the moisture when moisture absorbed explosively vaporizes the semiconductor device. This is a phenomenon in which cracks are generated and peeling occurs at the interface between various plated joint portions on the semiconductor element, lead frame, and inner lead and the cured product of the epoxy resin composition, and the reliability is significantly reduced.

  In order to improve reliability reduction due to solder processing, increase the amount of inorganic filler in the epoxy resin composition to achieve low moisture absorption, high strength, low thermal expansion, and improve solder resistance. A technique of maintaining low fluidity and high fluidity during molding using a low melt viscosity resin is becoming common.

  On the other hand, in terms of reliability after soldering, the adhesiveness at the interface between a cured product of the epoxy resin composition and a substrate such as a semiconductor element or a lead frame existing inside the semiconductor device has become very important. If the adhesive strength at the interface is weak, peeling occurs at the interface with the base material after the solder treatment, and further, cracks occur in the semiconductor device due to this peeling.

  Conventionally, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane and γ- (methacryloxypropyl) trimethoxysilane have been added to epoxy resin compositions for the purpose of improving solder resistance. In recent years, however, these silane coupling agents are not enough to meet the increasingly demanding requirements for soldering resistance, such as an increase in reflow temperature during mounting and an increase in special packages with exposed die pads. ing.

  As a countermeasure, a lead frame surface treatment with an alkoxysilane coupling agent (see, for example, Patent Document 1), a resin composition containing a thiazole, sulfenamide, or thiuram compound and a resin seal A stationary semiconductor device (see, for example, Patent Document 2) has been proposed. However, the former silane coupling agent has poor heat stability and has a drawback that the effect of improving adhesion during solder treatment such as solder dipping and solder reflow is reduced. The latter compound has a large molecular weight and is unstable. Since many bonds (nitrogen-sulfur bonds) are included, it has been pointed out that adhesion may be reduced in the molded sealing resin.

JP-A-6-350,000 Japanese Patent Laid-Open No. 11-181240

  An object of the present invention is to provide an epoxy resin composition and a semiconductor device excellent in solder resistance and fluidity.

  The epoxy resin composition of the present invention is an epoxy resin composition used for semiconductor encapsulation, and (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) a phenolic hydroxyl group. And an organic compound having a carboxyl group.

  In the epoxy resin composition of the present invention, the organic compound (D) having a phenolic hydroxyl group and a carboxyl group may be a compound represented by the following general formula (1).

（式中、Ｒ１は単結合、二重結合、三重結合、エーテル結合、スルホン結合、エステル結合、アミド結合、イミド結合、ウレタン結合、及びケトン結合から選ばれる結合、あるいは芳香族環、脂肪族環、又は複素環を含む有機基、もしくは脂肪族基である。Ｒ２は、水素あるいは炭素数１〜１４の有機基、水酸基、アミノ基、カルボキシル基、シアノ基、ニトロ基、アルデヒド基、縮環した芳香族環、脂肪族環、又は複素環を表し、同一であっても、異なっていてもよい。ａは、１〜４の整数。）

(In the formula, R1 is a bond selected from a single bond, a double bond, a triple bond, an ether bond, a sulfone bond, an ester bond, an amide bond, an imide bond, a urethane bond, and a ketone bond, or an aromatic ring or an aliphatic ring. Or an organic group containing a heterocyclic ring or an aliphatic group, R2 is hydrogen or an organic group having 1 to 14 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a nitro group, an aldehyde group, or a condensed ring. Represents an aromatic ring, an aliphatic ring, or a heterocyclic ring, which may be the same or different, and a is an integer of 1 to 4.

  In the epoxy resin composition of the present invention, the organic compound (D) having a phenolic hydroxyl group and a carboxyl group may have a molecular weight of less than 500.

  The carboxyl group of the organic compound (D) having a phenolic hydroxyl group and a carboxyl group may be a carboxyl group bonded to an aliphatic carbon.

  In the epoxy resin composition of the present invention, the (A) epoxy resin may contain an epoxy resin represented by the following general formula (2).

  In the epoxy resin composition of the present invention, the (B) curing agent may include a phenol resin represented by the following general formula (3).

  The epoxy resin composition of the present invention may further contain (E) a curing accelerator.

  The epoxy resin composition of the present invention may further contain (F) a silane coupling agent and / or (G) a compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring.

  A semiconductor device of the present invention is characterized in that a semiconductor element is sealed with a cured product of the epoxy resin composition described above.

  According to the present invention, when a semiconductor element mounted on a lead frame such as copper or 42 alloy is sealed, an epoxy having good solder resistance that does not cause peeling or cracking even by high-temperature solder processing corresponding to lead-free solder. A resin composition and a semiconductor device can be obtained.

It is the figure which showed the cross-section about an example of the semiconductor device using the epoxy resin composition which concerns on this invention.

  Hereinafter, the epoxy resin composition and semiconductor device of the present invention will be described in detail. The epoxy resin composition of the present invention is an epoxy resin composition used for semiconductor encapsulation, and (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) a phenolic hydroxyl group. And an organic compound having a carboxyl group. A semiconductor device of the present invention is characterized in that a semiconductor element is sealed with a cured product of the epoxy resin composition described above.

  First, the epoxy resin composition will be described. The epoxy resin composition of the present invention contains an epoxy resin (A). 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. Epoxy resin, bisphenol type epoxy resin, stilbene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene Examples thereof include modified phenol type epoxy resins, phenol aralkyl type epoxy resins (having a phenylene skeleton, biphenylene skeleton, etc.), and these may be used alone or in combination of two or more. Among such epoxy resins, a phenol aralkyl type epoxy resin having a biphenylene skeleton represented by the following general formula (2) is preferable. Thereby, especially flame resistance and solder resistance can be improved. Although it does not specifically limit as a compounding ratio with respect to the whole epoxy resin (A) of the phenol aralkyl type epoxy resin which has a biphenylene skeleton represented by following General formula (2), It is 30 to 100 mass%. More preferably, it is 50 mass% or more and 100 mass% or less. Within the above range, the flame resistance and solder resistance can be stably improved.

  The blending ratio of the entire epoxy resin (A) used in the present invention is not particularly limited, but is preferably 2% by mass or more and 10% by mass or less, and 2.5% by mass in the total epoxy resin composition. As mentioned above, it is more preferable that it is 8 mass% or less. When the blending ratio of the entire epoxy resin (A) is within the above range, there is little risk of causing a decrease in solder resistance, a decrease in fluidity, and the like.

  The epoxy resin composition of the present invention contains a curing agent (B). The curing agent (B) used in the present invention is not particularly limited as long as it is cured by reacting with an epoxy resin. Specific examples thereof include phenolic resins, bisphenol compounds such as bisphenol A, maleic anhydride, Examples include acid anhydrides such as phthalic anhydride and pyromellitic anhydride, and aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. These may be used alone or in combination with two or more curing agents. May be.

  Among these curing agents, it is particularly preferable to use a phenolic resin. The phenolic resin used in the present invention is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, a phenol novolak resin, Examples include cresol novolac resin, dicyclopentadiene-modified phenol resin, terpene-modified phenol resin, triphenolmethane type resin, phenol aralkyl resin (having a phenylene skeleton, biphenylene skeleton, etc.), and these may be used alone. Two or more types may be used in combination. Among such phenol resins, a phenol aralkyl resin having a biphenylene skeleton represented by the following general formula (3) is preferable. Thereby, especially flame resistance and solder resistance can be improved. Although it does not specifically limit as a compounding ratio with respect to the whole hardening | curing agent (B) of the phenol aralkyl resin which has a biphenylene skeleton represented by following General formula (3), It is 30 mass% or more and 100 mass% or less. Is more preferable, and it is further more preferable that it is 50 to 100 mass%. Within the above range, the flame resistance and solder resistance can be stably improved.

  The blending ratio of the curing agent (B) used in the present invention is not particularly limited, but is preferably 1% by mass or more and 8% by mass or less, and preferably 2% by mass or more and 6% by mass in the total epoxy resin composition. % Or less is more preferable. When the blending ratio of the curing agent (B) is within the above range, there is little possibility of causing a decrease in solder resistance, a decrease in fluidity, and the like.

  As a blending ratio of the epoxy resin and the phenolic resin as the curing agent, the equivalent ratio (Ep / Ph) of the number of epoxy groups (Ep) of all epoxy resins and the number of phenolic hydroxyl groups (Ph) of all phenolic resins is 0. It is preferably 8 or more and 1.3 or less, and more preferably 0.9 or more and 1.25 or less. When the equivalence ratio is within the above range, it is less likely to cause a decrease in the curability of the epoxy resin composition, a decrease in the glass transition temperature of the cured product, a decrease in moisture resistance reliability, or the like.

  The epoxy resin composition of the present invention contains an inorganic filler (C). As an inorganic filler (C) used by this invention, what is generally used for the epoxy resin composition for semiconductor sealing can be used. Examples thereof include fused silica, crystalline silica, talc, alumina, silicon nitride and the like, and the most preferably used is spherical fused silica. These inorganic fillers may be used alone or in combination of two or more.

  Although the average particle diameter of the inorganic filler (C) used by this invention is not specifically limited, 5 micrometers or more and 50 micrometers or less are preferable, and 10 micrometers or more and 45 micrometers or less are more preferable. When the average particle size is within the above range, the fluidity is good, and when the average particle size is below the lower limit, sufficient fluidity cannot be obtained. There is.

  Although content of the inorganic filler (C) used by this invention is not specifically limited, 75 mass% or more and 94 mass% or less of the whole epoxy resin composition are preferable, and 80 mass% or more and 92 mass% or less are more. preferable. When the content is within the above range, there is a low possibility of causing a decrease in solder resistance and a decrease in fluidity.

  The epoxy resin composition of this embodiment contains the organic compound (D) which has a phenolic hydroxyl group and a carboxyl group. When the organic compound (D) having a phenolic hydroxyl group and a carboxyl group used in the present invention can be used, the adhesion between a lead frame such as copper or 42 alloy and the cured product of the epoxy resin composition can be improved. The effect of suppressing delamination at the interface can be obtained also during the solder treatment during surface mounting and under various environments thereafter. The organic compound (D) having a phenolic hydroxyl group and a carboxyl group is not particularly limited as long as it is an organic compound having a phenolic hydroxyl group and a carboxyl group, but preferably has a molecular weight of less than 500 and less than 300. Is more preferable. Within the above range, the viscosity of the organic resin (D) itself having a phenolic hydroxyl group and a carboxyl group is not too high, so that the viscosity of the epoxy resin composition is kept low. Further, the lower limit of the molecular weight of the organic compound (D) having a phenolic hydroxyl group and a carboxyl group is not particularly limited, but the substantial lower limit is 138. Furthermore, the organic compound (D) having a phenolic hydroxyl group and a carboxyl group is more preferably a compound represented by the following general formula (1).

（式中、Ｒ１は単結合、二重結合、三重結合、エーテル結合、スルホン結合、エステル結合、アミド結合、イミド結合、ウレタン結合、及びケトン結合から選ばれる結合、あるいは芳香族環、脂肪族環、又は複素環を含む有機基、もしくは脂肪族基である。Ｒ１は水酸基、アミノ基、カルボキシル基、シアノ基、ニトロ基、アルデヒド基等の置換基を１個以上有していてもよい。また、フェノールのベンゼン環に縮環していてもよい。Ｒ２は、水素あるいは炭素数１〜１４の有機基、水酸基、アミノ基、カルボキシル基、シアノ基、ニトロ基、アルデヒド基、縮環した芳香族環、脂肪族環、又は複素環を表し、同一であっても、異なっていてもよい。ａは、１〜４の整数。）

(In the formula, R1 is a bond selected from a single bond, a double bond, a triple bond, an ether bond, a sulfone bond, an ester bond, an amide bond, an imide bond, a urethane bond, and a ketone bond, or an aromatic ring or an aliphatic ring. Or an organic group containing a heterocyclic ring or an aliphatic group, and R 1 may have one or more substituents such as a hydroxyl group, an amino group, a carboxyl group, a cyano group, a nitro group, and an aldehyde group. R2 may be hydrogen or an organic group having 1 to 14 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a nitro group, an aldehyde group, or a condensed aromatic group. A ring, an aliphatic ring, or a heterocyclic ring, which may be the same or different, a is an integer of 1 to 4)

  Specific examples of the organic compound (D) having a phenolic hydroxyl group and a carboxyl group include 2-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3-hydroxybenzoic acid, 3-methylsalicylic acid, 4-methylsalicylic acid, 2,4-dihydroxybenzoic acid, 5-methylsalicylic acid, 2,5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3-hydroxy-p-toluic acid, 3,5-dihydroxybenzoic acid 3,4-dihydroxybenzoic acid, 3-hydroxy-o-toluic acid, caffeic acid, trans-p-coumaric acid, trans-o-coumaric acid, trans-m-coumaric acid, α-cyano-4-hydroxy Cinnamic acid, 3,4-dihydroxymandelic acid, homogentisic acid, diphenolic acid, 3,4-dihydride Xyphenylacetic acid, 3,5-dimethoxy-4-hydroxycinnamic acid, 3,5-dimethoxy-4-hydroxycinnamic acid, gentizulinic acid, trans-ferulic acid, DL-4-hydroxy-3-methoxymandelic acid, 4 -Hydroxyphenylacetic acid, N- (4-hydroxyphenyl) glycine, 4-hydroxyphenylpyruvic acid, 4-hydroxy-3-methoxyphenylacetic acid, 2-hydroxyphenylacetic acid, 3-hydroxyphenylacetic acid, 3-hydroxy-4- Methoxycinnamic acid, 4-hydroxy-3-methoxyphenylpyruvic acid, 3- (4-hydroxyphenyl) propionic acid, 2- (4-hydroxyphenyl) glycine, 2- (4-hydroxyphenoxy) propionic acid, 6- Hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (4-Hydroxyphenoxy) acetic acid, 2- (4-hydroxyphenyl) propionic acid, 3- (4-hydroxy-3-methoxyphenyl) propionic acid, DL-thyronine, tyrosine and their derivatives, etc. It is not limited.

  Among these compounds, compounds in which a carboxyl group is bonded to an aliphatic carbon are particularly preferable. When a compound in which a carboxyl group is bonded to an aliphatic carbon is used, the steric degree of freedom of the carboxyl is increased, and even after the phenol group is bonded to the epoxy group of the epoxy resin (A), a certain amount is obtained from the crosslinked structure. Since the distance can be maintained, it can work more efficiently for improving the adhesion between the resin and the lead frame.

  The content of the organic compound (D) having a phenolic hydroxyl group and a carboxyl group used in the present invention is not particularly limited, but is preferably 0.01% by mass or more and 1% by mass or less of the entire epoxy resin composition. 02 mass% or more and 0.5 mass% or less are more preferable. When the content is within the above range, excellent solder resistance can be obtained without causing an increase in elastic modulus.

  The epoxy resin composition of the present invention can further use a curing accelerator (E). The curing accelerator (E) may be anything that promotes the reaction between the epoxy resin (A) and the curing agent (B), and the one used in general epoxy resin compositions for semiconductor encapsulation should be used. Can do. Specific examples include phosphorus-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; 1,8-diazabicyclo (5 , 4, 0) Undecene-7, nitrogen atom-containing compounds such as benzyldimethylamine and 2-methylimidazole. These curing accelerators (E) may be used alone or in combination of two or more. Among these, a phosphorus atom-containing compound is preferable, and in particular, the tetra-substituted phosphonium compound can be improved in view of the fact that the fluidity can be improved by lowering the viscosity of the epoxy resin composition for semiconductor encapsulation, and further, the curing rising speed. In view of the low thermal modulus of the cured epoxy resin composition for semiconductor encapsulation, an adduct of a phosphobetaine compound, a phosphine compound and a quinone compound is preferable, and the latent curability is also considered. Then, the adduct of a phosphonium compound and a silane compound is preferable.

  Examples of the organic phosphine include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; and a third phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine.

  Examples of the tetra-substituted phosphonium compound include compounds represented by the following general formula (4).

  Although the compound represented by General formula (4) is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (4) can be precipitated. In the compound represented by the general formula (4), R7, R8, R9 and R10 bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols, and A Is preferably an anion of the phenol.

Examples of the phosphobetaine compound include compounds represented by the following general formula (5).

  The compound represented by the general formula (5) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt. However, the present invention is not limited to this.

Examples of the adduct of a phosphine compound and a quinone compound include compounds represented by the following general formula (6).

  The phosphine compound used as an adduct of a phosphine compound and a quinone compound has no substitution on aromatic rings such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, tris (benzyl) phosphine, etc. Or those having a substituent such as an alkyl group or an alkoxyl group are preferred, and examples of the alkyl group and alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.

  In addition, examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone, and anthraquinones. Among them, p-benzoquinone is preferable from the viewpoint of storage stability.

  As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both organic tertiary phosphine and benzoquinone. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, the present invention is not limited to this.

  In the compound represented by the general formula (6), R11, R12 and R13 bonded to the phosphorus atom are phenyl groups, and R14, R15 and R16 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl A compound to which phosphine has been added is preferred in that it reduces the elastic modulus of the cured resin thermal composition when heated.

Examples of the adduct of the phosphonium compound and the silane compound include compounds represented by the following general formula (7).

  In the general formula (7), examples of R17, R18, R19, and R20 include phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group, and the like. Among these, an aromatic group having a substituent such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, or the like. A substituted aromatic group is more preferred.

  Moreover, in General formula (7), X2 is an organic group couple | bonded with Y2 and Y3. Similarly, X3 is an organic group bonded to the groups Y4 and Y5. Y2 and Y3 are groups formed by proton-donating substituents releasing protons, and groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate structure. Similarly, Y4 and Y5 are groups formed by proton-donating substituents releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. The groups Y2 and Y3 may be the same or different from each other, and the groups Y2, Y3, Y4, and Y5 may be the same or different from each other.

  The groups represented by -Y2-X2-Y3- and -Y4-X3-Y5- in general formula (7) are composed of groups in which a proton donor releases two protons. Examples of proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, -Hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin and the like can be mentioned. Among these, catechol, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferable.

  Z1 in the general formula (7) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Group and aliphatic groups such as octyl group; aromatic groups such as phenyl group, benzyl group, naphthyl group and biphenyl group; having reactive substituents such as glycidyloxypropyl group, mercaptopropyl group, aminopropyl group and vinyl group An organic group and the like can be mentioned, and among these, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable from the viewpoint of thermal stability.

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

  As for the compounding quantity of the hardening accelerator (E) which can be used by this invention, 0.1 to 1 mass% is preferable in the resin composition for whole semiconductor sealing. When the lower limit of the blending amount of the curing accelerator (E) is within the above range, there is little possibility of causing a decrease in curability. Moreover, there is little possibility of causing the fall of fluidity | liquidity in the upper limit of the compounding quantity of a hardening accelerator (E) being in the said range.

  In the present invention, a silane coupling agent (F) can be further used. The silane coupling agent (F) is preferably an epoxy silane, amino silane, ureido silane, mercapto silane, etc., but is not particularly limited thereto, and reacts between the epoxy resin and the inorganic filler, and the epoxy resin and the inorganic filler. What is necessary is just to improve the interface strength. Further, a compound (G) (hereinafter also referred to as “compound (G)”) in which a hydroxyl group is bonded to two or more adjacent carbon atoms constituting an aromatic ring, which will be described later, is the silane coupling agent (F). The silane coupling agent (F) is also effective for obtaining the effect of the compound (G) sufficiently because it has the effect of lowering the viscosity of the resin composition for encapsulating semiconductors and improving the fluidity. It is. Examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Examples of aminosilane include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β- Aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltri Ethoxysilane, N- (6-aminohexyl) -3-aminopropyltrimethoxysilane, N- (3- (trimethoxysilyl) propyl) -1,3-benzenedimethanane, and the like. Examples of ureidosilane include γ-ureidopropyltriethoxysilane, Hexamethyldisilazane and the like can be mentioned, and examples of mercaptosilane include γ-mercaptopropyltrimethoxysilane and the like. These silane coupling agents (F) may be used alone or in combination of two or more.

  The blending amount of the silane coupling agent (F) that can be used in the present invention is preferably 0.01% by mass or more and 1% by mass or less in the resin composition for encapsulating all semiconductors, and 0.05% by mass. As mentioned above, it is more preferable that it is 0.8 mass% or less, and it is especially preferable that it is 0.1 mass% or more and 0.6 mass% or less. When the lower limit value of the amount of the silane coupling agent (F) is within the above range, a sufficient viscosity reduction and fluidity improvement effect of the resin composition for semiconductor encapsulation can be obtained due to a synergistic effect with the compound (G). Obtainable. Moreover, if the lower limit of the compounding amount of the silane coupling agent (F) is within the above range, there is a risk of causing a decrease in solder resistance in the semiconductor device due to a decrease in the interface strength between the epoxy resin and the inorganic filler. Few. Moreover, if the upper limit of the compounding quantity of a silane coupling agent (F) is in the said range, there exists a possibility of causing the fall of solder resistance by the water absorption of the hardened | cured material of the resin composition for semiconductor sealing increasing. Few.

  In the present invention, a compound (G) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring can be used. A compound (G) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring (hereinafter also referred to as “compound (G)”) is used as a resin composition for semiconductor encapsulation. It has the effect of lowering the viscosity of the product and improving the fluidity. As the compound (G), a monocyclic compound represented by the following general formula (8) or a polycyclic compound represented by the following general formula (9) can be used. It may have a substituent.

  Specific examples of the monocyclic compound represented by the general formula (8) include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof. Specific examples of the polycyclic compound represented by the general formula (9) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Among these, a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring is preferable because of easy control of fluidity and curability. In consideration of volatilization in the kneading step, it is more preferable that the mother nucleus is a compound having a low volatility and a highly stable weighing naphthalene ring. In this case, specifically, the compound (G) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof. These compounds (G) may be used individually by 1 type, or may use 2 or more types together.

  The compounding amount of the compound (G) is preferably 0.01% by mass or more and 1% by mass or less, and 0.03% by mass or more and 0.8% by mass or less in the total semiconductor sealing resin composition. It is more preferable that it is 0.05 mass% or more and 0.5 mass% or less. When the lower limit value of the compounding amount of the compound (G) is within the above range, the resin composition for semiconductor encapsulation has sufficient viscosity reduction and fluidity improvement effect due to a synergistic effect with the silane coupling agent (F). Obtainable. Moreover, there exists little possibility of causing the fall of sclerosis | hardenability of a resin composition for semiconductor sealing, and the fall of physical property of hardened | cured material as the upper limit of the compounding quantity of a compound (G) is in the said range.

  A release agent is used in the epoxy resin composition of the present invention as necessary. As the mold release agent, conventionally known ones can be used, and examples thereof include higher fatty acids, higher fatty acid metal salts, ester waxes, polyethylene waxes, and the like. You may use together a seed or more. Of these, polyethylene waxes are preferable, and it is more preferable to use polyethylene wax and montanic acid ester wax in combination. The compounding amount of the release agent is not particularly limited, but is preferably 0.05% by mass or more and 3% by mass or less, and preferably 0.1% by mass or more and 1% by mass or less of the entire epoxy resin composition. Is more preferable. If the blending amount is less than the above lower limit value, the releasability may be lowered, and if it exceeds the upper limit value, the adhesion and solder resistance may be lowered.

  In the epoxy resin composition of the present invention, an ion trap agent is used as necessary. As the ion trapping agent, conventionally known ones can be used. Examples thereof include hydrotalcites and hydrated oxides of elements selected from magnesium, aluminum, bismuth, titanium, and zirconium. It may be used alone or in combination of two or more. Of these, hydrotalcites are preferred. Although the compounding quantity of an ion trap agent is not restrict | limited in particular, 0.05 mass% or more and 3 mass% or less of the whole epoxy resin composition are preferable, More preferably, they are 0.1 mass% or more and 1 mass% or less. When the blending amount is within the above range, sufficient ion scavenging action is exhibited and there is little adverse effect on other material properties.

  The epoxy resin composition of the present invention comprises an epoxy resin (A), a phenol resin (B), an inorganic filler (C), and an organic compound (D) having a phenolic hydroxyl group and a carboxyl group as main components, and as necessary. , A curing accelerator (E), a silane coupling agent (F), a compound (G) in which a hydroxyl group is bonded to two or more adjacent carbon atoms constituting an aromatic ring, a release agent, an ion trapping agent, etc. Furthermore, colorants such as carbon black, low stress additives such as silicone oil and rubber, flame retardants such as brominated epoxy resin, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, etc. These additives may be appropriately blended.

  In addition, the epoxy resin composition of the present invention is obtained by mixing the raw materials sufficiently uniformly using a mixer or the like, and then melt-kneading with a hot roll or a kneader, pulverizing after cooling, etc. as necessary. What adjusted the dispersion degree etc. suitably can be used.

  Next, a semiconductor device will be described. In order to manufacture the semiconductor device of the present invention by sealing various electronic components such as semiconductor elements using the epoxy resin composition described above, a conventional molding method such as transfer molding, compression molding, injection molding or the like is used. A semiconductor device can be obtained by curing.

  The semiconductor element that performs sealing in the present invention is not particularly limited, and examples thereof include an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.

  Although it does not specifically limit as a semiconductor device of this invention, For example, a dual in-line package (DIP), a chip carrier with a plastic lead (PLCC), a quad flat package (QFP), a small outline package ( SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package (TCP), Ball Grid Array ( BGA), chip size package (CSP) and the like.

  A semiconductor device sealed by a molding method such as a transfer mold is mounted on an electronic device or the like as it is or after being completely cured at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours. Is done.

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

  Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto. The blending ratio was part by mass.

Example 1
Epoxy resin 1: epoxy resin represented by the following formula (10) (phenol aralkyl type epoxy resin having a biphenylene skeleton: manufactured by Nippon Kayaku Co., Ltd., trade name: NC3000P, softening point: 58 ° C., epoxy equivalent: 273, formula (10 ), The average value of n is 2.3.)
6.34 parts by mass

無機充填材１：溶融球状シリカ（平均粒径３０μｍ） ８８．００質量部
化合物Ｄ１：３−（４−ヒドロキシフェニル）プロピオン酸（東京化成工業（株）製、分子量：１６６．１７） ０．１０質量部
硬化促進剤１：トリフェニルホスフィン ０．２０質量部
シランカップリング剤１：Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン
０．１０質量部
シランカップリング剤２：３−グリシドキシプロピルトリメトキシシラン
０．１０質量部
シランカップリング剤３：３−メルカプトプロピルトリメトキシシラン
０．１０質量部
化合物Ｇ１：２，３−ジヒドロキシナフタレン ０．１０質量部
離型剤１：モンタン酸エステル系ワックス（クラリアントジャパン（株）製、商品名リコルブＷＥ４） ０．３０質量部
イオントラップ剤１：ハイドロタルサイト（協和化学工業（株）製、商品名ＤＨＴ−４Ｈ） ０．２０質量部
着色剤１：カーボンブラック ０．３０質量部
をミキサーにて常温混合し、８０〜１００℃の加熱ロールで溶融混練し、冷却後粉砕し、エポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物を用いて、以下の方法で評価を行った。評価結果を表１に示す。 Curing agent 1: Phenol aralkyl resin having a biphenylene skeleton represented by the following formula (11) (Maywa Kasei Co., Ltd., trade name: MEH-7851SS, softening point: 65 ° C., hydroxyl equivalent: 204, m in formula (11) The average value is 1.6.)
4.26 parts by mass

Inorganic filler 1: fused spherical silica (average particle size 30 μm) 88.00 parts by mass Compound D1: 3- (4-hydroxyphenyl) propionic acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 166.17) 0.10 Mass parts Curing accelerator 1: Triphenylphosphine 0.20 parts by mass Silane coupling agent 1: N-phenyl-γ-aminopropyltrimethoxysilane
0.10 parts by mass Silane coupling agent 2: 3-glycidoxypropyltrimethoxysilane
0.10 parts by mass Silane coupling agent 3: 3-mercaptopropyltrimethoxysilane
0.10 parts by mass Compound G1: 2,3-dihydroxynaphthalene 0.10 parts by mass Mold release agent 1: Montanate ester wax (manufactured by Clariant Japan Co., Ltd., trade name Recolve WE4) 0.30 parts by mass Ion trapping agent 1: Hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., trade name DHT-4H) 0.20 parts by mass Colorant 1: Carbon black 0.30 parts by mass is mixed at room temperature with a mixer and heated at 80 to 100 ° C. The mixture was melt-kneaded with a roll, cooled and pulverized to obtain an epoxy resin composition. Evaluation was performed by the following method using the obtained epoxy resin composition. The evaluation results are shown in Table 1.

1. Spiral flow Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a mold for spiral flow measurement conforming to EMMI-1-66, a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, The epoxy resin composition was injected under a pressure holding time of 120 seconds, and the flow length was measured. The unit was cm.

2. Curability (curing torque ratio)
Using a curast meter (Orientec Co., Ltd., JSR curast meter IVPS type), the torque value after 60 seconds at 175 ° C. was divided by the torque value after 300 seconds. The larger this value, the better the curability. The unit is%.

3. Solder resistance 1
Using a low-pressure transfer molding machine (Daiichi Seiko Co., Ltd., GP-ELF), a chip (chip size 6.0 mm × 6. 6) under the conditions of a molding temperature of 175 ° C., an injection pressure of 8.3 MPa, and a curing time of 120 seconds. An epoxy resin composition is injected into a mold cavity in which a Cu lead frame having a thickness of 0 mm × 0.35 mm) is inserted and cured, and then 80-pin QFP (Quad Flat Package, package size: 14 mm × 20 mm × 2 mm thickness) ) And heat-treated as an after bake at 175 ° C. for 8 hours. Then, after performing the humidification process for 120 hours at 60 degreeC and 60% of relative humidity, the IR reflow process of 260 degreeC was performed. Peeling and cracks inside the package were confirmed with an ultrasonic flaw detector (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., mi-scope hyper II), and any one of either peeling or cracking was regarded as defective. The number of defective packages among the 10 packages evaluated is shown.

4). Solder resistance 2
Using a low-pressure transfer molding machine (Daiichi Seiko Co., Ltd., GP-ELF), a chip (chip size 6.0 mm × 6. 6) under the conditions of a molding temperature of 175 ° C., an injection pressure of 8.3 MPa, and a curing time of 120 seconds. An epoxy resin composition is injected into a mold cavity in which a Cu lead frame having a thickness of 0 mm × 0.35 mm) is inserted and cured, and then 80-pin QFP (Quad Flat Package, package size: 14 mm × 20 mm × 2 mm thickness) ) And heat-treated as an after bake at 175 ° C. for 8 hours. Then, after performing the humidification process for 120 hours at 85 degreeC and 60% of relative humidity, IR reflow process of 260 degreeC was performed. Peeling and cracking inside the package were confirmed with an ultrasonic flaw detector (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., mi-scope hyper II), and any of the peeling and cracking was regarded as defective. The number of defective packages among the 10 packages evaluated is shown.

Examples 2-11, Comparative Examples 1-4
According to the composition of Table 1, an epoxy resin composition was produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.
The components used in other than Example 1 are shown below.
Epoxy resin 2: biphenyl type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name YX-4000, epoxy equivalent 190, melting point 105 ° C.)
Curing agent 2: Phenol aralkyl resin having a phenylene skeleton (manufactured by Mitsui Chemicals, trade name: XLC-LL, hydroxyl group equivalent: 165, softening point: 79 ° C.)
Compound D2: 4-hydroxy-3-methoxyphenylacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 182.17)
Compound D3: trans-p-coumaric acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 164.16)
Compound D4: 4-hydroxybenzoic acid (Tokyo Chemical Industry Co., Ltd., molecular weight: 138.12)
Comparative compound 1: phenol (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 94.11)
Comparative compound 2: Propionic acid (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: 74.08)

  As is apparent from Table 1, the semiconductor package molded using the epoxy compositions obtained in Examples 1 to 11 was excellent in solder resistance.

  As described above, in all of the examples according to the present invention, an epoxy resin composition for semiconductor encapsulation having good solder resistance that does not cause peeling or cracking even by high-temperature solder processing corresponding to lead-free solder is obtained. is there.

  According to the present invention, when a semiconductor element mounted on a lead frame such as copper or 42 alloy is sealed, it has good solder resistance that does not cause peeling or cracking even by high-temperature solder processing corresponding to lead-free solder. Since the epoxy resin composition for semiconductor sealing which has is obtained, it can be used suitably especially for manufacture of a surface mount type semiconductor device.

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

Claims (9)

An epoxy resin composition used for semiconductor encapsulation,
(A) an epoxy resin;
(B) a curing agent;
(C) an inorganic filler;
(D) an organic compound having a phenolic hydroxyl group and a carboxyl group;
An epoxy resin composition comprising: The epoxy resin composition according to claim 1, wherein the organic compound (D) having a phenolic hydroxyl group and a carboxyl group is a compound represented by the following general formula (1).

(In the formula, R1 is a bond selected from a single bond, a double bond, a triple bond, an ether bond, a sulfone bond, an ester bond, an amide bond, an imide bond, a urethane bond, and a ketone bond, or an aromatic ring or an aliphatic ring. Or an organic group containing a heterocyclic ring or an aliphatic group, R2 is hydrogen or an organic group having 1 to 14 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a nitro group, an aldehyde group, or a condensed ring. Represents an aromatic ring, an aliphatic ring, or a heterocyclic ring, which may be the same or different, and a is an integer of 1 to 4.   The epoxy resin composition according to claim 2, wherein the organic compound (D) having a phenolic hydroxyl group and a carboxyl group has a molecular weight of less than 500.   The epoxy resin composition according to claim 3, wherein a carboxyl group of the organic compound (D) having a phenolic hydroxyl group and a carboxyl group is a carboxyl group bonded to an aliphatic carbon. The epoxy resin composition according to claim 4, wherein the (A) epoxy resin contains an epoxy resin represented by the following general formula (2).

The epoxy resin composition according to any one of claims 1 to 5, wherein the (B) curing agent contains a phenol resin represented by the following general formula (3).

  The epoxy resin composition according to any one of claims 1 to 6, further comprising (E) a curing accelerator.   Furthermore, (F) Silane coupling agent and / or (G) The compound which the hydroxyl group couple | bonded with the 2 or more adjacent carbon atom which comprises an aromatic ring respectively is included. Epoxy resin composition.   A semiconductor device, wherein a semiconductor element is sealed with a cured product of the epoxy resin composition according to any one of claims 1 to 8.

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