JP5673237B2 - Resin composition for sealing and electronic component device - Google Patents

Description

  The present invention relates to a sealing resin composition and an electronic component device.

  In recent years, as electronic component devices such as integrated circuits (ICs), large-scale integrated circuits (LSIs), and very large-scale integrated circuits (VLSIs) and semiconductor devices become more dense and highly integrated, their mounting methods are insertion mounting. To surface mounting. Along with this, lead pins are required to have a large number of pins and lead pitches are narrowed. Surface mount type QFP (Quad Flat Package), which is small and light, and can accommodate a large number of pins, is used in various semiconductor devices. It has been. And since the semiconductor device is excellent in balance of productivity, cost, reliability, etc., sealing by transfer molding using an epoxy resin composition has become the mainstream.

Since the resin composition leaks to the metal terminal part of the semiconductor device due to insufficient precision or aging of the transfer molding die, burrs are generated. Conventionally, removal of burrs by laser, water jet, etc. The process has been generally performed. However, in the former method, the plating layer on the surface of the terminal is easily damaged, and in the latter method, burrs may not be sufficiently removed. In either case, there is a problem that a solder plating defect is induced. As a technique for solving these problems, a burr removal method combining electrolytic treatment and a water jet has become widespread. Electrolytic treatment means that a cathode is connected to a metal lead frame and an anode is connected to an electrolytic treatment liquid layer, and a voltage is applied while immersed in an alkaline aqueous solution. By generating bubbles, minute damage is caused, and by high-speed water jet treatment, burrs are removed, and there is also an advantage of excellent productivity.
However, this method may impair the adhesion between the resin composition and the metal lead frame depending on the electrolysis conditions and the design of the semiconductor device. Specifically, the pad-exposed quad flat package (QFP), low profile quad flat package (LQFP), quad with the backside of the device mounting pad exposed on the surface of the device -When a flat non-lead package (QFN) is subjected to a solder mounting process after an electrolytic process, there has been a problem that peeling is likely to occur on the outer periphery of the pad.
In addition, against the background of environmental issues in recent years, there has been an increasing social demand to eliminate the use of flame retardants such as brominated epoxy resins and antimony oxide, which have been used in the past, and these flame retardants are not used. In addition, a technique for imparting the same flame retardance as that of the prior art is required. As such an alternative flame-retarding technique, for example, a technique of applying a low-viscosity crystalline epoxy resin and blending more inorganic fillers has been proposed (see, for example, Patent Document 1 and Patent Document 2). However, it cannot be said that these methods sufficiently satisfy the resistance to electrolytic treatment, solder resistance and flame retardancy.

  As described above, in sealing resin compositions, it has become an important subject to be excellent in electrolytic deburring resistance, solder resistance and flame resistance.

JP-A-7-130919 JP-A-8-20673

  The present invention provides a sealing resin composition excellent in electrolytic deburring resistance, solder resistance and flame resistance, and an electronic component device excellent in reliability in which an element is sealed with a cured product thereof. Is.

  The encapsulating resin composition of the present invention comprises one or more polymers having a structure represented by the following general formula (1), and in the following general formula (1), at least (b-1) / d> An epoxy resin (A) containing any one of a polymer to be 1 and a polymer to be (b-1) / d <1, and one or more polymers having a structure represented by the following general formula (2) A phenol resin-based curing agent (B) containing an inorganic filler (C).

(In the general formula (1), R1 and R2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is an integer of 0 to 3, and c is an integer of 1 to 4. Both ends of the structural formula are hydrogen atoms, b and d are integers of 1 to 20. b repeating units that are substituted or unsubstituted glycidoxyphenylene groups and d that is a substituted phenylene group. (Each repeating unit may be continuously arranged, or may be alternately or randomly arranged with each other, but always has a methylene group between them.)

(In the general formula (2), R3 is independently a hydrocarbon group having 1 to 6 carbon atoms, e is an integer of 0 to 3, and both ends of the structural formula are hydrogen atoms. f is an integer of 1 to 20, and g, h, and i are integers of 0 to 19. Including any polymer in which h is 1 or more, or i is 1 or more. .
F repeating units which are substituted or unsubstituted hydroxyphenylene groups;
G repeating units which are unsubstituted biphenylene groups;
H repeating units that are biphenylene groups having one hydroxyphenylmethyl as a substituent and i repeating units that are biphenylene groups having two hydroxyphenylmethyl as a substituent are:
Each of them may be continuously arranged, or may be alternately or randomly arranged, but each must always have a methylene group. )

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

  In the encapsulating resin composition of the present invention, the curing accelerator (D) comprises a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, or an adduct of a phosphonium compound and a silane compound. It may contain at least one curing accelerator selected from the group.

  The sealing resin composition of the present invention may further include a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring.

  The sealing resin composition of the present invention may further contain a coupling agent (F).

  In the sealing resin composition of the present invention, the coupling agent (F) may contain a silane coupling agent having a secondary amino group.

  In the sealing resin composition of the present invention, the coupling agent (F) may contain a silane coupling agent having a mercaptosilane group.

  The sealing resin composition of the present invention can further contain an inorganic flame retardant (G).

  In the sealing resin composition of the present invention, the inorganic flame retardant (G) may contain a metal hydroxide or a composite metal hydroxide.

  The electronic component device of the present invention is characterized in that an element is sealed with a cured product obtained by curing the above-described sealing resin composition.

  According to the present invention, the device is sealed with a resin composition for sealing having a good balance of electrolytic deburring resistance, solder resistance, flame resistance, and continuous moldability, and its cured product, and excellent in reliability. An electronic component device can be obtained economically.

It is the figure which showed the cross-sectional structure about an example of the electronic component apparatus with which the electronic component element mounted in the metal lead frame was sealed with the hardened | cured material of the resin composition for sealing which concerns on this invention. It is the figure which showed the cross-sectional structure about an example of the single-side sealing type | mold electronic component apparatus by which the electronic component element mounted in the organic substrate was sealed with the hardened | cured material of the sealing resin composition which concerns on this invention. . An example of a single-sided sealing type electronic component device of a batch molding method in which an electronic component element mounted on a metal lead frame is sealed with a cured product of the sealing resin composition according to the present invention is collectively sealed. It is the figure which showed the cross-section of the electronic component apparatus of the state before separating into pieces. An electronic component device in which an electronic component element mounted on a metal lead frame is sealed with a cured product of the sealing resin composition according to the present invention, wherein the back surface of the pad on which the element is mounted is the surface of the device It is the figure which showed the cross-sectional structure about an example of the pad-exposed type exposed to. It is a FD-MS chart of the epoxy resin 1 used in the Example. It is a FD-MS chart of the phenol resin 1 used in the Example.

  The encapsulating resin composition of the present invention comprises one or more polymers having a structure represented by the following general formula (1), and in the following general formula (1), at least (b-1) / d> An epoxy resin (A) containing any one of a polymer to be 1 and a polymer to be (b-1) / d <1, and one or more polymers having a structure represented by the following general formula (2) A phenol resin-based curing agent (B) containing an inorganic filler (C). Thereby, the resin composition for sealing excellent in the balance with respect to the electrolytic deburring process, the solder resistance, and the flame retardancy can be obtained. Moreover, the electronic component device of the present invention is characterized in that an element is sealed with a cured product of the above-described sealing resin composition. Thereby, the electronic component apparatus excellent in reliability can be obtained economically. Hereinafter, the present invention will be described in detail. In addition, the numerical range represented by “to” in the present specification includes both the upper limit value and the lower limit value.

[Epoxy resin (A)]
As an epoxy resin (A) used for the resin composition for semiconductor encapsulation of the present invention, it consists of one or more polymers having a structure represented by the following general formula (1). In the following general formula (1), At least one of a polymer satisfying (b-1) / d> 1 and a polymer satisfying (b-1) / d <1 is included.

(In the general formula (1), R1 and R2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is an integer of 0 to 3, and c is an integer of 1 to 4. Both ends of the structural formula are hydrogen atoms, b and d are integers of 1 to 20. b repeating units that are substituted or unsubstituted glycidoxyphenylene groups and d that is a substituted phenylene group. (Each repeating unit may be continuously arranged, or may be alternately or randomly arranged with each other, but always has a methylene group between them.)

In the general formula (1), examples of the known polymer in which a = 0, c = 0, and (b-1) / d = 1 include a phenol aralkyl type epoxy resin having a phenylene skeleton. The resin composition using this has good curability, flame resistance, and solder resistance.
The epoxy resin (A) used in the present invention has a similar skeleton structure as compared with a phenol aralkyl type epoxy resin having a phenylene skeleton, and generally shows the same characteristics, but by having a substituent R2, Alkali resistance is improved, and the following characteristics are exhibited. Since the substituent R2 of the general formula (1) is hydrophobic and has a bulky structure, the resin composition can be reduced in water absorption and cured at a reflow temperature (240 ° C. to 260 ° C.). The elastic modulus at the reflow temperature can be reduced. Therefore, the solder resistance of the electronic component device such as a semiconductor sealed package is further improved, and in particular, it has an effect of suppressing the occurrence of internal cracks. Furthermore, since the elastic modulus in the high temperature range is reduced, a foamed layer can be quickly formed in a combustion test, and better flame resistance can be obtained. Moreover, even when the epoxy resin (A1) is a copper oxide surface or a gold plating surface which is generally difficult to maintain adhesion with the resin composition, the effect of reducing and preventing the interfacial peeling between these metals and the resin composition. Even when the above-described metal lead frame is used, good solder resistance can be obtained. The reason for this is not clear, but one reason is due to the electron donating property of the substituent R1.

In the general formula (1), the polymer satisfying (b-1) / d <1 has d repeats which are substituted phenylene groups as compared with the polymer where (b-1) / d = 1. A resin composition having a high unit ratio, excellent in flame resistance and alkali resistance, and excellent in solder resistance can be obtained by reducing the elastic modulus during heating by reducing the crosslinking density.
In the general formula (1), the polymer in which (b-1) / d> 1 is a substituted or unsubstituted glycidoxyphenylene group as compared with the polymer in which (b-1) / d = 1. The proportion of the b repeating units is relatively high, the density of the epoxy group is locally increased, and the curability and adhesion are improved.
By including any one of (b-1) / d> 1 polymer and (b-1) / d <1 polymer, not only flame resistance and solder resistance, but also alkali resistance and adhesion. It is possible to obtain an excellent resin composition.
In addition, as a polymer satisfying (b-1) / d <1, a polymer satisfying b = 1 can be included, and the content ratio is not limited, but with respect to 100% by mass of the epoxy resin (A). , Preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 10% by mass or more. On the other hand, the upper limit of the content of the polymer for b = 1 is not particularly limited, but is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 30% by mass or less, based on 100% by mass of the epoxy resin (A). Preferably it is 25 mass% or less. When the content of the polymer in which b = 1 is equal to or higher than the lower limit, solder resistance, flame resistance, and fluidity can be improved. When the content of the polymer in which b = 1 is not more than the above upper limit value, the curability is high, a sufficient molded product hardness can be obtained during molding, and the moldability is excellent. Moreover, when the polymer which becomes b = 1 is the said range content, the crosslinking density of an epoxy resin (A) reduces moderately, a foaming layer is formed at the time of combustion, and flame resistance improves.
The content of the polymer with b = 1 in the epoxy resin (A) (or all epoxy resins) can be determined by, for example, a field desorption mass spectrometry (FD-MS) measurement method. In this measurement method, the molecular weight and the number of repetitions can be obtained from the detected mass (m / z) for each peak detected by FD-MS analysis measured in the detected mass (m / z) range of 50 to 2000. it can. Then, by calculating the intensity ratio of each peak as a content ratio (mass), the content of the polymer in the epoxy resin (A) with b = 1 can be obtained.

[Synthesis Method of Epoxy Resin (A)]
The epoxy resin (A) according to the present invention is obtained by reacting a precursor phenol compound (P) represented by the following general formula (3) with epihalohydrin.

In the general formula (3), R1, R2, a, b, c, and d are the same as those in the general formula (1).

  As an example of the synthesis method of the epoxy compound (A), after adding an excess epihalohydrin to the precursor phenol compound (P) represented by the general formula (3) and dissolving it, sodium hydroxide, potassium hydroxide, etc. Examples include a method of reacting at 50 to 150 ° C., preferably 60 to 120 ° C. for 1 to 10 hours in the presence of an alkali metal hydroxide. After completion of the reaction, excess epihalohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the epoxy compound is removed by distilling off the solvent. (A) can be obtained.

[Precursor phenol compound (P)]
Next, a synthesis example of a compound having a structure represented by the general formula (3) (precursor phenol compound (P)) will be described.

The method for synthesizing the precursor phenol compound (P) is not particularly limited. For example, the phenol compound represented by the following general formula (4) and the compound represented by the following general formula (5), A method obtained by reacting the compound represented by the general formula (6) with an aldehyde is used (first synthesis method).
In addition, an alkyl-substituted aromatic compound represented by the following general formula (7) and an aldehyde are subjected to a polymerization reaction, and then polycondensation is performed by adding an aldehyde and a phenol compound represented by the general formula (4). (Hereinafter, also referred to as “second production method”), and the like, and these polymerization methods may be combined in an appropriate combination.

  Among these, the 2nd manufacturing method is preferable at the point that a raw material can be obtained cheaply. Further, commercially available phenol resins having the same structure may be used, and examples thereof include Nicanol GLP manufactured by Mitsubishi Gas Chemical Co., Ltd. and SYSTER GP-90 manufactured by FUDO Co., Ltd.

In the general formula (4), R1 and a are the same as those in the general formula (1).

In the general formula (5), R2 and c are the same as those in the general formula (1). X is a halogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

In the general formula (6), R2 and c are the same as those in the general formula (1). X is a halogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.

In the general formula (7), R2 and c are the same as those in the general formula (1).

Examples of the phenol compound that can be used for the synthesis of the precursor phenol compound (P) include phenol, o-cresol, p-cresol, m-cresol, phenylphenol, ethylphenol, n-propylphenol, and iso-propylphenol. Tert-butylphenol, xylenol, methylpropylphenol, methylbutylphenol, dipropylphenol, dibutylphenol, nonylphenol, mesitol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, and the like. It is not limited. Among these, phenol and o-cresol are preferable, and phenol is preferable because it exhibits good reactivity. In the synthesis and production of the precursor phenol compound (P), these phenol compounds may be used alone or in combination of two or more.

In the compounds represented by the general formula (5), general formula (6), and general formula (7) that can be used for the synthesis of the precursor phenol compound (P), R2 is a hydrocarbon group having 1 to 6 carbon atoms. If there is no particular limitation, for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, tert-pentyl Group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 2,4 -Dimethylbutyl group, 3,3-dimethylbutyl group, 3,
Examples include 4-dimethylbutyl group, 4,4-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, cyclohexyl group, and phenyl group. In particular, when R2 is a methyl group, methyl-substituted benzenes that are decomposed during combustion readily form aggregates due to the CH-soot interaction, and a resin composition having excellent flame resistance can be obtained.

In the compounds represented by the general formula (5), general formula (6), and general formula (7) that can be used for the synthesis of the precursor phenol compound (P), the substitution number c is an integer of 1 to 4. Although there is no particular limitation, in particular, when the number of substitutions c = 2, a resin composition having an excellent balance of moisture resistance, alkali resistance and continuous moldability can be obtained.

Examples of the compound represented by the general formula (7) that can be used in the second production method of the precursor phenol compound (P) include toluene, o-xylene, m-xylene, p-xylene, 1,3,5-trimethyl. Benzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, ethylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,3,5-triethylbenzene, 1,2,3-tri Ethylbenzene, n-1,2,4-triethylbenzene, cumene, o-cymene, m-cymene, p-cymene, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, pentylbenzene, dipentylbenzene, tetramethyl Examples include benzene.
Among these, xylene is preferable from the viewpoint of the balance of flame resistance, moisture resistance, alkali resistance and continuous moldability of the encapsulating resin composition of the present invention, and m-xylene is more preferable from the viewpoint of economy.

Examples of aldehydes used in the production of the precursor phenol compound (P) include formaldehyde, paraformaldehyde, formalin, trioxane and the like.

  As an example of the first synthesis method of the precursor phenol compound (P), the compound represented by the general formula (5), the general formula (6) with respect to 1 mol of the phenol compound represented by the general formula (4). ), A total of 2 to 10 moles of aldehydes, formic acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Lewis acid, etc. 0.05 mol is reacted at a temperature of 40 to 180 ° C. for 2 to 20 hours while discharging the generated gas out of the system by nitrogen flow, and the monomer remaining after the reaction is distilled by a method such as vacuum distillation or steam distillation. Can be obtained by leaving. When X in the general formula (5) or the general formula (6) is a halogen, the generated hydrogen halide can be used as an acidic catalyst by adding a small amount of water to the reaction system.

  As a second synthesis method of the precursor phenol compound (P), 0.1 to 0.8 mol of an aldehyde is used as a catalyst with respect to 1 mol of the alkyl-substituted aromatic compound represented by the general formula (7). Add 0.05-2.0 mol of strong acid such as p-toluenesulfonic acid, xylenesulfonic acid, sulfuric acid, etc., react at 100-150 ° C for 0.5-5 hours, and remove unreacted components by steam distillation. To obtain a reaction intermediate. Here, as this reaction intermediate, a commercially available aromatic hydrocarbon-formaldehyde resin may be used. Specifically, as a commercially available product, xylene-formaldehyde resins such as Nikanol G, Nikanol L, Nikanol H, etc., manufactured by Fudou Co., Ltd. And mesitylene-formaldehyde resins such as Nikanol Y5001, Nikanol Y1001, Nikanol Y101, Nikanol Y51, and Nikanol M manufactured by Mitsubishi Gas Chemical Co., Ltd. Subsequently, 0.2 to 1.2 mol of a phenol compound represented by the general formula (4), an acidic catalyst such as oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Lewis acid 0 Add ~ 0.05 mol in small portions and conduct a condensation reaction for 1 to 5 hours while discharging the generated gas out of the system at a temperature of 50 to 170 ° C by nitrogen flow. After the reaction, unreacted components and water are distilled under reduced pressure It can be obtained by distilling off by a method such as steam distillation.

  Examples of epihalohydrins used for the synthesis of the epoxy resin (A) include, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepiiodohydrin, and the like. Can be mentioned.

  The softening point of the epoxy resin (A) used in the present invention is 60 ° C. from the viewpoint that melting of the sealing resin composition is easy, blocking of the resulting resin composition hardly occurs, and handling properties are good. The temperature is preferably 110 ° C. or lower.

  The ICI viscosity at 150 ° C. of the epoxy resin (A) used in the present invention is preferably 0.8 dPa · s to 10 dPa · s. Thereby, when melt-kneading the resin composition for sealing, it can mix favorably and the obtained resin composition for sealing can express a favorable flow characteristic.

  Moreover, the lower limit of the compounding amount of the epoxy resin (A) in the sealing resin composition of the present invention is preferably 0.5% by mass or more with respect to the total mass of the sealing resin composition. Preferably it is 1 mass% or more, More preferably, it is 1.5 mass% or more. When the lower limit is within the above range, the resulting resin composition has good fluidity. Moreover, the upper limit of the compounding quantity of the epoxy resin (A) in the sealing resin composition is preferably 12% by mass or less, more preferably 10% by mass or less, with respect to the total mass of the sealing resin composition. More preferably, it is 8 mass% or less. When the upper limit is within the above range, the resulting resin composition has good solder resistance and curability.

  In the sealing resin composition of the present invention, other epoxy resins can be used as long as the effects of using the epoxy resin (A) are not impaired.

Other epoxy resins that can be used in combination are not particularly limited. For example, crystalline epoxy resins such as biphenyl type epoxy resins, bisphenol type epoxy resins, stilbene type epoxy resins, dihydroanthracene diol type epoxy resins; phenol novolac type epoxies Resin, novolak type epoxy resin such as cresol novolac type epoxy resin; polyfunctional epoxy resin such as triphenolmethane type epoxy resin and alkyl-modified triphenolmethane type epoxy resin; aralkyl type epoxy such as phenol aralkyl type epoxy resin having phenylene skeleton Resin: Epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene-type epoxy resin, hydroxynaphthalene and / or dihydroxynaphthalene dimer, phenylene skeleton Epoxidizing a novolak naphthol resin obtained by reacting naphthols such as naphthol aralkyl type epoxy resin, hydroxynaphthalene or dihydroxynaphthalene with aldehyde compounds such as formaldehyde, acetaldehyde, benzaldehyde and salicylaldehyde in the presence of an acid catalyst Naphthol type epoxy resins such as obtained resins; modified novolak type epoxy resins having a methoxynaphthalene skeleton; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; dicyclopentadiene modified phenol type epoxy resins Examples thereof include, but are not limited to, a bridged cyclic hydrocarbon compound-modified phenol type epoxy resin. These epoxy resins preferably do not contain Na ⁺ ions and Cl ⁻ ions, which are ionic impurities, as much as possible from the viewpoint of moisture resistance reliability of the resulting sealing resin composition. From the viewpoint of curability of the resin composition, the epoxy equivalent of the epoxy resin is preferably 100 g / eq or more and 500 g / eq or less.
When the epoxy resin (A) and the other epoxy resin are used in combination, the lower limit value of the total amount of the epoxy resin is preferably 0.5% by mass with respect to the total mass of the sealing resin composition. It is above, More preferably, it is 1 mass% or more, More preferably, it is 1.5 mass% or more. When the lower limit is within the above range, the resulting resin composition has good fluidity. Moreover, the upper limit of the compounding quantity of all the epoxy resins in the resin composition for sealing is preferably 12% by mass or less, more preferably 10% by mass or less, with respect to the total mass of the resin composition for sealing. More preferably, it is 8 mass% or less. When the upper limit is within the above range, the resulting resin composition has good solder resistance and curability.

Among the epoxy resins that can be used in combination, from the viewpoint of solder resistance and fluidity, an epoxy resin having crystallinity such as a biphenyl type epoxy resin, a bisphenol type epoxy resin, a dihydroanthracene diol type epoxy resin is preferable. If it is an epoxy resin, by using it in combination with the epoxy resin (A), the balance between electrolytic deburring resistance, solder resistance, flame resistance and continuous formability is stably improved while improving fluidity. The effect is obtained. Among them, when combined with a dihydroanthracenediol type epoxy resin, the packing density of polycyclic aromatics is locally increased, thereby reducing warpage and improving metal adhesion in an electronic component device after molding. In particular, when used in pad-exposed type electronic component devices such as MAP-QFN that are collectively encapsulated and molded, not only has excellent anti-electrolytic deburring properties, but also low warpage handling. This is preferable in that it brings about effects such as improvement and reduction of stress.

[Phenolic resin curing agent (B)]
The phenol resin curing agent (B) used in the encapsulating resin composition of the present invention contains one or more polymers having a structure represented by the following general formula (2).

(In the general formula (2), R3 is independently a hydrocarbon group having 1 to 6 carbon atoms, e is an integer of 0 to 3, and both ends of the structural formula are hydrogen atoms. f is an integer of 1 to 20, and g, h, and i are integers of 0 to 19. Including any polymer in which h is 1 or more, or i is 1 or more. F repeating units that are substituted or unsubstituted hydroxyphenylene groups, g repeating units that are unsubstituted biphenylene groups, and h phenyl groups that are biphenylene groups having one hydroxyphenylmethyl as a substituent. The repeating unit and the i repeating units which are biphenylene groups having two hydroxyphenylmethyl as substituents may be arranged consecutively or alternately or randomly. The In the present application, a part of the bond of the biphenylene structural formula may be represented by a dotted line as shown in the following general formula (X), but this represents a substituent (hydroxyphenylmethyl). ) Is any one of the following general formula (X-1) or general formula (X-2).

R3 is not particularly limited as long as it is a hydrocarbon group having 1 to 6 carbon atoms. For example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 3-methylbutyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,2-dimethylbutyl Group, 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 3,3-dimethylbutyl group, 3,4-dimethylbutyl group, 4,4-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl Group, cyclohexyl group and phenyl group. Especially, when R3 is a methyl group, a resin composition excellent in moisture resistance can be obtained. Moreover, when the substitution number e is 0, it can be set as the resin composition excellent in sclerosis | hardenability, and when the substitution number e is 1-3, the resin composition excellent in flame resistance and alkali resistance can be obtained. .

Examples of the structure in which f repeating units that are substituted or unsubstituted hydroxyphenylene groups and g repeating units that are unsubstituted biphenylene groups are arranged alternately include, for example, a phenol aralkyl-type heavy chain having a biphenylene group. The resin composition exhibits excellent flame resistance, low water absorption, and solder resistance. These characteristics are considered to be the effects of the biphenylene group.

  On the other hand, the phenol resin-based curing agent (B) used in the present invention is a biphenylene group having one hydroxyphenylmethyl as a substituent in addition to the structure of the above-mentioned phenol aralkyl type polymer having a biphenylene group. Repeating units and i repeating units which are biphenylene groups having two hydroxyphenylmethyls as substituents. The presence of this biphenylene group having one or two hydroxyphenylmethyls locally increases the density of the phenolic hydroxyl group, resulting in the reactivity, curability, heat resistance, hot hardness of the resin composition, and Adhesion can be improved. In addition, f repeating units that are substituted or unsubstituted hydroxyphenylene groups, g repeating units that are unsubstituted biphenylene groups, and h number that are biphenylene groups having one hydroxyphenylmethyl as a substituent. And i repeating units, which are biphenylene groups having two hydroxyphenylmethyl as substituents, are arranged in a random manner, so that more reactive phenolic hydroxyl groups and hydrophobic, highly flame-resistant biphenyls can be obtained. It can be expected that the density distribution of the structure becomes non-uniform and the above-described effect is further enhanced.

As a manufacturing method of the phenol resin curing agent (B) comprising one or more polymers having a structure represented by the general formula (2), for example,
(1) A tetrafunctional biphenyl compound represented by the following general formula (8), a trifunctional biphenyl compound represented by the following general formula (9), and a bifunctional biphenyl compound represented by the following general formula (10) A method of reacting a monofunctional biphenyl compound represented by the formula (11) with a phenol compound represented by the following general formula (12) in the presence of a strong acid catalyst (hereinafter also referred to as “first production method”); Biphenyl and formaldehyde are reacted in the presence of hydrogen halide and a catalyst to synthesize a reaction intermediate mainly composed of methylated biphenyl, and then reacted with a phenol compound represented by the following general formula (12) The method (hereinafter also referred to as “second production method”) and the like can be mentioned, but are not limited thereto. You may synthesize | combine using one of these manufacturing methods independently, or may synthesize | combine combining 2 or more types.

In the said General formula (8), X is a halogen atom, a hydroxyl group, or a C1-C6 alkoxy group.

In the said General formula (9), X is a halogen atom, a hydroxyl group, or a C1-C6 alkoxy group.

In the general formula (10), X is a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

In the said General formula (11), X is a halogen atom, a hydroxyl group, or a C1-C6 alkoxy group.

In the general formula (12), R3 and e are the same as those in the general formula (2).

The tetrafunctional biphenyl compound used in the first production method of the phenol resin curing agent (B) is not particularly limited as long as it has a chemical structure represented by the general formula (8). For example, 2, 4, 2 ', 4
'-Tetrachloromethylbiphenyl, 2,4,2', 4'-tetrabromomethylbiphenyl, 2,4,2 ', 4'-tetraiodomethylbiphenyl, 2,4,2', 4'-tetrahydroxymethyl Biphenyl, 2,4,2 ′, 4′-tetramethoxymethylbiphenyl, 2
, 4,6,4′-tetrachloromethylbiphenyl, 2,4,6,4′-tetrabromomethylbiphenyl, 2,4,6,4′-tetraiodomethylbiphenyl, 2,4,6,4′- Examples thereof include, but are not limited to, tetrahydroxymethylbiphenyl and 2,4,6,4′-tetramethoxymethylbiphenyl. These may be used alone or in combination of two or more.
Among these, 2,4,2 ′, 4′-tetramethoxymethylbiphenyl is preferable from the viewpoint that the reaction can be performed at a relatively low temperature and the reaction by-product can be easily distilled off and handled. 2,4,2 ′, 4′-tetrachloromethylbiphenyl is preferred in that hydrogen halide generated due to the presence of moisture can be used as an acid catalyst.

The trifunctional biphenyl compound used for the 1st manufacturing method of a phenol resin type hardening | curing agent (B) will not be specifically limited if it is a chemical structure represented by General formula (9). For example, 2,4,4′-trichloromethylbiphenyl, 2,4,4′-tribromomethylbiphenyl, 2,4,4′-triiodomethylbiphenyl, 2,4,4′-trihydroxymethylbiphenyl, 2 , 4,4′-trimethoxymethylbiphenyl, 2,4,2′-trichloromethylbiphenyl, 2,4,2′-tribromomethylbiphenyl, 2,4,2′-triiodomethylbiphenyl, 2,4,2 Examples include, but are not limited to, 2′-trihydroxymethylbiphenyl, 2,4,2′-trimethoxymethylbiphenyl, and the like. These may be used alone or in combination of two or more.
Among these, 2,4,4′-trimethoxymethylbiphenyl is preferable from the viewpoint that the reaction can be performed at a relatively low temperature and the reaction by-product can be easily distilled off and handled. 2,4,4′-trichloromethylbiphenyl or 2,4,2′-trichloromethylbiphenyl is preferred in that hydrogen halide generated due to the above can be used as an acid catalyst.

The bifunctional biphenyl compound used in the first production method of the phenol resin curing agent (B) is:
If it is a chemical structure represented by General formula (10), it will not specifically limit. For example, 4,4′-bischloromethylbiphenyl, 4,4′-bisbromomethylbiphenyl, 4,4′-bisiodomethylbiphenyl, 4,4′-bishydroxymethylbiphenyl, 4,4′-bismethoxymethyl Biphenyl and the like can be mentioned, but are not limited thereto. These may be used alone or in combination of two or more.
Among these, 4,4′-bismethoxymethylbiphenyl is preferable from the viewpoint that the reaction can be performed at a relatively low temperature and the reaction by-product can be easily distilled off and handled. Thus, 4,4′-bischloromethylbiphenyl is preferable in that the hydrogen halide generated can be used as an acid catalyst.

The monofunctional biphenyl compound used for the 1st manufacturing method of a phenol resin type hardening | curing agent (B) will not be specifically limited if it is a chemical structure represented by General formula (11). For example, 4-chloromethylbiphenyl, 4-bromomethylbiphenyl, 4-iodomethylbiphenyl, 4-hydroxymethylbiphenyl, 4-methoxymethylbiphenyl, 2-chloromethylbiphenyl, 2-bromomethylbiphenyl, 2-iodomethylbiphenyl, Examples include 2-hydroxymethylbiphenyl and 2-methoxymethylbiphenyl, but are not limited thereto. These may be used alone or in combination of two or more.
Among these, methoxymethylbiphenyl is preferable from the viewpoint that the reaction can be performed at a relatively low temperature, and the reaction by-product can be easily distilled off and handled, and the halogenation generated due to the presence of a small amount of moisture. Chloromethylbiphenyl is preferred in that hydrogen can be used as an acid catalyst.

The phenol compound used in the first or second production method of the phenol resin-based curing agent (B) is not particularly limited as long as it has a chemical structure represented by the general formula (12). For example, phenol, o-cresol, p-cresol, m-cresol, phenylphenol, ethylphenol, n-propylphenol, isopropylphenol, tert-butylphenol, xylenol, methylpropylphenol, methylbutylphenol, dipropylphenol, dibutylphenol, Examples include, but are not limited to, mesitol, 2,3,5-trimethylphenol, and 2,3,6-trimethylphenol. These may be used alone or in combination of two or more.
Among these, phenol and o-cresol are preferable, and phenol is more preferable from the viewpoint of reactivity with the epoxy resin. These phenol compounds may be used alone or in combination of two or more.

Examples of formaldehydes used in the second production method of the phenol resin-based curing agent (B) include formaldehyde, paraformaldehyde, formalin, and the like.

As a hydrogen halide used for the 2nd manufacturing method of a phenol resin type hardening | curing agent (B), hydrogen chloride, hydrogen bromide, hydrogen iodide etc. are mentioned, for example. Among these, it is preferable to use hydrogen chloride in the form of gas from the viewpoint that the neutralization treatment of the gas continuously discharged from the reaction system can be easily performed. In addition, it is desirable to supply these hydrogen halides excessively as a gas to the reaction system from the viewpoint of reaction efficiency.

  The reaction intermediate mainly composed of methylated biphenyl obtained by the second production method of the phenol resin curing agent (B) is a mixture of the above general formulas (8) to (11), and the following general formula (13 Or a compound represented by the following general formula (14).

In the said General formula (13), X is a halogen atom, a hydroxyl group, or a C1-C6 alkoxy group. X reflects the halogen atom of the hydrogen halide used in the synthesis.

In the said General formula (14), X is a halogen atom, a hydroxyl group, or a C1-C6 alkoxy group. X reflects the halogen atom of the hydrogen halide used in the synthesis.

Of the methods for synthesizing the phenol resin curing agent (B), in the case of the first production method, the general formula (8), the general formula (9), and the general formula (10) with respect to 1 mol of the phenol compound. And a total of 0.05 to 0.8 mol of the biphenyl compound represented by the general formula (11), and a strong acid such as paratoluenesulfonic acid, xylenesulfonic acid and sulfuric acid as a catalyst at a temperature of 80 to 170 ° C. by nitrogen flow. While discharging the generated gas outside the system, the reaction is performed for 1 to 20 hours, and unreacted monomers, reaction by-products (for example, hydrogen halide, methanol), and catalyst remaining after the reaction are distilled by a method such as vacuum distillation or steam distillation. Can be obtained by leaving. In addition, when X in the general formula (8), the general formula (9), the general formula (10), and the general formula (11) is a halogen atom, it is generated by adding a small amount of water to the reaction system. Hydrogen halide can be used as an acid catalyst.

As a preferable range of the blending ratio of the above-mentioned biphenyl compound, with respect to 100% by mass of the total amount of biphenyl compound,
The monofunctional biphenyl compound is preferably 1 to 10% by mass, more preferably 1.5 to 6% by mass. If the blending ratio of the monofunctional biphenyl compound is not less than the above lower limit, the resulting resin composition can be excellent in fluidity. If the blending ratio of the monofunctional biphenyl compound is not more than the above upper limit, the resulting resin composition has excellent heat resistance and high-temperature storage characteristics, and has sufficient hardness at the molding temperature, and therefore has excellent continuous moldability. It can be.
50-90 weight% of a bifunctional biphenyl compound is preferable, More preferably, it is 60-80 mass%, More preferably, it is 65-75 mass%. If the blending ratio of the bifunctional biphenyl compound is not less than the above lower limit value, the resulting resin composition can be excellent in fluidity and curability. If the blending ratio of the bifunctional phenol compound is not more than the above upper limit value, the resulting resin composition can be excellent in moisture resistance and flame resistance.
The trifunctional biphenyl compound is preferably 5 to 25% by mass, more preferably 10 to 20% by mass. If the blending ratio of the trifunctional biphenyl compound is equal to or more than the above lower limit, the resulting resin composition can be excellent in moisture resistance adhesion and continuous moldability. If the blending ratio of the trifunctional biphenyl compound is not more than the above upper limit, the resulting resin composition can be excellent in fluidity.
The tetrafunctional biphenyl compound is preferably 1 to 15% by mass, more preferably 2 to 10% by mass. If the blending ratio of the tetrafunctional biphenyl compound is not less than the above lower limit value, it can be excellent in moisture resistance adhesion and continuous moldability. If the blending ratio of the tetrafunctional biphenyl compound is less than or equal to the above upper limit value, the fluidity can be improved.

Among the methods for synthesizing the phenol resin curing agent (B), in the case of the second production method, 2 to 8 mol of formaldehyde and 1 mol of biphenyl, sulfuric acid, aluminum chloride, iron chloride, tin chloride, chloride 0.1 to 1 mol of a catalyst such as zinc or trimethylbenzyl chloride is reacted at a temperature of 10 to 50 ° C. for 6 to 36 hours while hydrogen halide gas is blown into the reaction system to have methylated biphenyl as a main component. A reaction intermediate is obtained. In the above reaction, a solvent such as cyclohexane, hexane, or heptane may be used. Next, 2 to 6 mol of phenol compound and 0.1 to 1% by mass of water are added, and at a temperature of 0 to 120 ° C., the generated gas is discharged out of the system by nitrogen flow, and reacted for 1 to 20 hours. It can be obtained by distilling off unreacted monomers, reaction by-products (for example, hydrogen halide, methanol), and catalyst remaining after the reaction by a method such as distillation under reduced pressure or steam distillation. In the above reaction, a solvent such as cyclohexane, hexane, or heptane may be used.

  Although there is no restriction | limiting in particular in the lower limit of the hydroxyl equivalent of a phenol resin type hardening | curing agent (B), 180 g / eq or more is preferable, More preferably, it is 190 g / eq or more. If it is more than the said lower limit, the resin composition obtained can have a small amount of wire flow and excellent in low water absorption. The upper limit of the hydroxyl group equivalent of the phenol resin-based curing agent (A) is preferably 220 g / eq or less, more preferably 210 g / eq or less, and still more preferably 205 g / eq or less. If it is below the said upper limit, the resin composition obtained will be excellent in continuous moldability and adhesiveness.

  Although there is no restriction | limiting in particular in the upper limit of the softening point of a phenol resin type hardening | curing agent (B), 110 degrees C or less is preferable and 105 degrees C or less is more preferable. If it is below the said upper limit, the resin composition obtained can be heat-melted rapidly at the time of manufacture of a resin composition, and shall be excellent in productivity. Although there is no restriction | limiting in particular in the lower limit of the softening point of a phenol resin type hardening | curing agent (B), 55 degreeC or more is preferable and 60 degreeC or more is more preferable. If it is more than the said lower limit, the obtained resin composition cannot be blocked easily and can be excellent in continuous moldability.

  About the compounding quantity of a phenol resin type hardening | curing agent (B), it is preferable that it is 0.5 mass% or more and 10 mass% or less with respect to all the resin compositions, and it is 2 mass% or more and 8 mass% or less. Is more preferably 4% by mass or more and 7.5% by mass or less. If it is in the said range, the resin composition obtained shall be excellent in balance of sclerosis | hardenability, heat resistance, and solder resistance.

  The resin composition for semiconductor encapsulation of the present invention can be used in combination with another curing agent as long as the effect of using the phenol resin curing agent (B) is not impaired. Although it does not specifically limit as a hardening | curing agent which can be used together, For example, a polyaddition type hardening | curing agent, a catalyst type hardening | curing agent, a condensation type hardening | curing agent etc. can be mentioned.

Examples of polyaddition type curing agents include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and metaxylenediamine, aromatic polyamines such as diaminodiphenylmethane, m-phenylenediamine, and diaminodiphenylsulfone, dicyandiamide, and organic acid dihydrazide. Polyamine compounds including: Acids including alicyclic acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, aromatic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic acid Anhydrides; Polyphenol compounds such as novolak-type phenol resins and phenol polymers; Polymercaptan compounds such as polysulfides, thioesters, and thioethers; Isocyanate prepolymers and blocks Isocyanate compounds such as isocyanate; and organic acids such as carboxylic acid-containing polyester resins.

Examples of the catalyst-type curing agent include tertiary amine compounds such as benzyldimethylamine and 2,4,6-trisdimethylaminomethylphenol; imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole; Examples include Lewis acids such as BF ₃ complex.

  Examples of the condensation type curing agent include phenolic resin-based curing agents such as novolak type phenolic resin and resol type phenolic resin; urea resin such as methylol group-containing urea resin; melamine resin such as methylol group-containing melamine resin, and the like. Can be mentioned.

  Among these, a phenol resin-based curing agent is preferable from the viewpoint of balance between flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like. The phenol resin-based curing agent is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak Resin, novolak resin such as naphthol novolak resin; polyfunctional phenol resin such as triphenolmethane phenol resin; modified phenol resin such as terpene modified phenol resin and dicyclopentadiene modified phenol resin; phenylene skeleton and / or biphenylene skeleton Aralkyl resins such as phenol aralkyl resins having phenylene and / or naphthol aralkyl resins having a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F These may be used in combination of two or more be used one kind alone. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.

  In the case where such other curing agents are used in combination, the blending ratio of the phenol resin curing agent (B) is preferably 25% by mass or more and 35% by mass or more with respect to the total curing agent. It is more preferable, and it is especially preferable that it is 45 mass% or more. When the blending ratio is within the above range, it is possible to obtain the effect of improving the flame resistance and high temperature storage characteristics while maintaining good continuous formability.

  Although it does not specifically limit about the lower limit of the compounding ratio of the whole hardening | curing agent, It is preferable that it is 0.8 mass% or more in all the resin compositions, and it is more preferable that it is 1.5 mass% or more. When the lower limit value of the blending ratio is within the above range, sufficient fluidity can be obtained. Further, the upper limit of the blending ratio of the entire curing agent is not particularly limited, but is preferably 10% by mass or less, and more preferably 8% by mass or less in the entire resin composition. When the upper limit of the blending ratio is within the above range, good solder resistance can be obtained.

[A combination of epoxy resin (A) and phenolic resin curing agent (B)]
In the sealing resin composition of the present invention, by combining the epoxy resin (A) and the phenol resin-based curing agent (B), the occurrence of peeling in the electrolytic deburring process is reduced, and the resistance in the subsequent mounting process is further reduced. Solderability can also be improved. The details of the mechanism are unknown, but the following reasons are presumed.
Focusing on the interface between the resin composition immediately after molding of the semiconductor device and the metal lead frame, the surface of the metal lead frame and the glycidyl group, hydroxyl group, or secondary hydroxyl group generated by a crosslinking reaction between the glycidyl group and the hydroxyl group in the resin composition Adhesiveness is developed by forming a hydrogen bond between the two. In the electrolytic deburring step, the semiconductor device obtained by molding is immersed in a sodium hydroxide aqueous solution (concentration: 10 to 30% by mass) heated to 40 to 70 ° C., and a cathode is placed on the metal lead frame of the semiconductor device. By installing an anode in the aqueous solution tank and applying a voltage, hydrogen bubbles are generated on the surface of the cathode (lead frame) to give minute scratches. At this time, water molecules and alkali components are diffused to the interface between the resin composition and the metal lead frame, and the above-described hydrogen bond is impaired, and there is a risk of causing separation at the resin composition-metal interface that should be in close contact. . Specifically, after the pad-exposed type semiconductor device is subjected to the electrolytic deburring step, peeling is observed on the side surface of the pad or the outer periphery of the pad, or after the electrolytic deburring step, 150 After performing the main curing at ˜180 ° C. and then performing the surface mounting process, peeling of the outer periphery of the pad and internal cracks may occur.

The epoxy resin (A) and the phenol resin-based curing agent (B) used in the present invention have an epoxy group or a hydroxyl group that is an adhesive driving force at the interface between the resin composition and the metal in each structure. These include polymers in which the distribution of these polar groups is not uniform. The above-mentioned dense part of the polar group forms a denser hydrogen bond with the metal surface, and good adhesion can be obtained. On the other hand, in the portion where the polar group is sparse, an alkyl-substituted phenylene group having excellent alkali resistance is present in the epoxy resin (A), and a highly hydrophobic biphenylene group is present in the phenol resin curing agent (B). The ratio becomes high. The resin composition of the present invention only adheres well to the metal surface after molding by allowing such highly adhesive sites and alkali-resistant and highly water-resistant sites to exist non-uniformly (or irregularly). In addition, it is considered that there is an effect of maintaining good adhesion even after the electrolytic deburring step.

  In the sealing resin composition of the present invention, (C) an inorganic filler can be further used. As the inorganic filler (C) that can be used in the encapsulating resin composition of the present invention, those generally used in encapsulating resin compositions can be used, such as fused silica and spherical silica. , Crystalline silica, alumina, silicon nitride, aluminum nitride and the like. The particle size of the inorganic filler (C) is preferably 0.01 μm or more and 150 μm or less in consideration of the filling property into the mold cavity.

  As a lower limit of the content rate of an inorganic filler (C), it is preferable that it is 75 mass% or more of the whole resin composition for sealing, it is more preferable that it is 80 mass% or more, and it is 83 mass% or more. It is particularly preferred. When the lower limit value of the content ratio of the inorganic filler (C) is within the above range, the sealing resin composition can obtain good tablet moldability, and as its cured product properties, the moisture absorption increases. The strength does not decrease, and good solder crack resistance can be obtained. Moreover, as an upper limit of the content rate of an inorganic filler (C), it is preferable that it is 93 mass% or less of the whole sealing resin composition, it is more preferable that it is 91 mass% or less, and 90 mass% or less. It is particularly preferred that When the upper limit value of the content ratio of the inorganic filler (C) is within the above range, the flowability is not impaired and good moldability can be obtained.

In the sealing resin composition of the present invention, a curing accelerator (D) can be further used. The curing accelerator (D) only needs to promote the reaction between the epoxy group of the epoxy resin (A) and the phenolic hydroxyl group of the phenol resin-based curing agent (B). You can use what is being used. Specific examples include phosphorus-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; 1,8-diazabicyclo (5 , 4, 0) Undecene-7, benzyldimethylamine, nitrogen atom-containing compounds such as 2-methylimidazole. Of these, phosphorus atom-containing compounds are preferred. From the viewpoint of the balance between fluidity and curability, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and additions of phosphonium compounds and silane compounds. A catalyst having latency such as a product is more preferable. In view of fluidity, a tetra-substituted phosphonium compound is particularly preferred, and a phosphobetaine compound in view of low thermal modulus of the cured resin composition and low mold contamination during continuous molding, An adduct of a phosphine compound and a quinone compound is particularly preferable. Also, the wire flow rate is small, and a molded array process ball grid array (
(MAP-BGA) and Molded Array Process Quad Flat Non-Lead Package (MAP-QFN), which is capable of reducing warpage of large-size single-sided molded products, such as phosphonium compounds and silane compounds. The adduct is particularly preferred.

  Examples of the organic phosphine that can be used in the sealing resin composition of the present invention include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, and tributylphosphine. And a third phosphine such as triphenylphosphine.

  Examples of the tetra-substituted phosphonium compound that can be used in the encapsulating resin composition of the present invention include compounds represented by the following general formula (15).

(However, in the said General formula (15), P represents a phosphorus atom. R4, R5, R6, and R7 represent an aromatic group or an alkyl group. A is a functional group chosen from a hydroxyl group, a carboxyl group, and a thiol group. Represents an anion of an aromatic organic acid having at least one of the following: AH is an aromatic organic acid having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring X and y are integers of 1 to 3, z is an integer of 0 to 3, and x = y.

  Although the compound represented by General formula (15) is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (15) can be precipitated. In the compound represented by the general formula (15), R4, R5, R6 and R7 bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols, and A Is preferably an anion of the phenol.

  Examples of the phosphobetaine compound that can be used in the encapsulating resin composition of the present invention include compounds represented by the following general formula (16).

(However, in the said General formula (16), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group. F is an integer of 0-5, and g is an integer of 0-4.)

  The compound represented by the general formula (16) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt, and replacing the triaromatic substituted phosphine with a diazonium group having a diazonium salt. However, the present invention is not limited to this.

  Examples of the adduct of a phosphine compound and a quinone compound that can be used in the sealing resin composition of the present invention include compounds represented by the following general formula (17).

(However, in the said General formula (17), P represents a phosphorus atom. R8, R9, and R10 represent a C1-C12 alkyl group or a C6-C12 aryl group, and they are mutually the same. R11, R12 and R13 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R11 and R12 are bonded to form a cyclic structure. May be.)

  Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent such as a substituent or an alkyl group or an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.

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

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

  In the compound represented by the general formula (17), R8, R9 and R10 bonded to the phosphorus atom are phenyl groups, and R11, R12 and R13 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl A compound to which phosphine has been added is preferred in that it reduces the thermal modulus of the cured product of the encapsulating resin composition.

  Examples of the adduct of a phosphonium compound and a silane compound that can be used in the sealing resin composition of the present invention include compounds represented by the following general formula (18).

(However, in the said General formula (18), P represents a phosphorus atom and Si represents a silicon atom. R14, R15, R16, and R17 are respectively an organic group or an aliphatic group which has an aromatic ring or a heterocyclic ring. X2 is an organic group bonded to the groups Y2 and Y3, where X3 is an organic group bonded to the groups Y4 and Y5. And Y3 represent a group formed by releasing a proton from a proton donating group, and groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate structure, and Y4 and Y5 are proton donating groups. The group represents a group formed by releasing a proton, and the groups Y4 and Y5 in the same molecule are bonded to a silicon atom to form a chelate structure.X2 and X3 are the same or different from each other. Well Y2, Y3, Y4, and Y5 is .Z1 which may be the same or different from each other is an organic group or an aliphatic group, an aromatic ring or a heterocyclic ring.)

  In the general formula (18), as R14, R15, R16 and R17, for example, phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, ethyl group, n-butyl group, n-octyl group, cyclohexyl group, and the like. Among these, an aromatic group having a substituent such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, or the like. A substituted aromatic group is more preferred.

Moreover, in General formula (18), X2 is an organic group couple | bonded with Y2 and Y3. Similarly, X3 is an organic group bonded to the groups Y4 and Y5. Y2 and Y3 are groups formed by proton-donating groups releasing protons, and groups Y2 and Y3 in the same molecule are combined with a silicon atom to form a chelate structure. Similarly, Y4 and Y5 are groups formed by proton-donating groups releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. The groups X2 and X3 may be the same or different from each other, and the groups Y2, Y3, Y4, and Y5 may be the same or different from each other. In the general formula (18), the groups represented by -Y2-X2-Y3- and -Y4-X3-Y5-
The proton donor is composed of a group formed by releasing two protons. Examples of the proton donor include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2, 2′-biphenol, 1,1′-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1, Examples include 2-cyclohexanediol, 1,2-propanediol, and glycerin. Among these, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable.

  Z1 in the general formula (18) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Reactions such as aliphatic hydrocarbon groups such as octyl group and aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxypropyl group, mercaptopropyl group, aminopropyl group and vinyl group Among them, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable from the viewpoint of thermal stability.

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

  The blending ratio of the curing accelerator (D) that can be used in the sealing resin composition of the present invention is more preferably 0.1% by mass or more and 1% by mass or less in the total resin composition. When the blending ratio of the curing accelerator (D) is within the above range, sufficient curability can be obtained. Moreover, sufficient fluidity | liquidity can be obtained as the mixture ratio of a hardening accelerator (D) exists in the said range.

  In the sealing resin composition of the present invention, a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring can be used. The compound (E) (hereinafter also referred to as “compound (E)”) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting the aromatic ring is used as an epoxy resin (A). Even when a phosphorus atom-containing curing accelerator having no latent property is used as a curing accelerator for promoting the crosslinking reaction with the phenol resin-based curing agent (B), the reaction during the melt-kneading of the resin composition The resin composition for sealing can be obtained stably. The compound (E) also has an effect of lowering the melt viscosity of the sealing resin composition and improving fluidity. As the compound (E), a monocyclic compound represented by the following general formula (19) or a polycyclic compound represented by the following general formula (20) can be used. It may have a substituent.

(In the general formula (19), one of R18 and R22 is a hydroxyl group, and when one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group. R19, R20 and R21 are hydrogen atoms) An atom, a hydroxyl group or a substituent other than a hydroxyl group.)

(However, in the general formula (20), one of R23 and R29 is a hydroxyl group, and when one is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group. R24, R25, R26, R27) And R28 is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group.)

  Specific examples of the monocyclic compound represented by the general formula (19) include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof. Specific examples of the polycyclic compound represented by the general formula (20) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Among these, a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring is preferable because of easy control of fluidity and curability. In consideration of volatilization in the kneading step, it is more preferable that the mother nucleus is a compound having a low volatility and a highly stable weighing naphthalene ring. In this case, specifically, the compound (E) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof. These compounds (E) may be used individually by 1 type, or may use 2 or more types together.

  The compounding ratio of the compound (E) is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.03% by mass or more and 0.8% by mass in the total sealing resin composition. % Or less, particularly preferably 0.05% by mass or more and 0.5% by mass or less. When the lower limit value of the compounding ratio of the compound (E) is within the above range, a sufficient viscosity reduction and fluidity improving effect of the sealing resin composition can be obtained. Moreover, there is little possibility of causing the fall of sclerosis | hardenability of a resin composition for sealing, and the fall of physical property of hardened | cured material as the upper limit of the compounding ratio of a compound (E) is in the said range.

In the sealing resin composition of the present invention, in order to improve the adhesion between the epoxy resin (A) and the inorganic filler (C), an adhesion assistant (F) such as a silane coupling agent is further added. Can do. Examples thereof include, but are not limited to, epoxy silane, amino silane, ureido silane, mercapto silane, etc., which react between the epoxy resin and the inorganic filler to improve the interfacial strength between the epoxy resin and the inorganic filler. If it is. Moreover, a silane coupling agent can also raise the effect of the compound (E) of reducing the melt viscosity of the resin composition for sealing and improving fluidity | liquidity by using together with the above-mentioned compound (E). It is.

More specifically, examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β- (3,4 epoxy). (Cyclohexyl) ethyltrimethoxysilane and the like.
Examples of the aminosilane include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-aminopropyl. Methyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3 -Aminopropyltrimethoxysilane, N-3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, etc. are mentioned.
Examples of ureidosilane include γ-ureidopropyltriethoxysilane and hexamethyldisilazane.
Examples of mercaptosilanes include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

  The blending ratio of the adhesion assistant (F) such as a silane coupling agent that can be used in the sealing resin composition of the present invention is preferably 0.01% by mass or more and 1% by mass or less in the total resin composition. More preferably, they are 0.05 mass% or more and 0.8 mass% or less, Most preferably, they are 0.1 mass% or more and 0.6 mass% or less. If the blending ratio of the adhesion assistant (F) such as a silane coupling agent is not less than the above lower limit value, the interface strength between the epoxy resin and the inorganic filler does not decrease, and it is good in electronic component devices such as semiconductor devices Resistance to solder cracks can be obtained. Moreover, if the blending ratio of the adhesion assistant (F) such as a silane coupling agent is within the above range, the water absorption of the cured product of the resin composition does not increase, and it is good in an electronic component device such as a semiconductor device. Resistance to solder cracks can be obtained.

Mercaptosilane is preferred in terms of the balance between solder resistance and continuous moldability, aminosilane is preferred in terms of fluidity, and in terms of adhesion to organic components such as polyimide on the silicon chip surface and solder resist on the substrate surface. Epoxysilane is preferred. From the viewpoint of alkali resistance, a silane coupling agent having an N-phenyl γ-aminopropyl structure is preferred. Especially, the effect | action which reduces the contamination of the metal mold | die surface at the time of continuous molding is acquired by using together the silane coupling agent which has N-phenyl gamma-aminopropyl structure, and mercaptosilane.

In the sealing resin composition of the present invention, an inorganic flame retardant (G) can be further added to improve flame retardancy. Among these, a metal hydroxide or a composite metal hydroxide that inhibits the combustion reaction by dehydrating and absorbing heat during combustion is preferable in that the combustion time can be shortened. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and zirconia hydroxide. The composite metal hydroxide is a hydrotalcite compound containing two or more metal elements, wherein at least one metal element is magnesium, and the other metal elements are calcium, aluminum, tin, titanium, iron Any metal element selected from cobalt, nickel, copper, or zinc may be used, and as such a composite metal hydroxide, a magnesium hydroxide / zinc solid solution is easily available on the market. Of these, aluminum hydroxide and magnesium hydroxide / zinc solid solution are preferable from the viewpoint of the balance between solder resistance and continuous moldability. An inorganic flame retardant (G) may be used independently or may be used 2 or more types. Further, for the purpose of reducing the influence on the continuous moldability, a surface treatment may be performed with a silicon compound such as a silane coupling agent or an aliphatic compound such as wax.

  In the sealing resin composition of the present invention, in addition to the components described above, colorants such as carbon black, bengara and titanium oxide; natural wax such as carnauba wax; synthetic wax such as polyethylene wax; stearic acid and zinc stearate; Release agents such as higher fatty acids and their metal salts or paraffin; low stress additives such as silicone oil and silicone rubber; inorganic ion exchangers such as bismuth oxide hydrate; zinc borate, zinc molybdate, phosphazene, trioxide You may mix | blend additives, such as flame retardants, such as antimony, suitably.

  The encapsulating resin composition of the present invention contains an epoxy resin (A), a phenol resin-based curing agent (B), an inorganic filler (C), and other components described above, for example, at room temperature using a mixer or the like. Mix evenly.

  Then, if necessary, melt kneading using a kneader such as a heating roll, a kneader or an extruder, and then adjusting to a desired degree of dispersion, fluidity, etc. by cooling and grinding as necessary. Can do.

Next, the electronic component device of the present invention will be described. The electronic component device of the present invention is characterized in that an element is sealed with a cured product obtained by curing the above-described sealing resin composition of the present invention.
As a method for producing an electronic component device using the sealing resin composition of the present invention, for example, after a lead frame or a circuit board on which an electronic component element is mounted is placed in a mold cavity, the sealing resin The method of sealing this electronic component element by shape | molding and hardening | curing a composition with shaping | molding methods, such as a transfer mold, a compression mold, and an injection mold, is mentioned.

  Examples of the electronic component element to be sealed include, but are not limited to, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.

  As a form of the obtained electronic component device, for example, dual in-line package (DIP), chip carrier with plastic lead (PLCC), quad flat package (QFP), low profile quad flat package (LQFP), Small Outline Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package (TCP), ball grid array (BGA), chip size package (CSP), and the like, but are not limited thereto.

  An electronic component device in which an electronic component element is sealed by a molding method such as transfer molding using a sealing resin composition is used as it is or at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours. The resin composition is completely cured by applying to the electronic device and the like.

FIG. 1 is a diagram showing a cross-sectional structure of an example of an electronic component device in which an electronic component element mounted on a metal lead frame is sealed with a cured product of a sealing resin composition according to the present invention. . The semiconductor element 1 is fixed on the die pad 3 via the die bond material cured body 2. The electrode pad of the semiconductor element 1 and the lead frame 5 are connected by a gold wire 4. The semiconductor element 1 is sealed with a cured body 6 of a sealing resin composition.

  FIG. 2 is a cured product of the sealing resin composition according to the present invention, and shows a cross-sectional structure of an example of a single-side sealed electronic component device in which an electronic component element mounted on an organic substrate is sealed. It is a figure. On the surface of the substrate 8, the semiconductor element 1 is fixed via the die-bonding material cured body 2 on the solder resist 7 of a laminate in which a layer of the solder resist 7 is formed. The electrode pad of the semiconductor element 1 and the electrode pad on the substrate 8 are connected by a gold wire 4. Only the single side | surface side in which the semiconductor element 1 of the board | substrate 8 was mounted is sealed by the hardening body 6 of the resin composition for sealing. The electrode pads on the substrate 8 are bonded to the solder balls 9 on the non-sealing surface side on the substrate 8 inside.

  FIG. 3 is a cured product of the sealing resin composition according to the present invention, and an example of a one-side sealed electronic component device of a batch molding method in which an electronic component element mounted on a metal lead frame is sealed. It is the figure which showed the cross-section. The semiconductor element 1 is fixed on the die pad 3 via the die bond material cured body 2. The electrode pad of the semiconductor element 1 and the lead frame 5 are connected by a gold wire 4. The semiconductor element 1 is sealed with a cured body 6 of a sealing resin composition. The surface of the die pad 3 on which the semiconductor element 1 is not mounted is not sealed with the cured body 6 of the sealing resin composition and is exposed to the device surface. FIG. 3 shows a state in which only one side of the metal lead frame is collectively encapsulated with the encapsulating resin composition, and the dotted line portion is diced by dicing or laser cutting.

    FIG. 4 is a cured product of the sealing resin composition according to the present invention, in which an electronic component element mounted on a metal lead frame is sealed, and the back surface of the pad on which the element is mounted is FIG. 3 is a diagram showing a cross-sectional structure of an example of a pad-exposed type exposed on the surface of the device. The semiconductor element 1 is fixed on the die pad 3 via the die bond material cured body 2. The electrode pad of the semiconductor element 1 and the lead frame 5 are connected by a gold wire 4. The semiconductor element 1 is sealed with a cured body 6 of a sealing resin composition. Note that the surface of the die pad 3 where the semiconductor element 1 is not mounted is not sealed by the cured body 6 of the sealing resin composition and is exposed to the device surface.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to description of these Examples at all. Unless otherwise specified, the amount of each component described below is part by mass.

The following epoxy resins 1-7 were used for the epoxy resin. Among these, the epoxy resins 1 and 2 correspond to the epoxy resin (A) of the present invention. Prior to the synthesis of the epoxy resins 1 and 2, the synthesis of the precursor phenol compound (P1) and the precursor phenol resin (P2) will be described.

Precursor phenol compound (P1): phenol (special grade reagent manufactured by Kanto Chemical Co., Inc., phenol, melting point 40.9 ° C., molecular weight 94, purity 99.3%) 100 parts by mass, 2,4-dimethylbenzyl chloride (MTRIX Scientific) 370 parts by mass, 370 parts by mass (boiling point 103 ° C., molecular weight 154, purity 98%) at 2000 Pa, and 0.5 parts by weight of pure water were weighed into a separable flask, and a stirrer, thermometer, reflux condenser, nitrogen inlet Was heated while nitrogen bubbling was started, and stirring was started at the start of melting, and the reaction was carried out for 3 hours while maintaining the temperature in the system in the range of 120 ° C to 130 ° C. From the start to the end of the reaction, hydrogen chloride gas generated in the system by the reaction was quickly discharged out of the system by a nitrogen stream. After completion of the reaction, unreacted components are distilled off under reduced pressure conditions of 160 ° C. and 2 mmHg, and a precursor phenol compound represented by the following formula (P1) (p in formula (P1) is an integer of 1 to 3, q is 1 A mixture of compounds having an integer of ˜3, a hydroxyl equivalent 366) was obtained.

  Precursor phenol resin (P2): A separable flask was equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet, xylene formaldehyde resin (Fudo Co., Ltd., Nicanol G, number average molecular weight 560, oxygen content 15 100% by mass), paratoluenesulfonic acid monohydrate (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd., melting point 105 ° C., molecular weight 192, purity 99%) 0.11 part by mass, phenol (manufactured by Kanto Chemical Co., Inc.) After adding 150 parts by mass of a special grade reagent, phenol, melting point 40.9 ° C., molecular weight 94, purity 99.3%), nitrogen substitution and heating were started, and stirring was started as the phenol dissolved. The mixture was further heated and stirred for 2 hours while maintaining the temperature in the system at 115 to 125 ° C. Further, 1.5 parts by mass of oxalic acid and 35 parts by mass of 37% formalin were added, and the system was stirred for 3 hours while maintaining the temperature in the temperature range of 95 to 105 ° C. After adding 250 parts by mass of toluene and dissolving it uniformly, transfer to a separatory funnel, add 150 parts by mass of distilled water, shake, and then discard the aqueous layer (washing). After repeating the above, the oil layer is treated under reduced pressure at 125 ° C. and 5 mmHg to distill off volatile components such as toluene, residual unreacted components and by-products, and the precursor phenol resin represented by the following formula (P2) (In the formula (P2), r is a mixture of compounds in which r is an integer of 0 to 10 and s is an integer of 1 to 10. The precursor phenol resin (P2) is a structural unit represented by a repeating number r. A mixture of alternating structural units represented by the number of repetitions s, those bonded in a block shape, those bonded irregularly, those bonded regularly, a hydroxyl equivalent 171) was obtained. .

Epoxy resin 1: A separable flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, 20 parts by mass of the precursor phenol compound (P1), 80 parts by mass of the precursor phenol resin (P2), epichlorohydrin 305 parts by mass and 60 parts by mass of dimethyl sulfoxide were added. After heating to 45 ° C. and dissolution, 22.5 parts by mass of sodium hydroxide (solid fine particles, 99% purity reagent) is added over 2 hours, the temperature is raised to 50 ° C., 2 hours, and further 70 ° C. The temperature was raised to 2 hours and reacted for 2 hours. After the reaction, after adding 150 parts by mass of distilled water and shaking, the operation of discarding the aqueous layer (water washing) was repeated until the washing water became neutral, and then the oil layer was epichlorohydrin under reduced pressure conditions of 125 ° C. and 2 mmHg. And dimethyl sulfoxide was distilled off. 250 parts by mass of methyl isobutyl ketone was added to the obtained solid and dissolved, heated to 70 ° C., 13 parts by mass of a 30% by mass aqueous sodium hydroxide solution was added over 1 hour, and the reaction was further continued for 1 hour. The water layer was discarded. After 150 parts by mass of distilled water was added to the oil layer and washed with water, the same washing operation was repeated until the washed water became neutral, and then methyl isobutyl ketone was distilled off by heating under reduced pressure to obtain epoxy resin 1 (the following formula It is a mixture of a monofunctional epoxy resin represented by (A-1) and an epoxy resin represented by the following formula (A-2): epoxy equivalent 263, softening point 65 ° C., ICI viscosity 2.5 dPa · s at 150 ° C. s) was obtained.

An FD-MS chart of the epoxy resin 1 is shown in FIG. For example, m / z = 386 in the FD-MS analysis of FIG. 5 is p × q = 2 in the formula (A-1), m / z = 504 is p × q = 3 in the formula (A-1), m / z = 622 corresponds to the component of p × q = 4 in the formula (A-1), and these correspond to the component of (b-1) / d <1 in the general formula (1). m / z = 430 corresponds to the component (r, s) = (1, 1) in the formula (A-2), and the component (b-1) / d = 1 in the general formula (1). , M / z = 592 corresponds to the component (r, s) = (2, 1) in the formula (A-2), and the component (b-1) / d <1 in the general formula (1). M / z = 548 corresponds to a component of (r, s) = (1, 2) in the formula (A-2), and (b-1) / d> 1 in the general formula (1). The epoxy resin 1 corresponds to each component, and the epoxy resin 1 is a polymer represented by the general formula (1), wherein (b-1) / d = 1, (b-1) / d> 1 It was confirmed that the polymer contained a polymer having (b-1) / d <1 and a polymer having b = 1. The total of monofunctional epoxy components represented by the formula (A-1) in the epoxy resin 1 (polymer corresponding to b = 1 in the general formula (1)) in the relative intensity ratio of FD-MS analysis. The amount is 20% and reflects the blending ratio of the precursor phenol compound (P1) and the precursor phenol resin (P2). The average values of p × q, r, and s obtained by calculating the relative intensity ratio of FD-MS analysis as a mass ratio are 2.3, 1.5, and 1.5.
The FD-MS measurement of the epoxy resin 1 was performed under the following conditions. After adding 1 g of the solvent dimethyl sulfoxide (DMSO) to 10 mg of the epoxy resin 1 sample and dissolving it sufficiently, it was applied to the FD emitter and subjected to measurement. The FD-MS system uses an MS-FD15A manufactured by JEOL Ltd. as the ionization unit and an MS-700 model name double-convergence mass spectrometer manufactured by JEOL Ltd. as the detector, and detects the detected mass. It measured in the range (m / z) 50-2000.

Epoxy resin 2: In the synthesis of epoxy resin 1, the same synthetic operation as epoxy resin 1 was performed except that the precursor phenol resin (P2) was changed to 100 parts by mass and the precursor phenol compound (P1) was changed to 0 parts by mass. The epoxy resin 2 represented by the general formula (A-2) (formula (A-2
) In which r is an integer of 0 to 10 and s is an integer of 1 to 10, and the values of r and s are as described above. Epoxy equivalent 241; softening point 81 ° C .; ICI viscosity 5.1 dPa · s at 150 ° C.). In the FD-MS analysis of the epoxy resin 2, the component derived from the formula (A-1) was not detected, and the peaks of m / z = 430, 548, and 592 were detected. A polymer represented by (1), wherein (b-1) / d = 1, a polymer (b-1) / d> 1, and (b-1) / d <1 It was confirmed that the polymer contained a polymer. In addition, the average value of p * q, r, and s obtained by calculating the relative intensity ratio of FD-MS analysis as mass ratio is 1.5 and 1.5.

Epoxy resin 3: Biphenyl type epoxy resin (Mitsubishi Chemical Corporation, YX4000K. Epoxy equivalent 185 g / eq, softening point 107 ° C.)

Epoxy resin 4: bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, YL6810. Epoxy equivalent 172 g / eq, softening point 45 ° C.)

Epoxy resin 5: bisphenol F type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YSLV-80XY. Epoxy equivalent 190 g / eq, softening point 80 ° C.)

Epoxy resin 6: dihydroxyanthracene type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX8800, epoxy equivalent 181, melting point 110 ° C.)

Epoxy resin 7: Phenol aralkyl type epoxy resin having a phenylene skeleton (Nippon Kayaku Co., Ltd., NC2000. Epoxy equivalent 238 g / eq, softening point 52 ° C.)

(Synthesis of phenol resin 1)
A separable flask is equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, and 100 parts by mass of biphenyl (special grade reagent manufactured by Wako Pure Chemical Industries, biphenyl, boiling point 70 ° C., molecular weight 154, purity 98.4%), Paraformaldehyde (special grade reagent manufactured by Wako Pure Chemical Industries, paraformaldehyde, melting point 164 ° C., purity 98%) 43 parts by mass, zinc chloride (special grade reagent manufactured by Wako Pure Chemical Industries, zinc chloride, melting point 293 ° C., purity 97%) 60 mass And 270 parts by mass of cyclohexane (special grade reagent manufactured by Wako Pure Chemical Industries, cyclohexane, boiling point 80 ° C., purity 96%) were heated, and heating was started while introducing hydrogen chloride gas into the system. While maintaining the temperature in the system in the temperature range of 40 to 50 ° C., the mixture was stirred for 0.5 hours, and after confirming that the inside of the reaction system was uniformly dissolved, the heating was stopped. While maintaining the temperature range, the mixture was stirred for 30 hours to obtain a reaction intermediate solution. Next, 800 parts by mass of phenol (special grade reagent manufactured by Kanto Chemical Co., Inc., phenol, melting point 40.9 ° C., molecular weight 94, purity 99.3%) is added to the reaction intermediate solution described above, and nitrogen substitution and stirring are performed. It heated while performing and it was made to react for 5 hours, maintaining system temperature in the range of 20-25 degreeC. The hydrochloric acid gas generated in the system by the above reaction was discharged out of the system by a nitrogen stream. After completion of the reaction, the solvent and unreacted components were subjected to reduced pressure treatment at 50 ° C. and 2 mmHg, followed by reduced pressure treatment at 150 ° C. and 2 mmHg, thereby distilling off cyclohexane and unreacted components. Next, 500 parts by mass of toluene was added and uniformly dissolved, then the insoluble components were removed by passing through a glass filter, transferred to a separatory funnel, and 500 parts by mass of distilled water was added and shaken. After repeating the operation (water washing) until the washing water becomes neutral, the oil layer is treated under reduced pressure at 125 ° C. and 5 mmHg to distill off the volatile components, and the following formula (B-1) Phenol resin 1 having the structure represented (hydroxyl equivalent 198, softening point 66 ° C., ICI viscosity 1.0 dPa · s at 150 ° C., both ends of the structural formula being hydrogen atoms) was obtained.

  An FD-MS chart of the phenol resin 1 is shown in FIG. For example, m / z = 260 in the FD-MS analysis of FIG. 6 is (f1, g1, h1, i1) = (1, 1, 0, 0) in formula (B-1), and m / z = 366 is , (F1, g1, h1, i1) = (2, 1, 0, 0) and m / z = 472 in the formula (B-1) are expressed as (f1, g1, h1, i1 in the formula (B-1). ) = (2, 0, 1, 0), m / z = 578 is equal to (f1, g1, h1, i1) = (2, 0, 0, 1) of formula (B-1), m / z = 744 represents (f1, g1, h1, i1) = (3, 1, 1, 0) in the formula (B-1), and m / z = 850 represents (f1, g1, h1 in the formula (B-1). , I1) = (3,1,0,1), or (f1, g1, h1, i1) = (3,0,2,0), and h is 1 or more. Or any polymer of polymers in which i is 1 or more It was confirmed.

Phenol resin 2: In the synthesis of phenol resin 1, the same synthesis operation as phenol resin 1 was performed except that the blending amount of phenol was changed to 400 parts by mass, and phenol resin 2 represented by the general formula (B-1) (Hydroxyl equivalent 196, softening point 71 ° C., ICI viscosity at 150 ° C. 2.1 dPa · s) was obtained. As a result of FD-MS analysis of the phenol resin curing agent 2, m / z = 260, 366, 472, 578, 744, and 850 were detected in the same manner as the phenol resin curing agent 1, and similarly to the phenol resin curing agent 1. , H is 1 or more, or i is 1 or more.

  Curing agent 3: Phenol aralkyl resin having a biphenylene skeleton (Maywa Kasei Co., Ltd., MEH-7851SS. Hydroxyl equivalent 203 g / eq, softening point 67 ° C., ICI viscosity 1.1 dPa · s at 150 ° C.).

(Inorganic filler)
As the inorganic filler, 100 parts by mass of fused spherical silica FB560 (average particle size 30 μm) manufactured by Denki Kagaku Kogyo Co., Ltd., 6.5 parts by mass of synthetic spherical silica SO-C2 (average particle size 0.5 μm) manufactured by Admatex, A blend of 7.5 parts by mass of synthetic spherical silica SO-C5 (average particle size 1.5 μm) manufactured by Mattex was used.

(Curing accelerator)
The following curing accelerators 1-5 were used.

  Curing accelerator 1: Curing accelerator represented by the following formula (D-1)

  Curing accelerator 2: Curing accelerator represented by the following formula (D-2)

  Curing accelerator 3: Curing accelerator represented by the following formula (D-3)

  Curing accelerator 4: Curing accelerator represented by the following formula (D-4)

  Curing accelerator 5: Triphenylphosphine (Hokuko Chemical Industries, Ltd., TPP)

(Compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring)
As compound E, 2,3-naphthalenediol (Tokyo Chemical Industry Co., Ltd., 2,3-naphthalenediol, purity 98%) was used.

(Silane coupling agent)
The following silane coupling agents 1 to 3 were used.

Silane coupling agent 1: γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-803).
Silane coupling agent 2: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403).
Silane coupling agent 3: N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-573)

(Flame retardants)
The following flame retardants 1-2 were used.
Flame retardant 1: Aluminum hydroxide (Sumitomo Chemical Co., Ltd., CL-303)
Flame retardant 2: Magnesium hydroxide / zinc hydroxide solid solution composite metal hydroxide (Echo Mug Z-10, manufactured by Tateho Chemical Co., Ltd.)

(Coloring agent)
Carbon black (MA600) manufactured by Mitsubishi Chemical Industries, Ltd. was used as a colorant.

(Release agent)
As a release agent, carnauba wax (Nikko carnauba, melting point 83 ° C.) manufactured by Nikko Fine Co., Ltd. was used.

The following measurements and evaluations were performed on the resin compositions for semiconductor encapsulation obtained in Examples and Comparative Examples described later.
(Evaluation item)

  Spiral flow: Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a spiral flow measurement mold according to EMMI-1-66 was applied at 175 ° C., injection pressure 6.9 MPa, pressure holding time The sealing resin composition was injected under the condition of 120 seconds, and the flow length was measured. The spiral flow is a fluidity parameter, and the larger the value, the better the fluidity. The unit is cm.

Initial failure evaluation of MAP-QFN: using a low-pressure transfer molding machine (GP-ELF, manufactured by Daiichi Seiko Co., Ltd.) under the conditions of a mold temperature of 180 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. A lead resin or the like on which a semiconductor element (silicon chip) is mounted is molded by injecting a resin composition for stopping, and then MAP-QFN (Mold Array Packaging-Quad Flat Non-Leaded Package, strike plating on a Cu lead frame. The size of the sealed portion is 45 mm × 62 mm × thickness 0.65 mm, and by dicing this, a 40 mm semiconductor device of QFN-16L having a size of 4 mm × 4 mm × thickness 0.65 mm is obtained. The semiconductor element is 1.5 mm × 1.5 mm × thickness 0.2 mm. The passivation types SiN, are bonded with gold wires of 25μm diameter and the semiconductor element and the inner lead portion of the lead frame, which is sealed only the semiconductor element surface) was created one. In the state of MAP-QFN, the presence or absence of peeling and cracks inside the semiconductor device is observed with an ultrasonic flaw detector (manufactured by Hitachi Construction Machinery Finetech Co., Ltd., mi-scope 10). It was. In addition, the number of defects is displayed as n / 40 when one MAP-QFN is regarded as 40 QFN-16L and the number of defective semiconductor devices in 40 is n. The sealing resin composition obtained in Example 1 showed good characteristics of 0/40.

Electrolytic deburring evaluation of MAP-QFN: A cathode was connected to the lead frame of MAP-QFN, an anode was connected to the electrolytic treatment solution layer, an 18% by mass aqueous potassium hydroxide solution was added to the electrolytic treatment solution, and the temperature in the tank was 50. The electrolytic treatment was performed for 90 seconds under the conditions of ° C. and a current density of 20 A / cm ² . Next, the presence or absence of peeling and cracks inside the semiconductor device was confirmed with an ultrasonic flaw detector, and when the number of defective semiconductor devices out of 40 was n, it was displayed as n / 40. The sealing resin composition obtained in Example 1 showed good characteristics of 0/40.

  Solder resistance evaluation of QFN-16L-1: MAP-QFN subjected to electrolytic deburring treatment was heated at 175 ° C. for 4 hours, then separated into pieces using a dicer, and half of good products among the obtained semiconductor device QFN-16L (Up to 20) were treated at 85 ° C. and 60% relative humidity for 168 hours, followed by IR reflow treatment (260 ° C., according to JEDEC conditions). Next, the presence or absence of peeling and cracks inside the semiconductor device is confirmed with an ultrasonic flaw detector, and when the number of semiconductor devices subjected to solder resistance evaluation-1 is 20, of which n is the number of defects, n / 20. When the number of defective semiconductor devices was 1 or less, it was judged as a good result. The semiconductor device produced using the sealing resin composition obtained in Example 1 exhibited a good solder resistance of 0/20.

  Soldering resistance evaluation of QFN-16L-2: MAP-QFN subjected to electrolytic deburring treatment was heated at 175 ° C. for 4 hours, then separated into pieces using a dicer, and half of the non-defective semiconductor devices QFN-16L obtained. (Up to 20) were treated at 85 ° C. and 85% relative humidity for 72 hours, and then subjected to IR reflow treatment (260 ° C., according to JEDEC conditions). Next, the presence or absence of peeling and cracks inside the semiconductor device is confirmed with an ultrasonic flaw detector, and when the number of semiconductor devices subjected to the solder resistance evaluation-2 is 20 and the number of defects is n, n / 20. When the number of defective semiconductor devices was 2 or less, it was judged as a good result. The semiconductor device produced using the sealing resin composition obtained in Example 1 exhibited a good solder resistance of 1/20.

  Flame resistance: For sealing under the conditions of a mold temperature of 175 ° C., an injection time of 15 seconds, a curing time of 120 seconds, and an injection pressure of 9.8 MPa using a low-pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) The resin composition was injection molded to produce a 3.2 mm thick flame resistant test piece. About the obtained test piece, the flame resistance test was done according to the specification of UL94 vertical method. The table shows Fmax, ΣF, and the fire resistance rank (class) after determination.

  Panel warpage amount: As a measurement sample, a panel of MAP-QFN (before heat treatment at 175 ° C. for 4 hours and before individualization with a dicer) formed in the same manner as the evaluation of the initial failure of MAP-QFN described above It was. Set the measurement sample horizontally on the contact-type surface roughness meter so that the surface sealed with the resin composition faces up, and scan the contact in the longitudinal direction of the MAP-QFN panel. The displacement in the height direction was measured, and the maximum value of the displacement (height) difference was taken as the panel warpage. The number of measurement samples was n = 4 for each, and the average value was shown in the table. The measured value was displayed as a negative value in the case of an upward convex warpage displacement, and as a positive value in the case of a concave warpage displacement (the + sign was omitted). The smaller the absolute value, the smaller the warp and the better the handling and stress. If the absolute value of the numerical value was 300 or less, it was judged good. The unit is μm. The pre-separated MAP-QFN panel produced using the epoxy resin composition obtained in Example 1 showed a good low warpage of 210 μm.

Continuous moldability: The obtained sealing resin composition was adjusted to a weight of 15 g, a size φ18 mm × a height of about 30 mm using a powder molding press (S-20-A, manufactured by Tamagawa Machinery Co., Ltd.). Tablets were obtained by tableting at a tableting pressure of 600 Pa. A tablet supply magazine loaded with the obtained tablet was set in the molding apparatus. For molding, a low pressure transfer automatic molding machine (GP-ELF, manufactured by Daiichi Seiko Co., Ltd.) is used as a molding device, under conditions of a mold temperature of 175 ° C., a molding pressure of 9.8 MPa, and a curing time of 120 seconds. A silicon chip or the like is sealed with the composition, and an 80-pin QFP (Cu lead frame, package outer dimension: 14 mm × 20 mm × 2.0 mm thickness, pad size: 8.0 mm × 8.0 mm, chip size 7.0 mm × 7.0 mm × 0.35 mm thickness) was continuously performed up to 300 shots. At this time, after every 25 shots, the state of the mold surface and the molded state of the package (whether or not unfilled) are checked, and the number of shots where the mold can be confirmed for the first time, and mold contamination occurs. If there is no filling, mark the ○ mark in the “Mold surface condition” section of the table, and the number of shots that were first confirmed to be unfilled. ", Respectively. Note that the surface contamination of the mold may be transferred to the surface of the molded semiconductor device or may be an unfilled precursor, which is not preferable.

  Wire flow rate: 208 pin QFP package (dimension; 28 ×) for wire flow rate evaluation test using a tableted resin composition for sealing on a low-pressure transfer molding machine under conditions of 175 ° C., 6.9 MPa, 120 seconds 28 x 2.4 mm, Cu lead frame, test element: 9 x 9 mm, wire: Au, diameter 1.2 mils, length of about 5 mm) 10 packages each, and the molded 208 pin QFP package is a soft X-ray transmission device Observed at. As a method of calculating the wire flow rate, the flow rate of the most flowed (deformed) wire in one package is (F), the length of the wire is (L), and the flow rate = F / L × 100 (%) was calculated and the average value of 10 packages was shown. Note that a wire flow rate of less than 5% is judged good. The sealing resin composition obtained in Example 1 showed a good wire flow rate of 3.7%.

Examples 2-17, Comparative Examples 1-3
According to the composition in Table 1, a sealing resin composition was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  The encapsulating resin composition of the present invention comprises one or more polymers having a structure represented by the general formula (1). In the general formula (1), at least (b-1) / d> 1 An epoxy resin (A) containing any of the following: (b-1) / d <1; and a phenol containing one or more polymers having a structure represented by the general formula (2) A resin-based curing agent (B) and an inorganic filler (C) are included, and in any of Examples 1 to 17, fluidity (spiral flow), electrolytic deburring resistance, solder resistance, Excellent flame resistance and excellent balance of continuous formability, wire flowability, and low warpage were obtained.

Moreover, in Examples 5-8 and Examples 12-17, since the crystalline epoxy resin is used as an epoxy resin used together with an epoxy resin (A), this and a specific epoxy resin (A) are specified. It was found that the following effects can be obtained as an effect obtained by using the phenol resin-based curing agent (B) in combination.
In Examples 5 to 8 and 12 to 17 using the epoxy resins 3 to 6 which are crystalline epoxy resins as the epoxy resin used in combination with the epoxy resin (A), the solder resistance evaluation-2 after the electrolytic deburring treatment is The result was particularly excellent and the wire flow rate was also good. Moreover, in Example 8 which used the epoxy resin 6 which is a crystalline epoxy resin which has an anthracene skeleton as an epoxy resin used together with an epoxy resin (A), it became a result in which especially low curvature property and flame resistance were excellent.

On the other hand, instead of the phenol resin (B), in Comparative Example 1 using the curing agent 3 corresponding to a phenol resin composed only of a polymer component with h = 0 and i = 0 in the general formula (2), The soldering resistance after the deburring process was poor.
Further, in place of the epoxy resin (A), any of a polymer satisfying (b-1) / d> 1 and a polymer satisfying (b-1) / d <1 in the general formula (1) is included. In Comparative Example 2 using an epoxy resin 7 corresponding to a non-epoxy resin, peeling occurred after electrolytic deburring treatment, resulting in poor solder resistance and wire flow rate after electrolytic deburring treatment.
Further, in Comparative Example 3 using the above-described epoxy resin 7 and phenol resin 3 instead of the epoxy resin (A) and the phenol resin-based curing agent (B), peeling occurred after the electrolytic deburring treatment, and the electrolytic The soldering resistance, flame resistance, continuous formability and wire flow rate after the removal process were also inferior.

  As shown in the above results, only when the sealing resin composition of the present invention in which the epoxy resin (A) and the phenol resin curing agent (B) are combined is used, the electrolytic deburring resistance, after electrolytic deburring The result was excellent in the balance of solder resistance, wire flow rate, flame resistance, low warpage and continuous formability. Above all, this is because it is possible to achieve both the anti-electrolytic deburring property and the improved solder resistance after electrolytic deburring of a single-side sealed electronic component device equipped with a metal lead frame, which was difficult in the past. The invention has a remarkable effect that exceeds the category that can be predicted from the prior art.

  According to the present invention, there is provided a single-side sealed electronic component device having good electrolytic deburring resistance, solder resistance after electrolytic deburring, wire flow rate, flame resistance, and continuous formability and a metal lead frame. Since the resin composition for sealing an electronic component having excellent low warpage can be obtained, it is suitable for sealing an electronic component device, particularly for a single-side sealed electronic component device using a metal substrate.

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Die-bonding material hardening body 3 Die pad 4 Gold wire 5 Lead frame 6 Curing body of epoxy resin composition 7 Solder resist 8 Substrate 9 Solder ball

Claims (13)

It consists of one or more polymers having a structure represented by the following general formula (1), and in the following general formula (1), at least a polymer satisfying (b-1) / d> 1, (b-1) An epoxy resin (A) containing any of the polymers satisfying / d <1, and a phenol resin-based curing agent (B) containing one or more polymers having a structure represented by the following general formula (2): And an inorganic filler (C). A sealing resin composition characterized by comprising:

(In the general formula (1), R1 and R2 are each independently a hydrocarbon group having 1 to 6 carbon atoms, a is an integer of 0 to 3, and c is an integer of 1 to 4. Both ends of the structural formula are hydrogen atoms, b and d are integers of 1 to 20. b repeating units that are substituted or unsubstituted glycidoxyphenylene groups and d that is a substituted phenylene group. (Each repeating unit may be continuously arranged, or may be alternately or randomly arranged with each other, but always has a methylene group between them.)

(In the general formula (2), R3 is independently a hydrocarbon group having 1 to 6 carbon atoms, e is an integer of 0 to 3, and both ends of the structural formula are hydrogen atoms. f is an integer of 1 to 20, and g, h, and i are integers of 0 to 19. Including any polymer in which h is 1 or more, or i is 1 or more. .
F repeating units which are substituted or unsubstituted hydroxyphenylene groups;
G repeating units which are unsubstituted biphenylene groups;
H repeating units that are biphenylene groups having one hydroxyphenylmethyl as a substituent and i repeating units that are biphenylene groups having two hydroxyphenylmethyl as a substituent are:
Each of them may be continuously arranged, or may be alternately or randomly arranged, but a methylene group is always present between them. ) Furthermore, the resin composition for sealing of Claim 1 in which the polymer which becomes (b-1) / d <1 of an epoxy resin (A) contains the polymer which becomes b = 1. The content of the polymer of (b-1) / d <1, b = 1 in the epoxy resin (A) is 5% by mass to 40% by mass with respect to 100% by mass of the epoxy resin (A). The resin composition for sealing according to claim 2 which is.  Furthermore, a crystalline epoxy resin is contained, The description in any one of Claim 1 thru | or 3
A sealing resin composition. Furthermore, the resin composition for sealing of any one of Claims 1 thru | or 4 which contains a hardening accelerator (D). The curing accelerator (D) is at least one curing accelerator selected from the group consisting of tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. The sealing resin composition according to claim 5 , comprising an agent. Furthermore, the sealing resin composition of any one of Claim 1 thru | or 6 which contains the compound (E) which the hydroxyl group couple | bonded with the two or more adjacent carbon atoms which comprise an aromatic ring, respectively. Furthermore, the sealing resin composition of any one of Claim 1 thru | or 7 which contains a coupling agent (F). The sealing resin composition according to claim 8 , wherein the coupling agent (F) comprises a silane coupling agent having a secondary amino group. The sealing resin composition according to claim 8 , wherein the coupling agent (F) contains a silane coupling agent having a mercaptosilane group. Furthermore, the resin composition for sealing of any one of Claim 1 thru | or 10 which contains an inorganic flame retardant (G). The sealing resin composition according to claim 11 , wherein the inorganic flame retardant (G) contains a metal hydroxide or a composite metal hydroxide. An electronic component device, wherein an element is sealed with a cured product obtained by curing the sealing resin composition according to any one of claims 1 to 12 .