JP2007077291A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition having good latent curability and fluidity and to provide a semiconductor device having excellent reliability. <P>SOLUTION: The epoxy resin composition comprises a compound represented by general formula (1) [wherein, X represents an organic group], a silane compound represented by ZSi(OR)<SB>3</SB>(wherein, Z represents an organic group having a substituted or an unsubstituted aromatic ring or a heterocycle or a substituted or an unsubstituted aliphatic group; and R represents a 1-3C aliphatic group) and a curing accelerator. The epoxy resin composition is characterized in that the compound represented by general formula (1), silane compound and curing accelerator are melt mixed under reduced pressure. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  As a method for obtaining a semiconductor device by sealing semiconductor elements such as IC and LSI, transfer molding of an epoxy resin composition is widely used because it is suitable for mass production at low cost. In addition, in the epoxy resin composition, improvement in characteristics and reliability as a semiconductor device is achieved by improvement with an epoxy resin or a phenol resin as a curing agent.

  However, in the recent market trend of electronic devices that have been reduced in size, weight, and performance, higher integration of semiconductors has been progressing year by year, and surface mounting of semiconductor devices has been promoted. Along with this, the required characteristics for epoxy resin compositions used for sealing semiconductor elements have become increasingly severe. For this reason, the conventional epoxy resin composition also has a problem that cannot be solved (cannot be handled).

  In recent years, materials used for encapsulating semiconductor elements include improvements in rapid curability for the purpose of improving production efficiency in molding using the same, and heat resistance and reliability of semiconductor devices when encapsulating semiconductors. In order to improve the property, not only the improvement by the resin, but also the high fluidity that is not impaired even if the inorganic filler is highly filled has been demanded.

  Addition reaction product of tertiary phosphine and quinones with excellent fast curing properties is added to the epoxy resin composition for electrical and electronic materials as a curing accelerator for the purpose of accelerating the curing reaction of the resin during curing. (See, for example, Patent Document 1).

  By the way, such a curing accelerator has a temperature range that exhibits a curing acceleration effect up to a relatively low temperature, and therefore, at the initial stage of the curing reaction, the curing reaction of the epoxy resin is promoted little by little. Thus, the resin composition has a high molecular weight. Such high molecular weight causes an increase in resin viscosity. As a result, in a resin composition that is highly filled with a filler for improving reliability, problems such as molding defects due to insufficient fluidity are caused.

  In order to improve fluidity, various attempts have been made to protect reactive substrates using components that suppress curability. Such a means is called latentization. For example, a latent accelerating accelerator is obtained by converting a phosphonium ion into a salt with a strong anionic compound and protecting the active site of the accelerating accelerator with an ion pair. Is known (for example, see Patent Documents 2 to 3). However, in such salts, since there are always inhibiting components from the initial stage to the final stage of the curing reaction, it is difficult to improve curability and fluidity at the same time, which is not satisfactory.

On the other hand, in order to improve the reliability of the semiconductor device, efforts have been made to reduce the volatile matter from the epoxy resin composition and suppress the generation of cracks due to the generation of voids in the cured product. For example, there is a technique for preliminarily mixing a tetra-substituted phosphonium tetra-substituted borate and a curing agent under reduced pressure to remove the generated volatile matter (for example, see Patent Document 4), but the curing accelerator used here is There was a problem that latency was remarkably deteriorated by premixing and reacting.
Japanese Patent Laid-Open No. 10-25335 (page 2) JP 2001-98053 A (page 5) U.S. Pat. No. 4,171,420 (pages 2-4) JP 2005-162942 A (second page)

  An object of the present invention is to provide an epoxy resin composition having good latent curability and fluidity, and a semiconductor device having excellent reliability.

  As a result of intensive investigations to solve the problems as described above, the present inventors, as a result of melting and mixing a specific silane compound, a compound having a specific hydroxyl group, and a curing accelerator, It has been found that an epoxy resin composition excellent in latent curability can be obtained by performing the treatment under reduced pressure.

  Furthermore, the present inventors have shown that the epoxy resin composition obtained by the above method can exhibit high fluidity, good curability, and reliability even when highly filled with an inorganic filler. The headline and the present invention were completed.

That is, the present invention is achieved by the following (1) to (5).
(1) In an epoxy resin composition containing a compound represented by the following general formula (1), a silane compound represented by the following general formula (2) and a curing accelerator, a compound represented by the following general formula (1) The epoxy resin composition, wherein the silane compound and the curing accelerator represented by the following general formula (2) are melt-mixed under reduced pressure.

［式中、Ｘは有機基を表す。］

[Wherein X represents an organic group. ]

［式中、Ｒ¹、Ｒ²、およびＲ³は、炭素数１〜３の脂肪族基であり、互いに同一でも異なっていてもよい。Ｚは置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を示す。］

[Wherein R ¹ , R ² , and R ³ are aliphatic groups having 1 to 3 carbon atoms, and may be the same or different from each other. Z represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]

(2) The epoxy resin composition according to item (1), wherein the melt mixing is performed by heating at a temperature of 100 to 200 ° C.
(3) The epoxy resin composition according to (1) or (2), wherein the melt mixing includes an epoxy resin curing agent.
(4) The compound represented by the general formula (1) and the silane compound represented by the general formula (2) are mixed in a molar ratio satisfying the following formula, items (1) to (1) The epoxy resin composition according to any one of items (3).
Mc ≧ Md × 2
In the above formula, Mc is the number of moles of the compound represented by the general formula (1), and Md is the number of moles of the compound represented by the general formula (2).
(5) A semiconductor device formed by sealing an electronic component with a cured product of the epoxy resin composition according to any one of (1) to (4).

The epoxy resin composition of the present invention has excellent latent curability, fluidity and storage stability, and can exhibit good fluidity even when an inorganic filler is used.
In addition, the semiconductor device of the present invention can be obtained with excellent reliability in characteristics such as solder crack resistance and moisture resistance reliability.

The present invention is an epoxy resin composition comprising a compound represented by the general formula (1), a silane compound represented by the general formula (2), and a curing accelerator, and represented by the general formula (1). The compound, the silane compound represented by the following general formula (2) and the curing accelerator are characterized by being melt-mixed under reduced pressure, whereby the epoxy resin composition has latent curing properties. , And can exhibit excellent fluidity and storage stability.
In addition, when the semiconductor is encapsulated with the cured product using the epoxy resin composition, generation of voids can be reduced, and as a result, a highly reliable semiconductor device can be obtained.

The epoxy resin used in the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule.
Specific examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins and brominated bisphenol type epoxy resins; biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, and stilbene types. Epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins and dihydroxybenzene type epoxy resins; epichlorohydrin on the hydroxyl group of polyfunctional phenolic compounds Epoxy compounds produced by reacting olefins, epoxy resins obtained by oxidizing olefins with peracids, glycidyl ester epoxy resins, and glycidyl amine epoxy resins Resins and the like may be used singly or in combination of two or more of them.

  Examples of the epoxy resin curing agent used in the present invention include compounds having two or more phenolic hydroxyl groups in one molecule, but are not limited as long as they function as the epoxy resin curing agent.

  Specific examples of the compound having two or more phenolic hydroxyl groups in one molecule include phenol novolak resin, cresol novolak resin, bisphenol resin, phenol aralkyl resin, biphenyl aralkyl resin, trisphenol resin, xylylene-modified novolak resin, Examples include terpene-modified novolak resins and dicyclopentadiene-modified phenol resins, and one or more of these can be used in combination.

  The curing accelerator used in the present invention is not particularly limited in form and type as long as it accelerates the curing reaction of the epoxy resin, and specifically includes an imidazole compound, an amine compound, a phosphine compound, and a bicyclic diaza. Non-salts such as compounds, onium salts such as ammonium salt compounds, phosphonium salt compounds and sulfonium salt compounds, intramolecular salts such as phosphobetaine compounds, and encapsulation, inclusion, pulverization, nano-dispersion, etc. Although the form etc. which gave the process are mention | raise | lifted, since the outstanding compatibility of sclerosis | hardenability and latency is seen when using an onium salt and an intramolecular salt compound among these, it is preferable.

Specific examples of curing accelerators for the onium salt compounds and inner salts include onium halogen salts such as tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, trimethylammonium bromide, and diphenylsulfonium bromide; Phosphonium betaines such as 2- (triphenylphosphonio) phenolate and adducts of triphenylphosphine and 1,4-benzoquinone, 2- (triphenylphosphonio) phenolate, 3- (triphenylphosphonio) phenolate; Ammonium betaines such as 1-carboxyl-N, N, N-trimethylmethananium inner salt; bisphenols such as tetraphenylphosphonium and bisphenol A; And molecular compounds such as molecular compounds composed of tetrabutylphosphonium and dihydroxynaphthalenes such as 2,3-dihydroxynaphthalene; quaternary phosphonium salts formed from triphenylphosphine and phenolic compounds, etc. It is done.
Of these, molecular compounds such as molecular compounds of tetraphenylphosphonium and bisphenols and molecular compounds of tetraphenylphosphonium and dihydroxynaphthalene, adducts of triphenylphosphine and 1,4-benzoquinone, and 2- When phosphonium betaines such as (triphenylphosphonio) phenolate are used, an epoxy resin composition is preferable because it can achieve both extremely good curability and latency.

  The compound represented by the general formula (1) used in the present invention has an organic group as X in the formula (1). Specific examples of the organic group for X include substituted or unsubstituted aliphatic groups such as ethylene group and methylethylene group, and substituted or unsubstituted aromatic groups such as phenylene group and naphthalene group. Among them, in particular, aromatic groups such as 1,2-phenylene group and 2,3-naphthalene group increase the stability of the structure as a curing retardation component to be formed, and are excellent in latency. Particularly preferred. In addition, examples of the substituent in the aliphatic group and the aromatic group include a methyl group, an ethyl group, a tertiary butyl group, a methoxy group, an ethoxy group, and a hydroxyl group.

  Specific examples of the compound represented by the general formula (1) include 1,2-dihydroxybenzene (o-catechol), 4-methyl-o-catechol, 4-ethyl-o-catechol, 4- Bromo-o-catechol, 5-chloro-o-catechol, 4-nitro-o-catechol, 4-tertiarybutyl-o-catechol, 4-aminomethyl-o-catechol, 4-hydroxymethyl-o-catechol, etc. Catechols, naphthalene compounds such as 2,3-dihydroxynaphthalene, 7-methyl-2,3-dihydroxynaphthalene and 6-methyl-2,3-dihydroxynaphthalene, pyrogallol compounds such as pyrogallol, gallic acid and methyl gallate, etc. Substituted or unsubstituted aromatics with adjacent hydroxyl groups produce cure retarding components The preferred because the response is likely to proceed. Among these, when 2,3-dihydroxynaphthalene is used, it is preferable because the latent effect of the curing retardation component becomes better.

The silane compound represented by the general formula (2) used in the present invention has an aliphatic group having 1 to 3 carbon atoms as R ¹ , R ² , and R ³ in the formula (2). May be the same as or different from each other, and Z has an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group.
Examples of the aliphatic group having 1 to 3 carbon atoms as R ¹ , R ² and R ³ include a methyl group, an ethyl group and a propyl group.
Examples of the organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring as Z or a substituted or unsubstituted aliphatic group include a phenyl group, a methylphenyl group, an ethylphenyl group, and a naphthalene group. Organic groups having a substituted or unsubstituted aromatic ring, organic groups having a substituted or unsubstituted heterocyclic ring such as a pyridinyl group, substituted or unsubstituted such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a hexyl group Substituted aliphatic groups, and the like. Among these, an organic group having a substituted or unsubstituted aromatic ring having 4 to 8 carbon atoms, such as a phenyl group and a hexyl group, or a substituted or unsubstituted aliphatic group. The chelate structure is preferable because of its high stability. Examples of the substituent in the organic group having an aromatic ring, the organic group having a heterocyclic ring, and an aliphatic group include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a hydroxyl group, an amino group, a thiol group, and a glycidyl ether group. Is mentioned.

Specific examples of the silane compound represented by the general formula (2) include silanes having an aromatic substituent such as trimethoxyphenylsilane, triethoxyphenylsilane, tripropoxyphenylsilane, and dimethoxyethoxyphenylsilane. And silanes having an aliphatic substituent such as trimethoxyhexylsilane and diethoxymethoxyoctylsilane. Among these, those in which R ¹ , R ^2, and R ³ in the general formula (2) are methyl groups and Z is an aromatic group such as a phenyl group are preferable because of their excellent latent ability.

In the present invention, the mixing ratio of the compound represented by the general formula (1) and the silane compound represented by the general formula (2) can be adjusted according to the desired degree of delay in curing. It is more preferable to mix by molar ratio.
Mc ≧ Md × 2
In the above formula, Mc is the number of moles of the compound represented by the general formula (1), and Md is the number of moles of the compound represented by the general formula (2).

As said specific example, 2 mol or more of silane compounds represented by General formula (1) are preferable with respect to 1 mol of compounds represented by General formula (2), and it is more preferable that it is 2-6 mol. When the mixing ratio is within the range, the balance between curability and latent action is excellent, but when the silane compound represented by the general formula (1) is less than 2 mol, the balance is represented by the general formula (2). The reaction of the silane compound to be performed does not proceed sufficiently by melt mixing, which may cause voids during molding.

  In the epoxy resin composition of the present invention, the content (addition amount) of the compound represented by the general formula (1) and the silane compound represented by the general formula (2) depends on the desired degree of latentization. The amount of addition can be adjusted. Specifically, it is preferable to add the silane compound represented by the general formula (2) in the range of 0.1 to 5 moles with respect to 1 mole of the curing accelerator component, and in the range of 0.5 to 2 moles. It is more preferable to add. The compound represented by the general formula (1) is preferably added at an appropriate mixing ratio depending on the amount of the silane compound represented by the general formula (2). When the content (addition amount) is within the range, the balance between curability and latent action is more excellent.

In the present invention, at least the compound represented by the general formula (1), the silane compound represented by the general formula (2), and the curing accelerator are melt-mixed under reduced pressure conditions to perform these reactions. .
Here, the reduced pressure condition is to create a pressure atmosphere that allows the gas component in the composition to be sucked and released out of the system at the time of melt mixing. A reduced pressure state in which a gas component is sucked at the following pressure can be mentioned. In order to maintain such a condition, in addition to using a batch type apparatus such as a flask or a reaction kettle that can be heated and depressurized at the same time, a continuous twin-screw kneader or a heating kneader that can depressurize by sucking gas components. Etc. can be used. When the depressurization condition exceeds 0.8 atm, desorbed components such as alcohols that cause voids may not be efficiently removed.

Furthermore, in the present invention, it is more preferable to place the system under a heating condition of 100 to 200 ° C. in addition to the reduced pressure condition. By doing so, it is possible to promote the formation of a curing-inhibiting component and vaporize desorbing components such as alcohols and remove them out of the system.
The suitable heating temperature varies depending on the compound represented by the general formula (1) and the silane compound represented by the general formula (2) to be used, but it is necessary to exceed the boiling point at 1 atm of at least the alcohol to be eliminated. is there. For example, if R ₁ in the silane compound represented by the general formula (2) is a butyl group, the alcohol to be eliminated is butanol, and therefore it is necessary that the conditions be at least higher than 117 ° C. which is the boiling point of butanol. On the other hand, when the heating temperature exceeds 200 ° C., the formed curing-inhibiting component and the curing accelerator may be modified by a reaction such as oxidation or decomposition, which may adversely affect the curability.

  By performing the melt mixing, the compound represented by the general formula (1) reacts with the silane compound represented by the general formula (2) to obtain a silicate compound that functions as a curing retarding component. A typical example of the component generated by this reaction is a compound represented by the following formula (3).

［式中、Ｘ、Ｚは、一般式（１）で表される化合物および一般式（２）で表されるシラン化合物における有機基Ｘ、Ｚと同一である。］

[Wherein, X and Z are the same as the organic groups X and Z in the compound represented by the general formula (1) and the silane compound represented by the general formula (2). ]

  The compound represented by the formula (3) can be synthesized by itself and added to the resin composition, but the method in the present invention synthesizes the compound represented by the formula (3) in advance. Since there is no need to do this, man-hours and manufacturing costs can be greatly reduced.

  In the present invention, in the melt mixing, all or part of the epoxy resin curing agent can be mixed at the same time. By doing in this way, the formed hardening inhibitor component and hardening accelerator are uniformly disperse | distributed to a resin composition, and can show the outstanding curability.

In the present invention, during the melt mixing, alcohol is generated by the reaction of the compound represented by the general formula (1) and the silane compound represented by the general formula (2). Then, it is possible to confirm whether or not the reaction is sufficiently progressed by collecting alcohols generated by the reaction and confirming the weight thereof. Since the amount of generated alcohol is derived from OR ¹ to OR ³ in the formula of the compound represented by the general formula (1), it can be calculated from the addition amount of the compound represented by the general formula (1). . Preferably, 90% or more of the theoretical amount calculated in this manner is removed from the reaction product. If the removal amount is too small, the amount of voids generated during molding increases, which adversely affects the reliability of the molded product.

An inorganic filler can be added to the epoxy resin composition of the present invention for the purpose of improving physical strength and heat resistance.
Examples of such inorganic fillers include fused crushed silica, fused silica, crystalline silica, secondary agglomerated silica, alumina, titanium white, aluminum hydroxide, talc, clay, and glass fiber. One kind or a combination of two or more kinds can be used.

  In the epoxy resin composition of the present invention, the content (blending amount) of the curing accelerator is not particularly limited, but the epoxy resin and the curing agent, for example, have two or more phenolic hydroxyl groups in one molecule. The amount is preferably about 0.01 to 10% by weight, more preferably about 0.1 to 5% by weight, based on the resin component composed of the compound.

  Further, the blending ratio of the epoxy resin and the compound having two or more phenolic hydroxyl groups in one molecule is not particularly limited, but the phenolic hydroxyl group is contained in one molecule with respect to 1 mol of the epoxy group of the epoxy resin. It is preferable to use it so that the phenolic hydroxyl group of the compound which has 2 or more 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, the hardened | cured material of an epoxy resin composition can obtain sufficient intensity | strength.

  Further, the content (blending amount) of the inorganic filler is not particularly limited, but is preferably about 200 to 2400 parts by weight with respect to 100 parts by weight of the resin component composed of the epoxy resin and its curing agent. More preferably, it is about ˜1400 parts by weight. When the content of the inorganic filler is less than the above lower limit value, the reinforcing effect by the inorganic filler may not be sufficiently exhibited. On the other hand, when the content of the inorganic filler exceeds the upper limit value, the epoxy resin composition The fluidity of the resin deteriorates, and there is a possibility that poor filling or the like may occur when the epoxy resin composition is molded. In the present invention, the content of the inorganic filler can be increased by adjusting the fluidity with the curing accelerator and the curing delay component, and in that case, the effect obtained from the inorganic filler, A semiconductor device having excellent reliability such as solder crack resistance and moisture resistance reliability can be obtained.

  In addition, the content (mixing amount) of the inorganic filler may be handled by converting the weight part into volume% in consideration of the specific gravity of the epoxy resin, the curing agent and the inorganic filler itself. .

  In addition to the above, in the epoxy resin composition of the present invention, if necessary, for example, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, a brominated epoxy Various additives such as flame retardants such as resin and antimony oxide, phosphorus compounds, low stress components such as silicone oil and silicone rubber, release agents such as natural wax, synthetic wax, higher fatty acids or their metal salts and paraffin, and antioxidants You may make it mix | blend an agent.

  The epoxy resin composition of the present invention is obtained by cooling and pulverizing the aforementioned melt-mixed mixture under reduced pressure, and then epoxy resin, its curing agent, optionally inorganic filler, and, if necessary, other additives Etc. can be obtained by mixing using a mixer, and further by mixing the mixture at room temperature by heating and kneading using a kneader such as a hot roll and a heating kneader, followed by cooling and grinding. Can do.

  By using the epoxy resin composition obtained above as a mold resin, it is cured and molded by a molding method such as a transfer mold, a compression mold, and an injection mold, thereby sealing an electronic component such as a semiconductor element. 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 Heat Sink), ZIP (Zig-zag Inline Package), DIP (Dual Inline Package), SDIP (Shrink) Dual Inline Package), SOP (Small Small Package), SSOP (Shrink Small Outline Package), TSOP (Thin Small Outline Package), SOJ (Small Outline J-leaded Package P), SOJ (Small Outline J-leaded Package P) QFP Fine Pit h), 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 and moisture resistance reliability.

  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.

First, curing accelerators E1 to E3 used in Examples and Comparative Examples of the present invention were synthesized as follows.
(Synthesis of Compound E1)
In a beaker with a stirrer (capacity: 1000 mL), 25.2 g (0.060 mol) of tetraphenylphosphonium bromide, 27.4 g (0.120 mol) of bisphenol A, and 200 mL of methanol were charged and dissolved well with stirring. 60 ml of a 1 mol / L sodium hydroxide aqueous solution and 600 mL of pure water were sequentially added. The precipitated powder was washed with pure water, filtered and dried to obtain a white powder.

This compound was designated E1. As a result of analyzing compound E1 by ¹ H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target phosphonium molecular compound represented by the following formula (5). The yield of the obtained compound E1 was 83%.

(Synthesis of Compound E2)
In a separable flask (volume: 200 mL) equipped with a condenser and a stirrer, 10.4 g (0.060 mol) of 2-bromophenol, 17.3 g (0.066 mol) of triphenylphosphine, 0.65 g (5 mmol) of nickel chloride And 40 mL of ethylene glycol was charged, and the reaction was carried out at 160 ° C. with stirring. After cooling the reaction solution, 40 mL of pure water was added dropwise, and the precipitated powder was washed with toluene, filtered and dried to obtain a white powder.

  Next, the obtained powder was dissolved in 100 ml of methanol, and 60 ml of 1 mol / L sodium hydroxide aqueous solution and 500 ml of pure water were sequentially added. The obtained crystals were filtered and washed to obtain 12.7 g of pale yellow crystals.

This compound was designated E2. As a result of analyzing the compound E2 by ¹ H-NMR, mass spectrum, and elemental analysis, it was confirmed that it was the target phosphobetaine represented by the following formula (6). The yield of the obtained compound E2 was 83%.

(Synthesis of Compound E3)
A separable flask (volume: 200 mL) equipped with a condenser and a stirrer was charged with 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 mL of acetone and reacted at room temperature with stirring. . The precipitated crystals were washed with acetone, filtered and dried to obtain 20.0 g of brown crystals.

This compound was designated as E3. Compound E3 was analyzed by ¹ H-NMR, mass spectrum, and elemental analysis, and as a result, it was confirmed that it was the target phosphobetaine represented by the following formula (7). The yield of the obtained compound E3 was 84%.

  Next, it is necessary from the epoxy resin curing agent (B), the compound (C) represented by the general formula (1), the silane compound (D) represented by the general formula (2), and the curing accelerator (E) component. Reaction products P1 to P7, which were melt-mixed products prepared by selecting components, were prepared as follows.

[Adjustment of molten mixture]
(Adjustment of reactant P1)
As component (C), 44.0 g (0.4 mol) of catechol, 24.0 g (0.1 mol) of triethoxyphenylsilane as component (D), and tetramethylammonium acetate as a curing accelerator for component (E) 13. 3 g (0.1 mol), and 100 g of biphenyl aralkyl type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.), which is an epoxy resin curing agent, as a part of component (B) is mixed with a mixer under normal temperature and normal pressure. After that, this was put into a flask and melt-mixed for 60 minutes under reduced pressure conditions of 120 ° C. and 0.5 atm. In the melt mixing, 13.4 g (97% of the theoretical amount) of ethanol was recovered from the sucked gas phase, confirming that the expected reaction was sufficiently advanced. This was cooled and pulverized, and the resulting molten mixture was designated as a reaction product P1.

(Adjustment of reactant P2)
As component (C), 4-tertiarybutyl-o-catechol 33.2 g (0.2 mol), as component (D), 3-mercaptopropyltrimethoxysilane 19.6 g (0.1 mol), component (E) 41.9 g (0.1 mol) of tetraphenylphosphonium bromide and 100 g of phenol aralkyl resin (XLC-LL manufactured by Mitsui Chemicals, Inc.), which is an epoxy resin curing agent, as part of the component (B) After mixing with a mixer under normal pressure, this was put into a flask and melt-mixed for 60 minutes under reduced pressure at 110 ° C. and 0.5 atm. In melt mixing, 9.3 g (97% of the theoretical amount) of methanol was recovered from the sucked gas phase, confirming that the expected reaction had proceeded sufficiently. This was pulverized after cooling, and the obtained molten mixture was defined as a reactant P2.

(Adjustment of reactant P3)
As the component (C), 42.0 g (0.3 mol) of 2,3-dihydroxynaphthalene, as the component (D) 19.8 g (0.1 mol) of trimethoxyphenylsilane, as the curing accelerator of the component (E), 79.0 g (0.1 mol) of compound E1 and 100 g of biphenyl aralkyl type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.), which is an epoxy resin curing agent, as part of component (B) After mixing with a mixer under normal pressure, this was put into a flask and melt-mixed for 60 minutes at 105 ° C. under a reduced pressure of 0.4 atm. In melt mixing, 9.3 g (97% of the theoretical amount) of methanol was recovered from the sucked gas phase, confirming that the expected reaction had proceeded sufficiently. This was pulverized after cooling, and the resulting molten mixture was designated as reactant P3.

(Adjustment of reactant P4)
As component (C), 42.0 g (0.3 mol) of 2,3-dihydroxynaphthalene, as component (D), 19.6 g (0.1 mol) of 3-mercaptopropyltrimethoxylane, as a curing accelerator for component (E) As above, 35.4 g (0.1 mol) of the compound E2 and 100 g of a biphenylaralkyl-type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.), which is an epoxy resin curing agent, as a part of the component (B) After mixing with a mixer under normal temperature and normal pressure, this was put into a flask and melt-mixed for 60 minutes under reduced pressure at 105 ° C. and 0.4 atm. In melt mixing, 9.5 g (99% of the theoretical amount) of methanol was recovered from the sucked gas phase, confirming that the expected reaction had proceeded sufficiently. This was cooled and pulverized, and the resulting molten mixture was designated as a reaction product P4.

(Adjustment of reactant P5)
As the component (C), 42.0 g (0.3 mol) of pyrogallol, 27.8 g (0.1 mol) of 3-glycidylpropyltriethoxylane as the component (D), and the compound E3 as a curing accelerator of the component (E) 37.0 g (0.1 mol) was mixed with a mixer at room temperature and normal pressure, and then charged into a flask, and melt mixed for 90 minutes at 170 ° C. and 0.4 atm. In the melt mixing, 13.4 g (97% of the theoretical amount) of ethanol was recovered from the sucked gas phase, confirming that the expected reaction was sufficiently advanced. This was cooled and pulverized, and the obtained molten mixture was designated as a reaction product P5.

(Adjustment of reactant P6)
The reaction temperature after charging the flask was 120 ° C., and the mixture was blended and melt-mixed in the same manner as in the preparation of the reactant P1, except that no pressure reduction was performed. This was cooled and pulverized, and the obtained molten mixture was designated as a reaction product P6.

(Adjustment of reactant P7)
As component (C), 14.0 g (0.1 mol) of 2,3-dihydroxynaphthalene was used, and the mixture was melted and mixed in the same manner as in the preparation of the reactant P3 except that the heating temperature was 130 ° C. In this reactant, the ratio of component (C) to component (D) does not satisfy the relationship of claim 3. In melt mixing, 9.0 g (90% of the theoretical amount) of methanol was recovered from the sucked gas phase, confirming that the expected reaction had proceeded sufficiently. This was cooled and pulverized, and the resulting molten mixture was designated as a reaction product P7.

[Preparation of epoxy resin composition]
An epoxy resin composition containing the reactants P1 to P7 obtained above was prepared as follows.

(Examples 1-6, Comparative Examples 1-3)
According to the mixing ratio shown in Table 1, biphenyl aralkyl type epoxy resin (NC-3000P manufactured by Nippon Kayaku Co., Ltd.) or biphenyl type epoxy resin (YX manufactured by Japan Epoxy Resin Co., Ltd.), which is the epoxy resin of component (A). -4000HK), biphenyl aralkyl type phenol resin (MEH-7851SS manufactured by Meiwa Kasei Co., Ltd.) or phenol aralkyl resin (Mitsui Chemicals, Inc.) which is a compound having two or more phenolic hydroxyl groups in one molecule of component (B) XLC-LL), pre-reacted materials P1 to P7 obtained above, and fused spherical silica as an inorganic filler were first mixed at room temperature, and then kneaded at 95 ° C. for 8 minutes using a hot roll, Cooled and pulverized 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. .

[Characteristic evaluation of semiconductor devices]
Characteristic evaluations (1) to (4) of the semiconductor devices obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were performed as follows.

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

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

(2): Curing torque Using a curast meter (Orientec Co., Ltd., JSR curast meter IV PS type), the torque after 175 ° C. and 45 seconds was measured.
This hardening torque shows that curability is so favorable that a numerical value is large.

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

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

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

  These crack occurrence rate and peeling rate indicate that the smaller the numerical value, the better the solder crack resistance.

(4): Moisture resistance reliability A voltage of 20 V was applied to a 16-pin DIP in water vapor at 125 ° C. and a relative humidity of 100% to examine disconnection defects. The time until a defect appears in 8 or more of the 15 packages was defined as a defect time.

Note that the measurement time is 500 hours at the longest, and when the number of defective packages is less than 8 at that time, the defective time is indicated as over 500 hours (> 500).
This failure time indicates that the larger the numerical value, the better the moisture resistance reliability.
Table 1 shows the results of the characteristic evaluations (1) to (4).

  As shown in Table 1, since the epoxy resin compositions obtained in Examples 1 to 6 are all excellent in fluidity, it is possible to increase the filling amount of the inorganic filler, and as a result, the semiconductor element The package was reliable when soldered, and had good solder crack resistance and moisture resistance reliability.

  On the other hand, in Comparative Example 1, although fluidity and curability can be obtained, since the preliminary mixing is not performed at all, the alcohol component volatilizes during the curing reaction, which causes voids and remarkably increases the reliability. It is decreasing. Since the component which improves fluidity | liquidity is not added at all in the comparative example 2, when it is set as the material which contains many fillers, fluidity | liquidity is bad and a molding defect arises and reliability is reduced. In Comparative Example 3, phenylmethoxysilane corresponding to the component (D) is further added, and voids generated during the curing are further increased, thereby greatly reducing the reliability.

Claims (5)

In the epoxy resin composition containing the compound represented by the following general formula (1), the silane compound represented by the following general formula (2) and the curing accelerator, the compound represented by the following general formula (1), the following general An epoxy resin composition, wherein the silane compound and the curing accelerator represented by the formula (2) are melt-mixed under reduced pressure.

[Wherein X represents an organic group. ]

[Wherein R ¹ , R ² , and R ³ are aliphatic groups having 1 to 3 carbon atoms, and may be the same or different from each other. Z represents an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]   The epoxy resin composition according to claim 1, wherein the melt mixing is performed by heating at a temperature of 100 to 200 ° C.   The epoxy resin composition according to claim 1 or 2, wherein the melt mixing is performed by including an epoxy resin curing agent. The compound represented by the general formula (1) and the silane compound represented by the general formula (2) are mixed at a molar ratio satisfying the following formula, according to any one of claims 1 to 3. The epoxy resin composition as described.
Mc ≧ Md × 2
In the above formula, Mc is the number of moles of the compound represented by the general formula (1), and Md is the number of moles of the compound represented by the general formula (2).   The semiconductor device formed by sealing an electronic component with the hardened | cured material of the epoxy resin composition in any one of Claims 1-4.