JP2006016525A - Epoxy resin molding material for sealing and electronic component device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding material for sealing, excellent in molding properties such as fluidity and curability, flame reterdance, heat resistance and cold cycle resistance, and to provide electronic component devices having an element sealed with the epoxy resin molding material for sealing. <P>SOLUTION: The epoxy resin molding material for sealing comprises (A) an epoxy resin containing an epoxy resin obtained by glycidyl etherification of dimer of at least one of hydroxynaphthalene and dihydroxynaphthalene, (B) a curing agent containing a compound represented by general formula (I), (C) a phosphorus-based curing promoter, and (D) an inorganic filler, wherein the phosphorus content of the (C) component is 200-500 ppm based on the total molding materials. And, in general formula (I), n is 0 or a positive integer, and H of benzene ring and naphthalene ring in (A) and (B) may be replaced with a hydrocarbon. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an epoxy resin molding material for sealing, and an electronic component device including an element sealed with the epoxy resin molding material for sealing.

  Conventionally, in the field of element sealing of electronic component devices such as transistors, ICs, and LSIs, resin sealing has been the mainstream in terms of productivity, cost, etc., and epoxy resin molding materials have been widely used. This is because epoxy resins are balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts.

In recent years, electronic devices are also being developed in the automobile field. Electronic devices for automobiles are often required to be more reliable in terms of heat resistance and cold cycle resistance than so-called consumer applications such as personal computers and home appliances.
General techniques for increasing the heat resistance of electronic equipment include a technique for increasing the glass transition point of the package, and techniques for improving the thermal cycle resistance include thermal expansion of the semiconductor internal member and the epoxy resin molding material for sealing. A technique such as bringing the coefficients closer is mentioned.
In epoxy resin molding materials for sealing, halogenated resins such as decabromo and antimony compounds have been used as flame retardants in the past, but in recent years there has been a movement to regulate the amount of these compounds from the viewpoint of environmental protection. There is a demand for non-halogenation (non-bromo) and non-antimony. In addition, it is known that a bromo compound has an adverse effect on the high temperature storage characteristics of a plastic encapsulated IC. From this viewpoint, reduction of the amount of bromo resin is desired.
As one of the methods for achieving flame retardancy without using brominated resin or antimony oxide, a method of adding an organic phosphorus compound (for example, see Patent Document 1), a method of using a metal hydroxide (for example, Patent Document) However, it has not been able to solve problems such as a decrease in glass transition point and an adverse effect on formability.

In an epoxy resin molding material for sealing that does not use brominated resin or antimony oxide, when trying to bring the coefficient of linear expansion of the epoxy resin molding material for sealing close to that of the semiconductor internal member in order to increase the thermal cycle resistance, In particular, it is difficult to ensure flame retardancy in a package using a copper lead frame. On the other hand, when flame retardants such as organophosphorus compounds and metal hydroxides are used to ensure flame retardancy, there are problems such as lowering the glass transition point and adversely affecting moldability. Although there are reports of Patent Document 3 and the like for improving the moldability of an epoxy resin molding material for sealing using a metal hydroxide, the effect is not always sufficient.
JP 9-235449 A Japanese Patent Laid-Open No. 9-241383 JP 2003-253093 A

  The present invention has been made in view of such circumstances, and realizes good flame retardancy without using a halogenated resin or an antimony compound, such as moldability such as fluidity and curability, heat resistance and cold cycle resistance. An object of the present invention is to provide an epoxy resin molding material for sealing excellent in reliability, and an electronic component device including an element sealed thereby.

（一般式（I）で、ｎは０、又は正の整数を表し、A及びB中のベンゼン環及びナフタレン環上の水素原子は炭化水素基で置換されていてもよい。）
（２）ハロゲン系難燃剤及びアンチモン系難燃剤の含有量がいずれも成形材料全体の０.１重量％以下である前記（１）に記載の封止用エポキシ樹脂成形材料。
（３）ハロゲン系難燃剤及びアンチモン系難燃剤を含まない前記（２）に記載の封止用エポキシ樹脂成形材料、
（４）（Ｄ）無機充填剤量が成形材料全体の７０重量％以上８８重量％以下である前記（１）〜（３）のいずれかに記載の封止用エポキシ樹脂成形材料、
（５）前記（１）〜（４）のいずれかに記載の封止用エポキシ樹脂成形材料により封止された素子を備えた電子部品装置、
に関する。 As a result of intensive studies to solve the above problems, the present inventors have determined that an epoxy resin molding material for sealing has an epoxy resin having a specific structure, a curing agent having a specific structure, and a specific structure. It has been found that the above-mentioned object can be achieved by using a specific amount of the curing accelerator having the present invention, and the present invention has been completed.
That is, the present invention is (1) (A) an epoxy resin containing an epoxy resin obtained by glycidyl etherification of at least one dimer of hydroxynaphthalene and dihydroxynaphthalene, (B) represented by the following general formula (I) (C) a phosphorus-based curing accelerator, and (D) an inorganic filler, and the phosphorus content of the component (C) is 200 to 500 ppm of the entire molding material. Molding material,

(In general formula (I), n represents 0 or a positive integer, and the hydrogen atom on the benzene ring and naphthalene ring in A and B may be substituted with a hydrocarbon group.)
(2) The epoxy resin molding material for sealing according to the above (1), wherein the content of the halogen flame retardant and the antimony flame retardant is 0.1% by weight or less of the whole molding material.
(3) The epoxy resin molding material for sealing according to the above (2), which does not contain a halogen flame retardant and an antimony flame retardant,
(4) (D) The epoxy resin molding material for sealing according to any one of (1) to (3), wherein the amount of the inorganic filler is 70% by weight or more and 88% by weight or less of the entire molding material,
(5) An electronic component device including an element sealed with the sealing epoxy resin molding material according to any one of (1) to (4),
About.

  The epoxy resin molding material for sealing according to the present invention is excellent in moldability such as fluidity and curability, flame retardancy, heat resistance, reliability such as thermal cycle resistance, etc., and this epoxy resin molding material for sealing Is used to seal electronic components such as ICs and LSIs, an electronic component device excellent in moldability and reliability can be obtained, and its industrial value is great.

  In the present invention, an epoxy resin obtained by glycidyl etherification of at least one dimer of hydroxynaphthalene and dihydroxynaphthalene as (A) an epoxy resin in order to realize both a high glass transition point and high flame retardancy. It is necessary to contain singly or in combination of two or more. In order to realize a high glass transition point, it is preferable to use a trifunctional epoxy resin obtained by glycidyl etherification of a dimer of hydroxynaphthalene and dihydroxynaphthalene, and obtained by glycidyl etherification of a dihydroxynaphthalene dimer. It is more preferable to use a tetrafunctional epoxy resin, and a mixture thereof may be used. As an epoxy resin mainly composed of an epoxy resin obtained by glycidyl etherification of a dihydroxynaphthalene dimer, HP-4701 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) is available.

In order to sufficiently obtain the effects of the present invention, the epoxy resin obtained by glycidyl etherification of the dimer is preferably 40% by weight or more of the total component (A), more preferably 50% by weight or more. It is preferably 60% by weight or more. If it is less than 40% by weight, it tends to be difficult to achieve both a high glass transition point and high flame retardancy.
In the present invention, as the component (A), in addition to an epoxy resin obtained by glycidyl etherification of the dimer, an epoxy resin generally used for an epoxy resin molding material for sealing can be used in combination without any particular limitation. It is. Examples of resins that can be used in combination include phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, and other phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and / or α-naphthol, β An epoxidized novolak resin obtained by condensation or cocondensation of naphthols such as naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst; Diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, bisphenol A / D, and diglycidyl ethers of alkyl-substituted or unsubstituted biphenols Biphenyl type epoxy resin, which is ether, epoxidized products such as phenol aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl resin, stilbene type synthesized from phenol and / or naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Epoxy resin, hydroquinone type epoxy resin, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid and epichlorohydrin, diaminodiphenylmethane, isocyanuric acid etc. and glycidyl amine type epoxy obtained by reaction of epichlorohydrin Resin, dicyclopentadiene type epoxy resin and triphenolmethane type epoxy which are epoxidized products of co-condensation resin of dicyclopentadiene and phenols Fat, trimethylolpropane type epoxy resin, terpene modified epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, alicyclic epoxy resin, and these epoxy resins as silicone, Examples thereof include epoxy resins modified with acrylonitrile, butadiene, isoprene-based rubber, polyamide-based resin, and the like.

（一般式（I）で、ｎは０、又は正の整数を表し、A及びB中のベンゼン環及びナフタレン環上の水素原子は炭化水素基で置換されていてもよい。）
上記一般式（I）で表される化合物としては、一般式（II）で表されるフェノール・アラルキル樹脂、一般式（III）で表されるビフェニル・アラルキル樹脂、一般式（IV）、一般式（Ｖ）で表されるナフトール・アラルキル樹脂等を挙げることができ、難燃性の点からは一般式（III）で表されるビフェニル・アラルキル樹脂を単独又は併用して用いることが好ましく、（Ｂ）成分全体の４０重量％以上とすることがより好ましく、５０重量％以上とすることが特に好ましい。

（一般式（II）で、ｎは０又は１〜１０の整数を示す。）

（一般式（III）で、ｎは０又は１〜１０の整数を示す。）

（一般式（IV）で、ｎは０又は１〜１０の整数を示す。）

（一般式（Ｖ）で、ｎは０又は１〜１０の整数を示す。） The (B) curing agent of the present invention needs to contain a compound represented by the following general formula (I) alone or in combination of two or more, particularly from the viewpoint of flame retardancy.

(In general formula (I), n represents 0 or a positive integer, and the hydrogen atom on the benzene ring and naphthalene ring in A and B may be substituted with a hydrocarbon group.)
Examples of the compound represented by the general formula (I) include a phenol / aralkyl resin represented by the general formula (II), a biphenyl / aralkyl resin represented by the general formula (III), a general formula (IV), and a general formula The naphthol aralkyl resin represented by (V) can be mentioned, and from the viewpoint of flame retardancy, it is preferable to use the biphenyl aralkyl resin represented by the general formula (III) alone or in combination. It is more preferable to set it as 40 weight% or more of the whole B) component, and it is especially preferable to set it as 50 weight% or more.

(In general formula (II), n represents 0 or an integer of 1 to 10.)

(In general formula (III), n represents 0 or an integer of 1 to 10.)

(In general formula (IV), n represents 0 or an integer of 1 to 10.)

(In general formula (V), n represents 0 or an integer of 1 to 10.)

  As a phenol aralkyl resin represented by the above general formula (II), a trade name XLC manufactured by Mitsui Chemicals, Inc. may be mentioned as a commercially available product. As a biphenyl aralkyl resin represented by the above general formula (III), Meiwa Kasei Co., Ltd. product name MEH-7851 is mentioned. Moreover, as a naphthol aralkyl resin shown by the said general formula (IV), Nippon Steel Chemical Co., Ltd. brand name SN-170 is mentioned as a commercial item, The naphthol aralkyl resin shown by the said general formula (V) is mentioned. As a commercial item, Nippon Steel Chemical Co., Ltd. product name SN-475 is mentioned. In addition, in the compounds represented by the general formulas (II) to (V), a compound in which any one of the hydrogen atoms on the benzene ring and the naphthalene ring is substituted with a hydrocarbon group is also represented by the general formula (I). include.

  In the present invention, as the component (B), in addition to the curing agent represented by the general formula (I), a curing agent generally used for an epoxy resin molding material for sealing can be used in combination without any particular limitation. Examples of curing agents that can be used in combination include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, and formaldehyde. , Novolak-type phenolic resin, dicyclopentadiene-type phenolic resin, terpene-modified phenolic resin, triphenolmethane-type phenolic resin, etc. obtained by condensation or cocondensation with compounds having an aldehyde group such as benzaldehyde, salicylaldehyde, etc. under an acidic catalyst Is mentioned.

  The equivalent ratio of the (A) component epoxy resin and the (B) component curing agent, that is, the ratio of the number of epoxy groups in the epoxy resin / the number of hydroxyl groups in the curing agent is not particularly limited. Is preferably set in the range of 0.5 to 2, more preferably 0.6 to 1.5. In order to obtain an epoxy resin molding material for sealing which is excellent in moldability and reliability, it is more preferable to set in the range of 0.8 to 1.2.

The phosphorus-based curing accelerator component (C) of the present invention functions as a curing accelerator, and it is necessary to use a phosphorus-based curing accelerator from the viewpoint of moldability, reliability, and flame retardancy. In the present invention, it is possible to use a phosphorus-based curing accelerator generally used in an epoxy resin molding material for sealing without particular limitation, and the phosphorus-based curing accelerator is an alkyl group, a phenyl group, And a compound having a phosphorus atom directly bonded to at least one of phenyl group derivatives in which part or all of the hydrogen atoms of the phenyl group are substituted with an alkyl group or an alkoxy group. These include maleic anhydride, quinone compounds, diazophenyl. Also included are compounds having an intramolecular polarization formed by adding a compound having a π bond, such as methane and phenol resin, and a tetraphenylboron salt and derivatives thereof. For example, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine, and maleic anhydride, 1,4-benzoquinone, 2, 5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4- Organophosphorus compounds such as compounds having intramolecular polarization formed by adding a quinone compound such as benzoquinone and phenyl-1,4-benzoquinone, diazophenylmethane, and a compound having a π bond such as a phenol resin, tetraphenylphosphonium tetraphenylborate The trough And organic phosphorus compounds such as sulfonyl phosphine tetraphenyl borate and the like.
In the present invention, it is necessary that the content of phosphorus in the curing accelerator is 200 to 500 ppm of the entire molding material from the viewpoint of balance between moldability such as fluidity and curability and flame retardancy. If the phosphorus content is less than 200 ppm, the curability and flame retardancy may be adversely affected, and if it exceeds 500 ppm, the fluidity may be adversely affected. In addition, the content rate of phosphorus here is a value calculated | required by following formula (1).
(Phosphorus content) = (30.975 / M) × (w / W) × 10 ⁶ (ppm) (Formula 1)
(In formula (1), M: molecular weight of phosphorus-based curing accelerator, w: amount of phosphorus-based curing accelerator, W: total weight of molding material)
As the phosphorus curing accelerator, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination. When using 2 or more types of compounds together, it is necessary to make the total amount of phosphorus content in a hardening accelerator into the said range.

  In the present invention, in addition to the (C) phosphorus-based curing accelerator, 1,8-diaza-bicyclo (5,4,0) undecene-7, 1, Amine-based curing accelerators such as cycloamidine compounds such as 5-diaza-bicyclo (4,3,0) nonene and 5,6-dibutylamino-1,8-diaza-bicyclo (5,4,0) undecene-7 And imidazole curing accelerators such as 2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole, tetra such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate A phenylboron curing accelerator or the like can be used in combination as long as the effect is not impaired.

  (C) As mentioned above, the compounding quantity of a component needs to be set so that the phosphorus content rate in a hardening accelerator may be 200-500 ppm. When a curing accelerator other than the phosphorus curing accelerator is used in combination, the curing accelerator is preferably 50% by weight or less of the phosphorus curing accelerator, particularly from the viewpoint of reliability.

In the present invention, it is also necessary to blend (D) an inorganic filler for hygroscopicity, reduction of linear expansion coefficient, improvement of thermal conductivity and improvement of strength. Examples of the inorganic filler include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steer. Examples thereof include powders such as tight, spinel, mullite, and titania, or beads formed by spheroidizing these, and glass fibers. These may be used alone or in combination of two or more. From the viewpoint of reducing fluidity and linear expansion coefficient, it is preferable to use crystalline silica or fused silica, more preferably fused silica, and particularly preferably spherical fused silica. Furthermore, you may add metal hydroxide type inorganic fillers, such as aluminum hydroxide and magnesium hydroxide which have a flame-retardant effect, in the range which does not lose the effect of this invention.
The blending amount of the inorganic filler is preferably 70 to 88% by weight, particularly preferably 75 to 85% by weight based on the whole molding material, particularly from the viewpoint of cold heat cycle resistance in the copper lead frame package. Even if the component (D) is less than 70% by weight or more than 88% by weight, mismatch in the linear expansion coefficient between the epoxy resin molding material for sealing and the lead frame becomes remarkable, which is disadvantageous for the thermal cycle resistance.

  In the present invention, in addition to the components (A) to (D), in order to ensure smooth releasability from the mold during molding, higher fatty acid waxes such as stearic acid and montanic acid, stearates, Conventionally known release agents used for molding epoxy resin molding materials such as higher fatty acid ester waxes such as montanic acid esters, polyolefins including polyethylene, etc. can be used alone or in combination.

An anion exchanger can be added to the sealing epoxy resin molding material of the present invention from the viewpoint of improving the moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. Examples thereof include hydrotalcite and hydrated oxides of elements selected from bismuth, zirconium, titanium, tin, magnesium, and aluminum. These may be used alone or in combination of two or more. Among these, hydrotalcite and bismuth hydrous oxide represented by the following general formula (VI) are preferable.
(Chemical formula 7)
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (VI)
(0 <X ≦ 0.5, m is a positive integer)
The amount of the anion exchanger is not particularly limited as long as it is sufficient to capture ionic impurities such as halogen ions, but is preferably 0.1 to 30% by weight with respect to the epoxy resin of component (A). 1-10 weight% is more preferable, and 2-5 weight% is further more preferable. If the blending amount is less than 0.1% by weight, trapping of ionic impurities tends to be insufficient, and if it exceeds 30% by weight, there is no significant difference in the effect compared to the amount less than that, which is economically disadvantageous.

In the epoxy resin molding material for sealing of the present invention, epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, etc. are used as necessary to enhance the adhesion between the resin component and the inorganic filler. Various known coupling agents such as various silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be added. These may be used alone or in combination of two or more.
The amount of the coupling agent is preferably 0.05 to 5% by weight, more preferably 0.1 to 2.5% by weight, based on the inorganic filler. If it is less than 0.05% by weight, the moisture resistance tends to decrease, and if it exceeds 5% by weight, the moldability of the package tends to decrease.

In the molding material of the present invention, the content of halogen flame retardant such as brominated epoxy resin and the content of antimony flame retardant such as antimony trioxide, antimony tetroxide, and antimony pentoxide are both molding materials. The total content is preferably 0.1% by weight or less. More preferably, neither halogen-based flame retardant nor antimony-based flame retardant is included.
Furthermore, in the epoxy resin molding material for sealing of the present invention, the colorant such as carbon black, organic dye, organic pigment, titanium oxide, red lead, bengara, imidazole, triazole, as long as the effects of the present invention are not impaired. Adhesion promotion of tetrazole, triazine, etc. and their derivatives, anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline, etc. and their derivatives, aliphatic acid amide compounds, dithiocarbamates, thiadiazole derivatives, etc. An agent etc. can be mix | blended as needed.

The epoxy resin molding material for sealing of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. However, as a general method, a raw material having a predetermined blending amount is mixed with a mixer or the like. A method of sufficiently cooling and pulverizing after mixing and melting and kneading with a mixing roll, a kneader, an extruder or the like can be mentioned. It is easy to use if it is tableted with dimensions and weight that match the molding conditions.
Moreover, the epoxy resin molding material for sealing of the present invention can be dissolved in various organic solvents and used as a liquid epoxy resin molding material for liquid sealing. This liquid epoxy resin molding material for liquid sealing can be used on a plate or a film. It can also be used as an epoxy resin molding material for sealing in the form of a sheet or film obtained by coating thinly and scattering the organic solvent under conditions that do not allow the resin curing reaction to proceed so much.

  As an electronic component device obtained by sealing an element with the sealing epoxy resin molding material obtained in the present invention, a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, a support member such as a semiconductor Electronic components equipped with active elements such as chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils, and encapsulated with the epoxy resin molding material for sealing of the present invention. Examples thereof include devices. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, and a terminal portion and a lead portion of an element such as a bonding pad are connected by wire bonding or bump, and then the epoxy resin for sealing of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-) General resin-encapsulated ICs such as lead package (TSP), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package), and semiconductor chips connected to the tape carrier by bumps are molded with epoxy resin for sealing. TCP (Tape Carrier Package) sealed with materials, wire bonding, flip chip bonding to wiring formed on wiring boards and glass COB (Chip On) in which active elements such as semiconductor chips, transistors, diodes, thyristors and / or passive elements such as capacitors, resistors, coils, etc., which are connected by solder or the like, are sealed with the sealing epoxy resin molding material of the present invention. Board) module, hybrid IC, multi-chip module, an element mounted on an organic substrate on which a wiring board connection terminal is formed, and after connecting the element and the wiring formed on the organic substrate by bump or wire bonding, Examples thereof include BGA (Ball Grid Array) and CSP (Chip Size Package) in which the element is sealed with a sealing epoxy resin molding material. Moreover, the epoxy resin molding material for sealing of the present invention can also be used effectively for printed circuit boards.

As a method for sealing an element using the epoxy resin molding material for sealing of the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used. When the sealing epoxy resin molding material is liquid or pasty at normal temperature, a dispensing method, a casting method, a printing method, and the like can be given.
Also, not only a general sealing method for directly sealing an element with a resin, but also a hollow package system in which an epoxy resin molding material for sealing an electronic component is not in direct contact with the element, sealing for a hollow package Also suitable for use as an epoxy resin molding material.

(Examples 1-6 and Comparative Examples 1-11)
As the epoxy resin of component (A), an epoxy resin (epoxy resin 1, epoxy equivalent 168, softening point 70 ° C., trade name HP-manufactured by Dainippon Ink & Chemicals, Inc.) having an epoxidized product of dihydroxynaphthalene dimer as a main component 4701),
As a comparative epoxy resin of component (A), an epoxy equivalent of 196, a biphenyl type epoxy resin having a melting point of 106 ° C. (Comparative epoxy resin 1, trade name Epicoat YX-4000H manufactured by Japan Epoxy Resin Co., Ltd.),
A triphenolmethane type epoxy resin having an epoxy equivalent of 170 and a softening point of 60 ° C. (Comparative Epoxy Resin 2, trade name Epicoat 1032H60 manufactured by Japan Epoxy Resin Co., Ltd.) was prepared.
(B) Biphenyl aralkyl type phenol resin having a hydroxyl equivalent of 200 and a softening point of 65 ° C. as a curing agent for the component (curing agent 1, trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.),
Β-naphthol aralkyl resin having a hydroxyl group equivalent of 185 and a softening point of 67 ° C. (curing agent 2, trade name SN-170L manufactured by Nippon Steel Chemical Co., Ltd.),
As a comparative curing agent for component (B), a triphenylmethane type phenol resin (comparative curing agent 1, Meiwa Kasei Co., Ltd., trade name MEH-7500) having a hydroxyl group equivalent of 103 and a softening point of 83 ° C. was prepared.
(C) component triphenylphosphine (curing accelerator 1),
Addition reaction product of triphenylphosphine and p-benzoquinone (curing accelerator 2),
Addition reaction product of tributylphosphine and p-benzoquinone (curing accelerator 3),
(C) 1,8-diaza-bicyclo (5,4,0) undecene-7 and phenol novolac addition reaction product (comparative curing accelerator 1) as a comparative curing accelerator of component (C)
2-Phenyl-4-methylimidazole (Comparative curing accelerator 2) was prepared.
(D) Spherical fused silica having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² / g as an inorganic filler, oxidized polyethylene as a release agent, and γ-glycidoxypropyltrimethoxysilane (epoxy as a coupling agent) Silane) and carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Corporation) were prepared as a colorant.
These were blended in parts by weight shown in Table 1 and Table 2, respectively, and roll kneading was carried out under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes to produce epoxy resin molding materials for sealing of Examples and Comparative Examples. .

The produced epoxy resin molding materials for sealing of Examples and Comparative Examples were evaluated by the following tests. The evaluation results are shown in Tables 3 and 4.
The epoxy resin molding material for sealing was molded by a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. Further, post-curing was performed at 175 ° C. for 6 hours.
(1) Spiral flow (fluidity index)
The sealing epoxy resin molding material was molded under the above conditions using a spiral flow measurement mold in accordance with EMMI-1-66, and the flow distance (cm) was determined.
(2) Hardness when heated Using a varis mold made by Mitomi Metal Co., Ltd. having a cull part with a diameter of 30 mm and a depth of 4 mm in the center, the epoxy resin molding material for sealing is 30 mm in diameter and thickness under the above conditions. After forming into a 4 mm disk, immediately after molding, that is, 5 seconds after the lower mold of the transfer press starts to open, the mold is taken out, and immediately after that, the shore D of the molded product (the cull portion at the center of the mold) Hardness was measured.
(3) Flammability Using the post-cured test piece (test piece thickness 1/8 inch), the flammability was determined according to the 94UL standard.
(4) Heat resistance SOP-28p (42Alloy lead frame) with TEG-ML1020 chip (Line / Space = 20 μm / 20 μm area 2 locations: 1.90 × 4.20 mm, Line / Space = 10 μm / 10 μm area 2 locations: 1 .90 × 4.20 mm), and the lead frame and the chip were connected by a gold wire of φ20 μm. Then, sealing with the produced molding material was performed, and after post-curing, it was left in an environment of 195 ° C. for 1000 hours.
Of the manufactured packages N = 10 made of each molding material, the presence or absence of electrical continuity after being left was measured, and among the total of 4 wirings, the package having continuity failure even in one wiring was counted as an NG package.
(5) Cold and heat cycle resistance A silicon chip (8 × 10 mm / silicon nitride protective film) was mounted on QFP1420 × 2.0 mmt (EFTEC-64T lead frame / flat island). EN-4065D manufactured by Hitachi Chemical Co., Ltd. was used as the die bond material. The curing condition of the die bond material was 210 ° C./2 minutes. Sealing with a molding material was carried out, and after post-curing, a cooling cycle test was conducted in which the package was alternately immersed in liquid nitrogen (-196 ° C.) and silicone oil (150 ° C.) for 2 minutes each. The package after 50 cycles was observed using SAT manufactured by Hitachi, Ltd., and the presence or absence of chip peeling, lead frame peeling, or package cracking was determined. Of the production packages N = 10 made of each molding material, the packages with defects such as peeling and cracking were counted as NG packages.

In Comparative Examples 1 to 5 in which the component (A) or the component (B) in the present invention is not specified, the flame retardancy is inferior, and the comparative examples 4 and 5 are also inferior in the thermal cycle resistance. Comparative Examples 9 to 11 that do not contain the component (C) in the present invention are inferior to any one or a plurality of items of curability, flame retardancy, heat resistance, and cold and heat cycle resistance. Moreover, even if it contains (C) component in this invention, the comparative examples 6-8 from which the addition amount remove | deviates from prescription | regulation are inferior to fluidity | liquidity (spiral flow) or a flame retardance.
On the other hand, Examples 1-6 which contain all (A)-(D) component in this invention, and the addition amount of (C) component is appropriate are moldability, such as fluidity | liquidity and sclerosis | hardenability, and a flame retardance. It can be seen that both heat resistance and heat cycle resistance are excellent.

Claims (5)

(A) an epoxy resin containing an epoxy resin obtained by glycidyl etherification of at least one dimer of hydroxynaphthalene and dihydroxynaphthalene, (B) a curing agent containing a compound represented by the following general formula (I), An epoxy resin molding material for sealing containing C) a phosphorus-based curing accelerator and (D) an inorganic filler, wherein the phosphorus content of component (C) is 200 to 500 ppm of the entire molding material.

(In general formula (I), n represents 0 or a positive integer, and the hydrogen atom on the benzene ring and naphthalene ring in A and B may be substituted with a hydrocarbon group.)   2. The epoxy resin molding material for sealing according to claim 1, wherein the content of both the halogen-based flame retardant and the antimony-based flame retardant is 0.1% by weight or less of the entire molding material.   The epoxy resin molding material for sealing according to claim 2, which does not contain a halogen flame retardant and an antimony flame retardant.   The epoxy resin molding material for sealing according to any one of claims 1 to 3, wherein the amount of the inorganic filler (D) is 70 wt% or more and 88 wt% or less of the entire molding material.   The electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing in any one of Claims 1-4.