JP2006265415A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition having good curability, preservability and fluidity and to provide a semiconductor device having excellent solder crack resistance and reliability of moisture resistance. <P>SOLUTION: The epoxy resin composition comprises an epoxy resin (A), a phenol resin (B) and a curing accelerator (C). The epoxy resin composition contains boric acid or a boric ester (D) and a compound (E) having ≥2 proton-donative substituents forming a chelate ring with a boron atom and having a substituent other than the proton-donative substituents or no substituent in the molecule. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

Recently, semiconductor devices, productivity, cost, since it is excellent in balance such as reliability, being produced by sealing a semiconductor element using the epoxy resin composition has become mainstream. With the downsizing and thinning of semiconductor devices, there is a demand for further lowering the viscosity and increasing the strength of the epoxy resin composition for sealing. Against this background, the recent trend of epoxy resin compositions is becoming more likely to apply lower viscosity resins and incorporate more inorganic fillers. Further, as a new movement, when mounting a semiconductor device, the use of lead-free solder having a higher melting point than before is increasing. By applying this solder, it is necessary to raise the mounting temperature by about 20 ° C. compared to the conventional case, and there is a problem that the reliability of the semiconductor device after mounting is remarkably lowered compared to the current situation. For these reasons, the demand for improving the reliability of semiconductor devices by increasing the level of epoxy resin compositions has been accelerated, and it has spurred the reduction of resin viscosity and the increase of inorganic fillers. Yes.

  In order to maintain a low viscosity and a high fluidity during molding, a resin having a low melt viscosity is used (for example, refer to Patent Document 1), and an inorganic filler is used to increase the blending amount of the inorganic filler. A method is known in which surface treatment is performed with a silane coupling agent (see, for example, Patent Document 2). However, many of these methods alone satisfy only one of various required characteristics, and no method that satisfies all requirements and can be applied in a wide range has not yet been found. There has been a demand for a further technique that does not sufficiently lower the melt viscosity at the time of molding, does not impair the fluidity and curability, increases the blending amount of the inorganic filler, and satisfies the reliability.

  Further, in the presence of a curing accelerator that is generally blended into the resin composition, there is a problem that the progress of the curing reaction of the epoxy resin at the time of low-temperature storage is accelerated and the storage stability of the sealing material is lowered. For this reason, strict quality control when mixing various components, storage and transportation at low temperatures, and strict control of molding conditions are essential, and handling becomes extremely complicated, improving reliability. In addition to this, improvement in preservability has been demanded for the purpose of improving handling during distribution and storage.

JP-A-7-130919 (pages 2 to 5) JP-A-8-20673 (pages 2 to 4) JP 2000-17054 A (2-5) JP 2001-98053 A (pages 2 to 4)

  This invention provides the resin composition for semiconductor sealing excellent in fluidity | liquidity and storage stability, without impairing the sclerosis | hardenability at the time of shaping | molding.

  As a result of intensive studies to solve the above-described problems, the present inventors have found the following matters and have completed the present invention.

  That is, by adding boric acid or a boric acid ester and a compound (F) having a proton-donating substituent capable of forming a chelate ring with two or more boron atoms in the molecule to the epoxy resin composition, Even if the semiconductor device, which is excellent in fluidity and storage stability of the composition and encapsulates electronic parts such as semiconductor elements with a cured product of the above-mentioned epoxy resin composition, is exposed to high temperatures, it is cracked. And found that defects such as peeling and peeling hardly occur.

  That is, the present invention is achieved by the following (1) to (7).

(1) An epoxy resin composition comprising an epoxy resin (A), a phenol resin (B), and a curing accelerator (C), wherein boric acid or a boric acid ester (D) and a boron atom in the molecule are chelated An epoxy resin composition comprising a compound (E) having two or more proton-donating substituents capable of forming a ring and having or not having a substituent other than the proton-donating substituent .

(2) Compound (E) having two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule, and having or not having a substituent other than the proton-donating substituent The epoxy resin composition according to claim 1, wherein the proton-donating substituent has a hydroxyl group, a carboxyl group, and a mercapto group.

(3) Compound (E) having two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule, and having or not having a substituent other than the proton-donating substituent The epoxy resin composition according to claim 1 or 2, wherein two or more proton donating substituents are adjacent to each other on the aromatic ring.

(4) Compound (E) having two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule, and having or not having a substituent other than the proton-donating substituent The epoxy resin composition according to any one of claims 1 to 3, which has the proton-donating substituent on a benzene ring, a naphthalene ring, or a biphenyl ring.

(5) Compound (E) having two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule, and having or not having a substituent other than the proton-donating substituent The epoxy resin composition for semiconductor encapsulation according to claim 4, which has two hydroxyl groups on the biphenyl ring.

(6) The epoxy resin composition according to any one of claims 1 to 5, wherein the epoxy resin (A) contains at least one of the epoxy resins represented by the general formula (1) or (2) as a main component.

[Wherein R ¹ , R ² , R ³ and R ⁴ each represents one selected from a hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group and a halogen atom, They may be the same or different. ]

[Wherein, R ^{5 to} R ¹² each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, a is an integer of 1-10. ]

(7) The epoxy resin composition according to any one of claims 1 to 6, wherein the phenol resin (B) contains at least one of the phenol resins represented by the general formula (3) or (4) as a main component.

[In formula, R < ¹³ > -R < ¹⁶ > represents 1 type selected from a hydrogen atom, a C1-C4 alkyl group, and a halogen atom, respectively, and may mutually be same or different. However, b is an integer of 1-10. ]

[In formula, R < ¹⁷ > -R < ²⁴ > represents 1 type selected from a hydrogen atom, a C1-C4 alkyl group, and a halogen atom, respectively, and may mutually be same or different. However, c is an integer of 1-10. ]

(8) The epoxy resin composition according to any one of claims 1 to 7, comprising an inorganic filler.

(9) The epoxy resin composition according to any one of claims 1 to 8, wherein the epoxy resin composition is melt-mixed at a temperature equal to or higher than a softening point of the epoxy resin (A) or the phenol resin (B). .

(10) A semiconductor device comprising a semiconductor element sealed using the epoxy resin composition according to any one of claims 1 to 9.

  The epoxy resin composition of the present invention is excellent in fluidity and storage stability, and the semiconductor device encapsulated with the epoxy resin composition of the present invention is cracked or peeled even when exposed to high temperatures. Defects such as the above are hardly generated and the solder crack resistance is excellent.

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

The epoxy resin composition of this embodiment is
A resin composition mainly composed of an epoxy resin (A), a phenol resin (B), and a curing accelerator (C), wherein boric acid or boric acid ester (D) and a boron atom and a chelate ring are present in the molecule It includes a compound (E) having two or more proton-donating substituents that can be formed and having or not having a substituent other than the proton-donating substituent. Such an epoxy resin composition is excellent in fluidity and storage stability. In addition, a semiconductor device encapsulated with the epoxy resin composition is less susceptible to defects such as cracks and peeling even when exposed to high temperatures, and has excellent solder crack resistance.

  Hereinafter, each component will be sequentially described.

[Compound (A)]
The epoxy resin (A) used in the present invention is not particularly limited. For example, bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and brominated bisphenol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl. Type phenolic resin, stilbene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin and dihydroxybenzene type epoxy resin, etc. Epoxy compounds produced by reacting epichlorohydrin with hydroxyl groups such as epoxides, epoxy resins obtained by oxidizing olefins with peracids, glycidyl ester epoxy resin Resin and glycidylamine type epoxy resins may be used singly or in combination of two or more of them. In consideration of moisture resistance reliability as an epoxy resin composition for semiconductor encapsulation, it is preferable that Na ions and Cl ions, which are ionic impurities, be as small as possible. From the viewpoint of curability, the epoxy equivalent is 100 to 500 g / eq. Is preferred.

  Among these, the compound (A) particularly includes one or both of the biphenyl type epoxy resin represented by the general formula (1) and the biphenyl aralkyl type epoxy resin represented by the general formula (2). It is preferable to use the main component. Thereby, the fluidity at the time of molding of the epoxy resin composition (for example, at the time of manufacturing a semiconductor device) is improved, and the solder crack resistance of the obtained semiconductor device is further improved.

  Here, “improvement of solder crack resistance” means that the obtained semiconductor device is exposed to high temperatures in, for example, a solder dipping or solder reflow process, even if the cured product is cracked or peeled off. This means that the occurrence of defects is less likely to occur.

Here, the substituents R ^{1 to} R ⁴ in the biphenyl type epoxy resin represented by the general formula (1) are each a hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom. Represents one selected from the above, and these may be the same or different.

As these substituents R ^{1 to} R ⁴ , in addition to a hydrogen atom and a phenyl group, for example, a chain or cyclic alkyl group having 1 to 6 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, and Examples of the halogen atom include a chlorine atom and a bromine atom. Among these, a methyl group is particularly preferable. Thereby, the melt viscosity of the epoxy resin composition is lowered, and the handling thereof becomes easy, for example, at the time of manufacturing a semiconductor device. In addition, since the water absorption of the cured product is reduced, the obtained semiconductor device is preferably prevented from deterioration over time (for example, occurrence of disconnection) of the internal members, and the moisture resistance reliability is further improved. .

In addition, the substituents R ^{5 to} R ¹² in the biphenyl aralkyl type epoxy resin represented by the general formula (2) represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, These may be the same as or different from each other.

Examples of these substituents R ^{5 to} R ¹² include a methyl group, an ethyl group, a propyl group, a butyl group, a chlorine atom, and a bromine atom. Among these, a hydrogen atom or a methyl group is particularly preferable. Is preferred. As a result, the melt viscosity of the epoxy resin composition is reduced, and for example, when the semiconductor device is manufactured, the handling becomes easy, and the moisture resistance reliability of the semiconductor device is further improved.

  Moreover, a in the said General formula (2) represents the average repeating number of an epoxy resin unit. That is, a is preferably in the range of 1 to 10, more preferably about 1 to 5. By setting a in the above range, the fluidity of the epoxy resin composition is further improved.

[Compound (B)]
The phenol resin (B) used in the present invention functions (functions) as a curing agent for the compound (A).

  Although it does not specifically limit as this compound (B), For example, phenol novolak resin, cresol novolak resin, bisphenol resin, phenol aralkyl resin, biphenyl aralkyl resin, trisphenol resin, xylylene modified novolak resin, terpene modified novolak resin and dicyclo A pentadiene-modified phenol resin can be used, and one or more of these can be used in combination.

  Among these, the compound (B) is mainly composed of one or both of the phenol aralkyl resin represented by the general formula (3) and the biphenyl aralkyl resin represented by the general formula (4). It is preferable to use those that do. Thereby, the fluidity at the time of molding of the epoxy resin composition (for example, during the production of a semiconductor device) is improved, and the solder crack resistance and moisture resistance reliability of the obtained semiconductor device are further improved.

Here, the substituents R ^{13 to} R ¹⁶ in the phenol aralkyl resin represented by the general formula (3) and the substituents R ^{17 to} R ²⁴ in the biphenyl aralkyl resin represented by the general formula (4) are: Each represents one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and a halogen atom, and these may be the same or different from each other.

Examples of these substituents R ^{13 to} R ¹⁶ and R ^{17 to} R ²⁴ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a chlorine atom, and a bromine atom. Among these, a hydrogen atom or a methyl group is particularly preferable. Since such a phenol resin has a low melt viscosity per se, even when contained in the epoxy resin composition, the melt viscosity of the epoxy resin composition can be kept low. Moreover, the handling becomes easy. Moreover, the water absorption (hygroscopicity) of the cured product of the epoxy resin composition (obtained semiconductor device) is reduced, the moisture resistance reliability is further improved, and the solder crack resistance is further improved.

  Moreover, b in the said General formula (3) and c in the said General formula (4) each represent the average repeating number of a phenol resin unit. That is, b and c each preferably have a range of 1 to 10, more preferably about 1 to 5. By setting each of b and c within the above ranges, a decrease in fluidity of the epoxy resin composition is preferably prevented or suppressed.

[Curing accelerator (C)]
In the present invention, a curing accelerator can be added for the purpose of accelerating the curing reaction of the epoxy resin (A) and the phenol resin (B). The curing accelerator (C) is not limited as long as it has an action (function) that can accelerate the curing reaction of the epoxy resin composition.

Examples of these curing accelerators include triphenylphosphine, tris (4-tolyl) phosphine, tris (4-hydroxyphenyl) phosphine, tris (4-methylphenyl) phosphine, and tris (4-methoxyphenyl) phosphine). Tertiary phosphines, amidines such as 1,8-diazabicyclo (5,4,0) -7-undecene and 1,5-diazabicyclo (4,3,0) -5-nonene, 2-methylimidazole, 2- Examples include imidazoles such as phenylimidazole and 2-phenyl-4-methylimidazole, quaternary phosphonium salts such as tetraphenylphosphonium tetraphenylborate, and the like, which can be used alone or in combination of two or more.
In addition, the said hardening accelerator is an example and is not limited to these at all.

  In the epoxy resin composition of the present invention, the content (blending amount) of the curing accelerator (C) is not particularly limited, but is preferably about 0.01 to 10% by weight with respect to the entire composition. It is more preferably about 0.05 to 5% by weight. Thereby, the sclerosis | hardenability, preservability, fluidity | liquidity, and hardened | cured material characteristic of an epoxy resin composition are expressed with sufficient balance.

[Boric acid or boric acid ester (D)]
The boric acid used in the present invention includes metaboric acid, tetraboric acid and the like in addition to orthoboric acid usually called boric acid.
Examples of boric acid esters include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-n-octyl borate and stearyl borate. Alkoxy esters of acids, triaryloxy esters of boric acid such as triphenyl borate, tri-o-tolyl borate and tris (4-chlorophenyl) borate, and alkoxy esters of boric acid and boric acid Examples of the triaryloxyesters may include, but are not limited to, mono and di hydrolysates.
Do these boric acids or boric acid esters (D) have two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule, and have a substituent other than the proton-donating substituents? By reacting in the epoxy resin composition with or without the compound (E), a chelate-type borate anion is formed to form a curing accelerator and a salt, thereby effectively suppressing the low temperature activity of the curing accelerator. As a result, good fluidity and storage stability are imparted.
From the viewpoint of low-temperature activity suppression effect, uniform dispersibility, and cost, tri-substituted boric acid esters of lower alkoxy groups such as trimethyl borate, triethyl borate, tri-n-propyl borate, tri-n-butyl borate, etc. preferable.

[Component (E)]
The compound (E) having two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule and having or not having a substituent other than the proton-donating substituent includes carboxyl Those having a proton-donating substituent such as a group, a hydroxyl group and a mercapto group are preferred, and examples thereof include carboxylic acids, phenol compounds, alcohols, thiols and the like having two or more of these groups in the close position. Moreover, it is preferable to have these groups on aromatic rings, such as a benzene ring, a naphthalene ring, and a biphenyl ring. Specific examples include catechol, 2,3-dihydroxynaphthalene, pyrogallol, gallic acid having two or more hydroxyl groups at adjacent positions on the aromatic ring and deprotonating to form a 5-membered ring chelate with a boron atom. , Polyphenols such as methyl gallate, ethyl gallate, octyl gallate, and tannic acid, have a carboxyl group and a hydroxyl group at adjacent positions on the aromatic ring, and deprotonate to form a boron atom and a six-membered ring chelate Salicylic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, protocatechuic acid, 3,5-dihydroxy-2-naphthoic acid, 2-hydroxybiphenyl-3-carboxylic acid Having two hydroxyl groups adjacent to the single bond of an aromatic hydroxycarboxylic acid such as biphenyl ring or binaphthyl ring, 2,2'-biphenol, 1,1'-bee 2-naphthol, which forms protonated to form a 7-membered ring chelate with a boron atom, and other 2-hydroxybenzyl which forms a 6-membered ring chelate with a boron atom by deprotonation Alcohol, thiosalicylic acid, 3-hydroxypicolinic acid, 2-hydroxynicotinic acid, tropic acid, 2,3-dihydroxypyridine, 2,3-dihydroxyquinoxaline, deprotonated to form boron atom and 5-membered ring chelate, 4- Examples include methyl-1,2-benzenethiol, chloranilic acid, mandelic acid, inositol, ethylene glycol, propylene glycol, α-diphenylglyoxime that forms a seven-membered ring chelate with boron atom by deprotonation, etc. It is not limited to.
These compounds (E) react with boric acid or borate ester (D) in the epoxy resin composition to form a chelate-type borate anion, thereby forming a curing accelerator and a salt, thereby reducing the low temperature of the curing accelerator. The activity is effectively suppressed, and as a result, good fluidity and storage stability are imparted.
Among these compounds (E), those having a hydroxyl group as the proton-donating substituent are preferred, and those having two proton-donating substituents on the biphenyl ring are preferred, and are stable against heat and hydrolysis. 2,2′-biphenol and hydroxynaphthoic acids are preferred from the viewpoints of properties, low viscosity characteristics, and curability.

[Inorganic filler]
For example, when the epoxy resin composition of the present invention is used in a semiconductor device, the inorganic filler is blended (mixed) in the epoxy resin composition for the purpose of reinforcing the obtained semiconductor device. There is no restriction | limiting in particular about, What can generally be used for the sealing material can be used.

  Specific examples of the inorganic filler include, for example, fused crushed silica, fused silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, talc, clay, and glass fiber. These can be used alone or in combination of two or more. Among these, fused silica is particularly preferable. Since fused silica is poor in reactivity with the curing accelerator of the present invention, it is possible to prevent the curing reaction of the epoxy resin composition from being inhibited even when a large amount is blended (mixed) in the epoxy resin composition. Can do. Moreover, the reinforcement effect of the semiconductor device obtained improves by using a fused silica as an inorganic filler.

  Moreover, as a shape of an inorganic filler, what kind of things, such as a granular form, a lump shape, and a scale shape, may be sufficient, for example, It is preferable that it is granular (especially spherical shape).

  In this case, the average particle size of the inorganic filler is preferably about 1 to 100 μm, and more preferably about 5 to 35 μm. In this case, the particle size distribution is preferably wide. Thereby, the filling amount (use amount) of the inorganic filler can be increased, and the reinforcing effect of the obtained semiconductor device is further improved.

  In the epoxy resin composition of the present invention, the content (blending amount) of the curing accelerator (C) is not particularly limited, but is preferably about 0.01 to 10% by weight, preferably 0.1 to 5% by weight. More preferably, it is about. Thereby, the adhesion characteristic of an epoxy resin composition expresses preferably.

  In the epoxy resin composition of the present invention, the content (blending amount) of boric acid or boric acid ester (D) is preferably about 0.01 to 5% by weight, and about 0.1 to 3% by weight. More preferably. Further, the compound (E) contains two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule and has or does not have a substituent other than the proton-donating substituent. The amount (blending amount) is preferably about 0.01 to 5% by weight, and more preferably about 0.01 to 3% by weight. The molar ratio of the compound (E) to boric acid or boric acid ester (D) is preferably in the range of 0.1 to 10, more preferably 0.5 to 5. Thereby, the fluidity and storage stability of the epoxy resin composition are preferably expressed without adversely affecting the curability.

  Moreover, the compounding ratio of the epoxy resin (A) and the phenol resin (B) is not particularly limited, but the phenolic property of the phenol resin (B) with respect to 1 mol of the epoxy group of the epoxy resin (A). It is preferable to use it so that a hydroxyl group may be about 0.5-2 mol, and it is more preferable to use it so that it may become about 0.7-1.5 mol. Thereby, various characteristics improve more, maintaining the balance of the various characteristics of an epoxy resin composition to a suitable thing.

  The content (blending amount) of the inorganic filler (F) is not particularly limited, but is about 200 to 2400 parts by weight per 100 parts by weight of the total amount of the compound (A) and the compound (B). It is preferable that the amount is about 400 to 1400 parts by weight. When the content of the inorganic filler is within the above range, the reinforcing effect, and moldability such as fluidity and fillability during molding are further improved.

  In addition, if content (incorporation amount) of an inorganic filler is 400-1400 weight part per 100 weight part of total amounts of the said compound (A) and the said compound (B), the hardened | cured material of an epoxy resin composition The moisture absorption rate of the solder becomes low, and the occurrence of solder cracks can be prevented. Since such an epoxy resin composition also has good fluidity when heated and melted, it is suitably prevented from causing deformation of the gold wire inside the semiconductor device.

  In addition, the content (blending amount) of the inorganic filler is handled by converting the weight parts into volume%, taking into consideration the specific gravity of the compound (A), the compound (B) and the inorganic filler itself. May be.

  In the epoxy resin composition of the present invention, in addition to the compounds (A) to (E), if necessary, for example, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Coupling agents such as carbon black, colorants such as carbon black, flame retardants such as brominated epoxy resins, antimony oxide and phosphorus compounds, low stress components such as silicone oil and silicone rubber, natural waxes, synthetic waxes, higher fatty acids or their metals You may make it mix | blend (mix) various additives, such as mold release agents, such as salts and paraffin, and antioxidant.

  The epoxy resin composition of the present invention is prepared by mixing the compounds (A) to (E), optionally an inorganic filler, and, if necessary, other additives at room temperature using a mixer. It can be obtained by heating and kneading using a kneader such as a roll and a heating kneader, cooling and pulverizing. In addition, by melting and mixing at a temperature equal to or higher than the softening point of the epoxy resin (A) or the phenol resin (B), a boric acid or boric acid ester (D) as a component, a boron atom and a chelate ring in the molecule A compound (E) having two or more proton-donating substituents that can be formed and having or not having a substituent other than the proton-donating substituent reacts in the molten resin to form a chelate-type borate. An anion is formed, and a salt with the curing accelerator (C) is more easily generated. The formed salt of the curing accelerator effectively suppresses the low temperature activity of the curing accelerator, resulting in good fluidity and storage stability.

  The epoxy resin composition of the present invention thus obtained is superior in fluidity and storage stability as compared with conventional epoxy resin compositions. The reason is that in the present invention, boric acid or borate ester (D) has two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule, and the proton-donating substituents. Curing by reacting with the compound (E) having or not having a substituent other than in the epoxy resin composition at the time of thermoforming, forming a chelate-type borate anion, and forming a salt with a curing accelerator This is because the low temperature activity of the accelerator is effectively suppressed, and as a result, good fluidity and storage stability are imparted.

  The obtained epoxy resin composition is used as a molding resin, and is cured and molded by a molding method such as transfer molding, compression molding, or injection molding, thereby sealing electronic components such as semiconductor elements. Thereby, the semiconductor device of the present invention is obtained.

  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 crack resistance. The reason is that, in the epoxy resin composition of the present invention, the viscosity is reduced at the time of molding and the fluidity is excellent, so that peeling due to poor filling in the mold or poor adhesion to the substrate is unlikely to occur, and solder resistance Excellent cracking properties.

  Although this embodiment demonstrated the case where the epoxy resin composition of this invention was used as a sealing material of a semiconductor device, as an application of the epoxy resin composition of this invention, it is not limited to this. Further, in the epoxy resin composition of the present invention, mixing (compounding) of the inorganic filler can be omitted depending on the use of the epoxy resin composition.

  The preferred embodiments of the epoxy resin composition and the semiconductor device of the present invention have been described above, but the present invention is not limited thereto.

  Next, specific examples of the present invention will be described.

[Preparation of epoxy resin composition and manufacture of semiconductor device]
An epoxy resin composition was prepared as follows to manufacture a semiconductor device.

Example 1
First, a biphenyl type epoxy resin (YX-4000HK manufactured by Japan Epoxy Resin Co., Ltd.) represented by the following formula (5) as the compound (A), and a phenol aralkyl resin represented by the following formula (6) as the compound (B). (However, the number of repeating units: 3 represents an average value. XLC-LL manufactured by Mitsui Chemicals, Inc.), triphenylphosphine as compound (C), orthoboric acid as component (D), 2, as component (E) 2′-biphenol, fused spherical silica (average particle size 15 μm) as inorganic filler, and 3-glycidyloxypropyltrimethoxysilane, carbon black, brominated bisphenol A type epoxy resin and carnauba wax are prepared as other additives, respectively. did.

<Physical properties of the compound represented by the formula (5)>
Melting point: 105 ° C
Epoxy equivalent: 193
ICI melt viscosity at 150 ° C .: 0.15 poise

<Physical properties of the compound represented by the formula (6)>
Softening point: 77 ° C
Hydroxyl equivalent: 172
ICI melt viscosity at 150 ° C .: 3.6 poise

  Next, the biphenyl type epoxy resin: 52 parts by weight, the phenol aralkyl resin: 48 parts by weight, triphenylphosphine: 1.00 parts by weight, boric acid: 0.24 parts by weight, 2,2′-biphenol: 1. 42 parts by weight, fused spherical silica: 730 parts by weight, carbon black: 2 parts by weight, 3-glycidyloxypropyltrimethoxysilane: 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, then kneaded for 8 minutes at 95 ° C. using a hot roll, and then cooled and ground to obtain an epoxy resin composition.

  Next, using this epoxy resin composition as a mold resin, 8 100-pin TQFP packages (semiconductor devices) and 15 16-pin DIP packages (semiconductor devices) were produced, respectively.

  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)
First, as a compound (A), a biphenylaralkyl type epoxy resin represented by the following formula (7) (however, the number of repeating units: 3 represents an average value. NC-3000P manufactured by Nippon Kayaku Co., Ltd.), a compound ( B) a biphenyl aralkyl type phenol resin represented by the following formula (8) (however, the number of repeating units: 3 represents an average value. MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.), and triphenyl as the compound (C) Phosphine, orthoboric acid as component (D), 2,2′-biphenol as component (E), fused spherical silica (average particle size 15 μm) as inorganic filler, 3-glycidyloxypropyltrimethoxysilane as other additive, Carbon black, brominated bisphenol A type epoxy resin and carnauba wax were prepared.

<Physical properties of the compound represented by the formula (7)>
Softening point: 60 ° C
Epoxy equivalent: 272
ICI melt viscosity at 150 ° C .: 1.3 poise

<Physical properties of the compound represented by the formula (8)>
Softening point: 68 ° C
Hydroxyl equivalent: 199
ICI melt viscosity at 150 ° C .: 0.9 poise

  Next, the biphenyl aralkyl type epoxy resin: 57 parts by weight, the biphenyl aralkyl type phenol resin: 43 parts by weight, triphenylphosphine: 1.00 parts by weight, boric acid: 0.24 parts by weight, 2,2′-biphenol : 1.42 parts by weight, fused spherical silica: 650 parts by weight, carbon black: 2 parts by weight, 3-glycidyloxypropyltrimethoxysilane: 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, then kneaded for 8 minutes at 105 ° C. using a hot roll, and then cooled and ground to obtain an epoxy resin composition.

  Next, using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 3)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that trimethyl borate: 0.40 parts by weight was used instead of orthoboric acid as component D, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

Example 4
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that trimethyl borate: 0.40 part by weight was used instead of orthoboric acid as component D, and this epoxy resin was obtained. Using the composition, a package (semiconductor device) was produced in the same manner as in Example 2.

(Example 5)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that 0.88 parts by weight of tri-n-butyl borate was used instead of orthoboric acid as component D. Using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 1.

(Example 6)
An epoxy resin composition (thermosetting resin composition) was obtained except that 0.88 parts by weight of tri-n-butyl borate was used in place of boric acid as component D, and this epoxy resin composition was used. A package (semiconductor device) was manufactured in the same manner as in Example 2.

(Example 7)
An epoxy resin composition (thermosetting resin composition) in the same manner as in Example 5 except that instead of 2,2′-biphenol as component E, 2-hydroxybenzyl alcohol: 0.95 parts by weight was used. Using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 5.

(Example 8)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 6 except that salicylic acid: 1.05 parts by weight was used instead of 2,2′-biphenol as component E. A package (semiconductor device) was manufactured in the same manner as in Example 6 using the epoxy resin composition.

Example 9
An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 5 except that instead of 2,2′-biphenol as component E, 3-hydroxy-2-naphthoic acid: 1.44 parts by weight was used. The package (semiconductor device) was manufactured in the same manner as in Example 5 using this epoxy resin composition.

(Example 10)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 6 except that catechol: 0.84 parts by weight was used in place of 2,2′-biphenol as component E. A package (semiconductor device) was manufactured in the same manner as in Example 6 using the epoxy resin composition.

(Example 11)
An epoxy resin composition (thermosetting resin composition) was prepared in the same manner as in Example 5 except that 2,2-dihydroxynaphthalene: 1.22 parts by weight was used as component E instead of 2,2′-biphenol. And using this epoxy resin composition, a package (semiconductor device) was manufactured in the same manner as in Example 5.

(Example 12)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 6 except that pyrogallol: 0.96 parts by weight was used in place of 2,2′-biphenol as component E. A package (semiconductor device) was manufactured in the same manner as in Example 6 using the epoxy resin composition.

(Comparative Example 1)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that component D and component E were not added, and this epoxy resin composition was used as in Example 1 above. Thus, a package (semiconductor device) was manufactured.

(Comparative Example 2)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that Component D and Component E were not added, and this epoxy resin composition was used as in Example 2 above. Thus, a package (semiconductor device) was manufactured.

(Comparative Example 3)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that component D was not added. Using this epoxy resin composition, a package was obtained in the same manner as in Example 1. (Semiconductor device) was manufactured.

(Comparative Example 4)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that component D was not added. Using this epoxy resin composition, a package was obtained in the same manner as in Example 2. (Semiconductor device) was manufactured.

(Comparative Example 5)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 1 except that component E was not added, and a package was obtained in the same manner as in Example 1 using this epoxy resin composition. (Semiconductor device) was manufactured.

(Comparative Example 6)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 2 except that component E was not added. Using this epoxy resin composition, a package was obtained in the same manner as in Example 2. (Semiconductor device) was manufactured.

(Comparative Example 7)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 5 except that component E was not added, and a package was obtained in the same manner as in Example 5 using this epoxy resin composition. (Semiconductor device) was manufactured.

(Comparative Example 8)
An epoxy resin composition (thermosetting resin composition) was obtained in the same manner as in Example 6 except that component E was not added, and a package was obtained in the same manner as in Example 6 using this epoxy resin composition. (Semiconductor device) was manufactured.

[Characteristic evaluation]
Characteristic evaluation (1) to (3) of the epoxy resin composition obtained in each example and each comparative example, and characteristic evaluation (4) of the semiconductor device obtained in each example and each comparative example, This was done 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 45 seconds was measured.
This hardening torque shows that curability is so favorable that a numerical value is large.

(3): Flow residual ratio After the obtained epoxy resin composition was stored in the atmosphere at 30 ° C for 1 week, the spiral flow was measured in the same manner as in (1) above, and the percentage (% )
This flow residual ratio indicates that the larger the numerical value, the better the storage stability.

(4): Solder crack resistance 100-pin TQFP was humidified for 168 hours in an environment of 85 ° C. and 85% relative humidity, and then heat-treated in an IR reflow furnace at a maximum temperature of 260 ° C. for 2 minutes.

  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 occurrence rate and peeling rate indicate that the smaller the numerical value, the better the solder crack resistance.
Table 1 shows the results of the characteristic evaluations (1) to (4).

  As shown in Table 1, the epoxy resin compositions (epoxy resin compositions of the present invention) obtained in Examples 1 to 12 all have better fluidity and storage stability than the comparative examples. Each of the packages (semiconductor devices of the present invention) sealed with the cured product had good solder crack resistance.

  On the other hand, the epoxy resin compositions obtained in Comparative Examples 1 to 8 were inferior in balance between fluidity, storage stability and solder resistance as compared with Examples.

(Examples 13 to 18, Comparative Examples 9 and 10)
As the compound (A), the biphenyl type epoxy resin represented by the formula (12): 26 parts by weight, the biphenyl aralkyl type epoxy resin represented by the formula (14): 28.5 parts by weight, and the compound (B) ), Except that the phenol aralkyl resin represented by the formula (13): 45.5 parts by weight, respectively, Examples 1, 3, 5, 7, 9, 11, Comparative Examples 1, 3, In the same manner as in Examples 5 and 7, an epoxy resin composition (thermosetting resin composition) was obtained, and a package (semiconductor device) was manufactured using this epoxy resin composition.

  When the characteristics of the epoxy resin compositions and packages obtained in Examples 13 to 18 and Comparative Examples 9 and 10 were evaluated in the same manner as described above, the same results as in Table 1 were obtained.

(Examples 19 to 24, Comparative Examples 11 and 12)
As compound (A), biphenyl type epoxy resin represented by the formula (12): 54.5 parts by weight, as compound (B), phenol aralkyl resin represented by the formula (13): 24 parts by weight, and Biphenyl aralkyl type phenol resin represented by the formula (15): Except for blending 21.5 parts by weight, Examples 1, 3, 5, 7, 9 and 11, respectively, Comparative Examples 1, 3, In the same manner as in Examples 5 and 7, an epoxy resin composition (thermosetting resin composition) was obtained, and a package (semiconductor device) was manufactured using this epoxy resin composition.

  When the characteristics of the epoxy resin compositions and packages obtained in Examples 19 to 24 and Comparative Examples 11 and 12 were evaluated in the same manner as described above, the same results as in Table 1 were obtained.

  By using such an epoxy resin composition, an epoxy resin composition having good curability, storage stability and fluidity can be obtained. This epoxy resin can be suitably used in the electric / electronic material field, and in particular, an electronic component device in which an electronic component such as a semiconductor element excellent in solder crack resistance and moisture resistance reliability is sealed can be obtained.

Claims (10)

An epoxy resin composition comprising an epoxy resin (A), a phenol resin (B), and a curing accelerator (C), which forms a chelate ring with boric acid or boric acid ester (D) and a boron atom in the molecule An epoxy resin composition comprising a compound (E) having two or more possible proton-donating substituents and having or not having a substituent other than the proton-donating substituent. Compound (E) having two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule and having or not having a substituent other than the proton-donating substituent, The epoxy resin composition according to claim 1, which has a hydroxyl group, a carboxyl group, and a mercapto group as proton-donating substituents. Compound (E) having two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule and having or not having a substituent other than the proton-donating substituent, The epoxy resin composition according to claim 1 or 2, wherein two or more proton-donating substituents are adjacent to each other on the aromatic ring. Compound (E) having two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule and having or not having a substituent other than the proton-donating substituent, The epoxy resin composition according to claim 1, which has a proton-donating substituent on a benzene ring, naphthalene ring or biphenyl ring. Compound (E) having two or more proton-donating substituents capable of forming a chelate ring with a boron atom in the molecule and having or not having a substituent other than the proton-donating substituent is biphenyl. The epoxy resin composition for semiconductor encapsulation according to claim 4, wherein the epoxy resin composition has two hydroxyl groups on the ring. The epoxy resin composition according to any one of claims 1 to 5, wherein the epoxy resin (A) is mainly composed of at least one of the epoxy resins represented by the general formula (1) or (2).
[Wherein R ¹ , R ² , R ³ and R ⁴ each represents one selected from a hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group and a halogen atom, They may be the same or different. ]
[Wherein, R ^{5 to} R ¹² each represent one selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a halogen atom, and may be the same or different from each other. However, a is an integer of 1-10. ] The epoxy resin composition according to any one of claims 1 to 6, wherein the phenol resin (B) contains at least one of the phenol resins represented by the general formula (3) or (4) as a main component.
[In formula, R < ¹³ > -R < ¹⁶ > represents 1 type selected from a hydrogen atom, a C1-C4 alkyl group, and a halogen atom, respectively, and may mutually be same or different. However, b is an integer of 1-10. ]
[In formula, R < ¹⁷ > -R < ²⁴ > represents 1 type selected from a hydrogen atom, a C1-C4 alkyl group, and a halogen atom, respectively, and may mutually be same or different. However, c is an integer of 1-10. ]   The epoxy resin composition according to any one of claims 1 to 7, comprising an inorganic filler.   The epoxy resin composition according to any one of claims 1 to 8, wherein the epoxy resin composition is melt-mixed at a temperature equal to or higher than a softening point of the epoxy resin (A) or the phenol resin (B). A semiconductor device comprising a semiconductor element sealed using the epoxy resin composition according to claim 1.