JP2009074084A - Epoxy resin molding material for sealing, and electronic part device with element sealed by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin molding material for sealing which realizes high fluidity and satisfactory flame retardancy without practically using a halogenation resin and an antimony compound while making a high glass transition point and low-dielectric-low-dielectric tangent lowering compatible with each other, and is excellent in reliability, such as heat resistance, and moldability, and to provide an electronic part device with an element sealed by using the epoxy resin molding material for sealing. <P>SOLUTION: The epoxy resin molding material for sealing contains: (A) an epoxy resin; (B) a phenolic hardener expressed by general formula (1); (C) an inorganic filler; (D) a silane coupling agent; and (E) a compound having two or more vinyl benzene groups. The electronic part device is provided with the element sealed by using the epoxy resin molding material for sealing. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an epoxy resin molding material for sealing and an electronic component device including an element sealed using 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 and cost, 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 have higher reliability in terms of reliability such as heat resistance than so-called consumer applications such as personal computers and home appliances. In order to increase the heat resistance of the electronic device, it is desirable to increase the glass transition point of the sealing epoxy resin molding material forming the semiconductor package, and so-called polyfunctional resins are often used.

  In recent years, high-speed operation, high integration, high frequency, and the like of electronic devices have progressed, and the problem of dielectric loss that impairs the reliability by attenuating electrical signals has been highlighted. In order to suppress dielectric loss, it is necessary to reduce the dielectric constant and dielectric tangent of insulating materials such as semiconductor packages. However, the polyfunctional resin has a high functional group density, and generally has a high dielectric constant and dielectric tangent. Therefore, it is often difficult to achieve both a high glass transition point and a low dielectric loss / low dielectric loss.

For example, Patent Documents 1 and 2 disclose low dielectric loss and low dielectric loss of electronic devices. For example, Patent Document 3 discloses compatibility between a high glass transition point and low dielectric loss and low dielectric loss. is there.
Furthermore, as a feature of recent electronic equipment, there is a general trend toward miniaturization and thinning, and the molding method has been changed from conventional individual molding to sealing many packages by batch molding, and individual packages (individual) after sealing Many so-called map forming methods have been seen.

  In addition, the movement of transfer molding of a large module package which has been conventionally sealed with silicone gel has been seen in part. In these map molding and transfer molding in the silicone gel sealing field, high fluidity is often required for the sealing resin.

  On the other hand, halogenated resins such as decabromo and antimony compounds have conventionally been used as flame retardants for epoxy resin molding materials for sealing, but in recent years, the amount of these compounds has been restricted from the viewpoint of environmental protection. There is a demand for non-halogenation (non-bromination) and non-antimony formation. Further, it is known that a bromo compound has an adverse effect on the high temperature storage characteristics of a plastic encapsulated IC, and from this viewpoint, it is desired to reduce the amount of bromo resin.

  As described above, when a high glass transition point is realized by using a polyfunctional resin, it is generally difficult to achieve low dielectric constant and low dielectric loss tangent. In the said patent document, in order to aim at coexistence of these characteristics, using the compound which has a specific structure individually or in combination with another component is proposed.

JP 2003-212941 A Japanese Patent Laid-Open No. 2004-087737 JP 2002-249531 A

However, sufficient studies have not been made on the compatibility between the above characteristics and high fluidity, and the compatibility between flame retardancy and the like.
The present invention has been made in view of such a situation, and realizes high fluidity while achieving both a high glass transition point and a low dielectric constant / low dielectric loss tangent, and is excellent without using a halogenated resin or an antimony compound. An epoxy resin molding material for sealing that also achieves flame retardancy and has excellent reliability and moldability such as heat resistance, and an electronic component device comprising an element sealed using this epoxy resin molding material for sealing Is intended to provide.

  As a result of intensive studies to solve the above problems, the present inventors have added a phenolic curing agent having a specific structure and a compound having a specific structure to the epoxy resin molding material for sealing. The inventors have found that the above object can be achieved and have completed the present invention.

（一般式（Ｉ）中、ｎは０又は正の整数を表す。それぞれのベンゼン環に結合する水素原子は炭化水素基で置換されていてもよい。）

（一般式（ＩＩ）中、Ｒは置換基を有してもよい炭化水素骨格、Ｒ^１は水素原子、メチル基、又はエチル基を表し、ｍは１〜４、ｎは２以上の整数を表す。） The present invention
(1) (A) epoxy resin, (B) phenolic curing agent represented by the following general formula (I), (C) inorganic filler, (D) silane coupling agent, and (E) the following general formula (II) The epoxy resin molding material for sealing characterized by including the compound represented by this.

(In general formula (I), n represents 0 or a positive integer. The hydrogen atom bonded to each benzene ring may be substituted with a hydrocarbon group.)

(In general formula (II), R represents a hydrocarbon skeleton which may have a substituent, R ¹ represents a hydrogen atom, a methyl group, or an ethyl group, m is 1 to 4, and n is an integer of 2 or more. To express.)

(2) The epoxy resin molding material for sealing according to the above (1), wherein the component (D) is a silane coupling agent having an unsaturated bond.

(3) The epoxy resin molding material for sealing according to the above (1) or (2), which does not contain a halogen flame retardant and an antimony flame retardant.

(4) An electronic component device comprising an element sealed using the sealing epoxy resin molding material according to any one of (1) to (3).

  The epoxy resin molding material for sealing of the present invention is excellent in reliability such as heat resistance, low dielectric constant and low dielectric loss tangent property, fluidity, flame retardancy, etc. while having a high glass transition point. By sealing electronic components such as IC and LSI using molding materials, it is possible to obtain an electronic component device that is excellent in heat resistance, reliability such as low dielectric constant and low dielectric loss tangent, flame retardancy, etc. Industrial value is great.

<Epoxy resin molding material for sealing>
Hereinafter, the epoxy resin molding material for sealing of the present invention will be described first.
The sealing epoxy resin molding material of the present invention comprises (A) an epoxy resin, (B) a phenolic curing agent represented by the following general formula (I), (C) an inorganic filler, and (D) a silane coupling agent. And (E) a compound represented by the following general formula (II).

（一般式（Ｉ）中、ｎは０又は正の整数を表す。それぞれのベンゼン環に結合する水素原子は炭化水素基で置換されていてもよい。）

(In general formula (I), n represents 0 or a positive integer. The hydrogen atom bonded to each benzene ring may be substituted with a hydrocarbon group.)

（一般式（ＩＩ）中、Ｒは置換基を有してもよい炭化水素骨格、Ｒ^１は水素原子、メチル基、又はエチル基を表し、ｍは１〜４、ｎは２以上の整数を表す。）
以下に各成分について説明する。

(In general formula (II), R represents a hydrocarbon skeleton which may have a substituent, R ¹ represents a hydrogen atom, a methyl group, or an ethyl group, m is 1 to 4, and n is an integer of 2 or more. To express.)
Each component will be described below.

[(A) Epoxy resin]
In the present invention, as the component (A), an epoxy resin generally used for an epoxy resin molding material for sealing can be used without any particular limitation. Examples of epoxy resins applicable to the present invention include phenols such as phenol novolac epoxy resins and orthocresol novolac epoxy resins, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and / or Or a novolak resin obtained by condensation or cocondensation of naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and the like and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde in the presence of an acidic catalyst. Epoxidized, diglycidyl ether such as bisphenol A, bisphenol F, bisphenol S, bisphenol A / D, alkyl-substituted or unsubstituted biphenol Epoxides of biphenyl-type epoxy resins, phenol and / or naphthols and phenol-aralkyl resins, naphthol-aralkyl resins, biphenyl-aralkyl resins synthesized from dimethoxyparaxylene or bis (methoxymethyl) biphenyl , Stilbene type 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 obtained by reaction of epichlorohydrin Amine-type epoxy resin, dicyclopentadiene-type epoxy resin that is an epoxidized product of co-condensation resin of cyclopentadiene and phenol, has naphthalene ring Epoxy resins, triphenolmethane type epoxy resins, trimethylolpropane type epoxy resins, terpene modified epoxy resins, linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid, alicyclic epoxy resins and Examples include epoxy resins obtained by modifying these epoxy resins with silicone, acrylonitrile, butadiene, isoprene rubber, polyamide resin, or the like. These epoxy resins may be used alone or in combination of two or more.

  Among the above-mentioned epoxy resins, it is preferable that at least a part of the component (A) is an orthocresol novolak type epoxy resin from the viewpoint of achieving both a high glass transition point and low dielectric tangent and low dielectric loss tangent. In order to achieve a high glass transition point, it is more preferable to use an ortho-cresol novolak type epoxy resin having an ICI viscosity at 150 ° C. of 0.5 Pa · s or more.

  As a method for realizing both the high glass transition point and the low dielectric loss / low dielectric loss tangent, which are the effects of the present invention, for example, 70% by weight of the component (A) has an ICI viscosity of 1.0 Pa · s at 150 ° C. As an example, a certain ortho cresol novolac type epoxy resin is used, and the remaining 30% by weight is a triphenolmethane type epoxy resin classified as a so-called polyfunctional type epoxy resin.

[(B) Phenolic curing agent represented by general formula (I)]
In the present invention, as the (B) curing agent, the phenolic curing agent represented by the following general formula (I) is used singly or in combination from the viewpoint of achieving both low dielectric constant / low dielectric loss tangent and flame retardancy. It is necessary to use it.

（一般式（Ｉ）中、ｎは０又は正の整数を表す。それぞれのベンゼン環に結合する水素原子は炭化水素基で置換されていてもよい。）

(In general formula (I), n represents 0 or a positive integer. The hydrogen atom bonded to each benzene ring may be substituted with a hydrocarbon group.)

In the general formula (I), the positive integer represented by n is preferably 1 to 10, more preferably 1 to 5, particularly from the viewpoint of realizing high fluidity.
Further, the hydrogen atoms bonded to the benzene ring may be substituted with a linear or branched hydrocarbon group, but from the viewpoint of increasing the Tg of the cured product, all of them may be hydrogen atoms. preferable.
Specifically, MEH-7851 (manufactured by Meiwa Kasei Co., Ltd.) having n = 1 to 3 as a main component in general formula (I) and all benzene ring side chains being hydrogen atoms is commercially available.

The phenolic curing agent represented by the general formula (I) has relatively few hydrophilic functional groups such as hydroxyl groups, and is advantageous for realizing low dielectric constant and low dielectric loss tangent.
Further, since the phenolic curing agent represented by the general formula (I) is a so-called polycyclic aromatic compound, it is advantageous in terms of flame retardancy, such as easily forming char during combustion.

  In order to achieve both low dielectric and low dielectric loss tangent and flame retardancy, which are the effects of the present invention, the curing agent represented by the general formula (I) should be 30% by weight or more of the component (B). Is preferable, more preferably 40% by weight or more, and particularly preferably 50% by weight or more. When the curing agent represented by the general formula (I) is less than 30% by weight of the component (B), the flame retardancy may be particularly insufficient.

  Examples of the curing agent represented by the general formula (I) include MEH-7851 (trade name, manufactured by Meiwa Kasei Co., Ltd.) in which n = 1 to 10 and all side chains of the benzene ring are hydrogen atoms. It is available.

  In the present invention, in addition to the phenolic curing agent represented by the general formula (I) as the component (B), the curing agent generally used in the epoxy resin molding material for sealing does not lose the effect of the invention. Can be used in combination within a range. Examples of phenolic curing agents that can be used in combination include phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and / or naphthol such as α-naphthol, β-naphthol, and dihydroxynaphthalene. Is synthesized from a novolac-type phenolic resin obtained by condensation or cocondensation with a compound having an aldehyde group such as formaldehyde, benzaldehyde, salicylaldehyde, etc. in the presence of an acidic catalyst, the phenols and / or naphthols and dimethoxyparaxylene. Illustrate phenol-aralkyl resin, naphthol-aralkyl resin, dicyclopentadiene-type phenol resin, terpene-modified phenol resin, triphenolmethane-type phenol resin, etc. Is possible.

  As a method for realizing the high glass transition point and the low dielectric / low dielectric loss tangent, which is an effect of the present invention, for example, 70% by weight of the component (B) is phenol-based curing represented by the general formula (I) As an example, the remaining 30% by weight is a so-called polyfunctional type curing agent such as triphenolmethane type phenol resin.

  The equivalent ratio of the epoxy resin of component (A) and the curing agent of component (B), 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. In order to suppress the minute amount, it 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.

[(C) inorganic filler]
In the present invention, it is necessary to add (C) an inorganic filler for the purpose of reducing the linear expansion coefficient, reducing moisture absorption, improving the strength, and the like. Examples of inorganic fillers include fused silica, crystalline silica, synthetic silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, phosphor. Examples thereof include powders such as stellite, steatite, spinel, mullite, and titania, beads formed by spheroidizing these, and glass fibers.

  Furthermore, you may add metal hydroxide type inorganic fillers, such as aluminum hydroxide and magnesium hydroxide with a flame-retardant effect, in the range which does not lose the effect of this invention. From the viewpoint of fluidity, linear expansion coefficient, low dielectric constant and low dielectric loss tangent, it is preferable that part or all of the component (C) is crystalline silica, fused silica or synthetic silica. It is more preferable to use

From the viewpoint of flame retardancy, in particular, thermal cycle resistance in a package using a Cu lead frame, the amount of component (C) is preferably 70 to 90% by weight of the entire molding material, and 72 to 88% by weight. %, More preferably 75 to 85% by weight. If the component (C) is less than 70% by weight, the flame retardancy and the cold-heat cycle resistance may be insufficient, and if it exceeds 90% by weight, the cold-heat cycle property may be insufficient.
As the component (C), it is particularly advantageous in terms of flame retardancy to use crystalline silica, fused silica, or synthetic silica having a specific surface area of 3.0 m ² / g.

[(D) Silane coupling agent]
In the present invention, particularly from the viewpoint of fluidity, it is necessary to blend the (D) silane coupling agent alone or in combination of two or more. In the present invention, conventionally known silane coupling agents usually used for epoxy resin molding materials for sealing such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, etc. can be used. It is particularly effective in terms of fluidity when at least a part of is a silane coupling agent having an unsaturated bond such as vinyl silane or methacryl silane.

  Silane coupling agents having an unsaturated bond such as vinyl silane and methacryl silane are used as an affinity agent / dispersant for the component (A) or the component (B) and the component (E) represented by the general formula (II). It seems to play a role.

  Examples of the silane coupling agent having an unsaturated bond applicable to the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane and the like can be exemplified, but other coupling agents may be applied.

  As the coupling agent, for example, vinyltrimethoxysilane is “Z-6300” (trade name, manufactured by Toray Dow Corning Co., Ltd.), and methacryloxypropyltrimethoxysilane is “Z-6030” (Toray Dow Corning Co., Ltd.). Etc., which are available on the market.

  The amount of component (D) added is preferably 0.05 to 1% by weight of the total composition, more preferably 0.1 to 0.8% by weight, and 0.2 to 0.5% by weight. % Is particularly preferable. If the component (D) is less than 0.05% by weight, fluidity and moisture resistance reliability may exceed 1% by weight, and moldability such as curability may be insufficient.

  In the present invention, part or all of the component (D) is preferably a silane coupling agent having an unsaturated bond, but from the viewpoint of balance with reliability including fluidity and moisture resistance reliability, A silane coupling agent having reactivity with the component (A) or the component (B), such as epoxy silane, with 10 to 90% by weight of the component (D) as the silane coupling agent having an unsaturated bond; It is preferable to do.

[(E) Compound represented by general formula (II)]
In the present invention, it is necessary to add a compound represented by the following general formula (II) as the component (E) for the purpose of reducing the dielectric constant and the dielectric loss tangent. The component (E) generally initiates radical polymerization in the presence of a reaction initiator such as an organic peroxide. However, even when the reaction initiator is not present, the reaction proceeds slowly at a high temperature. Therefore, particularly good fluidity can be secured in a system in which no reaction initiator is added. Moreover, since the hardened | cured material formed after reaction contains many aromatic rings relatively with respect to chain hydrocarbons, such as an alkyl group, a flame retardance becomes favorable.

（一般式（ＩＩ）中、Ｒは置換基を有してもよい炭化水素骨格、Ｒ^１は水素原子、メチル基、又はエチル基を表し、ｍは１〜４、ｎは２以上の整数を表す。）

(In general formula (II), R represents a hydrocarbon skeleton which may have a substituent, R ¹ represents a hydrogen atom, a methyl group, or an ethyl group, m is 1 to 4, and n is an integer of 2 or more. To express.)

In general formula (II), the hydrocarbon skeleton represented by R is an n-valent hydrocarbon group, which may be linear or branched, and is preferably a hydrocarbon group having 1 to 4 carbon atoms, More preferred are 3 hydrocarbon groups. Specific examples include an ethylene group and a propylene group. When the number of carbon atoms is 4 or less, it is advantageous in terms of increasing the Tg of the cured product.
n is preferably 2 to 10, and more preferably 2 to 5. When n is 10 or less, the viscosity of the compound is hardly increased, which is advantageous from the viewpoint of realizing high fluidity.
When m is 2 or more, each R ¹ is the same or partly or entirely different. From the viewpoint of increasing the Tg of the cured product, R ¹ is preferably hydrogen.

  The compound represented by the general formula (II) is a method of coupling halogenoalkylstyrene with various halides by Grignard reaction, as described in JP-A-2002-249531, etc., Polymer Journal Vol. , P163 (1979), and can be synthesized by a synthesis method of a divinylbenzene oligomer having a vinyl group in a side chain.

  Among the compounds represented by the general formula (II), it is preferable to use a compound having a weight average molecular weight of 1000 or less from the viewpoint of fluidity, for example, 1,3-chloromethylvinylbenzene, 1,4-chloro. Embodiments such as using a compound represented by the following structural formulas (III) to (V) obtained by a Grignard reaction from methyl vinylbenzene or the like alone or in combination can be exemplified.

  In the present invention, the amount of component (E) is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, and more preferably 1 to 5% by weight of the entire composition. It is particularly preferred. When the blending amount of the component (E) is less than 0.1% by weight, the effect of low dielectric constant / low dielectric loss tangent is more than 10% by weight. , Each may be insufficient.

[Other ingredients]
(Curing accelerator)
In the present invention, in addition to the components (A) to (E), a curing accelerator can be added to accelerate the crosslinking reaction between the components (A) and (B). As the curing accelerator, it is possible to use conventionally known phosphorus-based and nitrogen-based curing accelerators that are usually used for sealing epoxy resin molding materials. , Triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, methyldiphenylphosphine, phenylphosphine, tributylphosphine, tetraphenylphosphinetetraphenylborate, triphenylphosphinetetraphenylborate, etc. 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1,8-diaza-bicyclo (5 , 4, 0) Undecene-7 and other cycloamidine compounds, benzyldimethylamine Tertiary amine compounds such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and derivatives thereof, imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and the like And derivatives thereof. These curing accelerators may be used alone or in combination of two or more.

  The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight with respect to the component (A). . If it is less than 0.1% by weight, the curability in a short time tends to be inferior, and if it exceeds 10% by weight, the curing rate tends to be too high and it becomes difficult to obtain a good molded product due to unfilling or the like.

(Reaction initiator)
In the present invention, in addition to the components (A) to (E), a reaction initiator can be added to promote the self-polymerization reaction of the component (E). Examples of the reaction initiator include benzoin compounds such as benzoin and benzoin methyl, acetophenone, acetophenone compounds such as 2,2-dimethoxy-2-phenylacetophenone, 2,5-dimethyl-2,5-di ( t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, radical polymerization catalysts such as organic peroxides such as dicumyl peroxide, boron tetrafluoride And cationic catalysts such as diallyl iodonium salts and triallyl sulfonium salts having phosphorus hexafluoride as a counter anion.

  Although there is no restriction | limiting in particular about the addition amount of a reaction initiator, 0.05 to 10 weight% is preferable with respect to (E) component represented by general formula (II). If it is less than 0.05% by weight, the effect of promoting the reaction may be insufficient. If it exceeds 10% by weight, the flow characteristics may be insufficient due to overreaction.

(Polymerization inhibitor)
In the present invention, a polymerization inhibitor can be added to control the reaction together with the (self-polymerization reaction) reaction initiator of the component (E). Examples of the polymerization inhibitor include quinones such as hydroquinone, trimethylquinone, and 4-t-butylpyrocatechol, aromatic diols, and the like.
The addition amount of the polymerization inhibitor is not particularly limited as long as the purpose can be achieved, but 0.0005 to 5% by weight is preferable with respect to the component (E).

(Release agent)
In the present invention, in order to ensure smooth releasability from the mold during molding, higher fatty acid waxes such as stearic acid and montanic acid, higher fatty acid ester waxes such as stearic acid ester and montanic acid ester, Conventionally known release agents used for polyethylene wax and the like and epoxy resin molding materials for sealing can be used.

  In the epoxy resin molding material for sealing of the present invention, particularly from the viewpoint of heat resistance, halogen flame retardants such as brominated epoxy resins, and antimony flame retardants such as antimony trioxide, antimony tetroxide, and antimony pentoxide. It is preferable that none of these are substantially contained. Here, “substantially free of halogenated flame retardant and antimony flame retardant” means that each component is 900 ppm (0.09 wt%) or less with respect to the entire composition.

  In the present invention, it is possible to add a flame retardant other than the halogen-based flame retardant and the antimony-based flame retardant as required, as long as the effects of the present invention are not impaired. Although there is no restriction | limiting in particular about the flame retardant which can be added, For example, illustration of organophosphorus compounds, such as a triphenylphosphine oxide, is possible.

An anion exchanger can also be added to the sealing epoxy resin molding material of the present invention from the viewpoint of improving the moisture resistance and heat resistance (high temperature storage resistance) of a semiconductor element such as an IC.
Although there is no restriction | limiting in particular about the anion exchanger applicable to this invention, For example, a hydrotalcite etc. can be illustrated.

  Although there is no restriction | limiting in particular also about the addition amount of an anion exchanger, 0.1-30 weight% is preferable with respect to the epoxy resin of (A) component, 1-10 weight% is more preferable, 2-5 weight% is Further preferred. 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.

  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 thinly coating and scattering the organic solvent under conditions that do not allow the resin curing reaction to proceed so much.

<Electronic component device>
The electronic component device of the present invention is an electronic component device including an element sealed using the above-described sealing epoxy resin molding material of the present invention, and the electronic component device includes a lead frame, Mounting elements such as active elements such as semiconductor chips, transistors, diodes, thyristors, and passive elements such as capacitors, resistors, coils, etc. are mounted on supporting members such as pre-wired tape carriers, wiring boards, glass, and silicon wafers. An electronic component device or the like in which such a portion is sealed with the sealing epoxy resin molding material of the present invention can be mentioned.

  As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, the terminal portion of the element such as a bonding pad and the lead portion are connected by wire bonding or bump, and then the epoxy resin molding for sealing of the present invention is performed. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead) General resin-encapsulated ICs such as package (TSOP), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package), and the semiconductor chip connected to the tape carrier by bumps, the epoxy resin molding material for encapsulation of the present invention TCP (Tape Carrier Package) sealed with wire, 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 terminals for wiring board connection are 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 an epoxy resin molding material for sealing. 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 1-8 and Comparative Examples 1-6]
As an epoxy resin of component (A), an ortho-cresol novolak epoxy resin having an epoxy equivalent of 200, a softening point of 75 ° C., and an ICI viscosity of 1.0 Pa · s at 150 ° C. (epoxy resin 1, manufactured by Dainippon Ink & Chemicals, Inc.) , Trade name EPICLON N500P-10), an epoxy equivalent of 170, and a triphenolmethane type epoxy resin having a softening point of 60 ° C. (Epoxy Resin 2, trade name: Epicoat 1032H60, manufactured by Japan Epoxy Resin Co., Ltd.) was prepared.

  As a curing agent for component (B), a hydroxyl group equivalent of 200, a softening point of 65 ° C., a curing agent 1 represented by the following structural formula (biphenyl-aralkyl type phenol resin, trade name MEH-7851 manufactured by Meiwa Kasei Co., Ltd.), hydroxyl group equivalent 103, a triphenolmethane type phenol resin having a softening point of 80 ° C. (curing agent 2, manufactured by Meiwa Kasei Co., Ltd., trade name MEH-7500-3S) was prepared.

硬化剤１は、ｎは０又は正の整数の混合物で、主成分はｎ＝２〜４のものである。

In the curing agent 1, n is a mixture of 0 or a positive integer, and the main component is n = 2-4.

As component (C), fused spherical silica (trade name FB-950, manufactured by Denki Kagaku Kogyo Co., Ltd.) having an average particle size of 25 μm and a specific surface area of 1.5 m ² / g, an average particle size of 0.5 μm, and a specific surface area of 6.5 m ² / G synthetic spherical silica (manufactured by Admatechs Co., Ltd., trade name SO-25R) was prepared as a 9/1 (weight ratio) mixture.

  As component (D), 3-glycidoxypropyltrimethoxysilane (D1 component, manufactured by Toray Dow Corning Co., Ltd., trade name Z-6040), methyltrimethoxysilane (D2 component, manufactured by Toray Dow Corning Co., Ltd., product) Name Z-6366), vinyltrimethoxysilane (D3 component, manufactured by Toray Dow Corning Co., Ltd., trade name Z-6300) and methacryloxypropyltrimethoxysilane (D4 component, manufactured by Toray Dow Corning Co., Ltd., trade name Z) -6030) was prepared.

  A mixture of compounds represented by the following structural formulas (III) to (V) as the component (E), triphenylphosphine as the curing accelerator, and 1,1-di (t-butylperoxide as the reaction initiator of the component (E) Oxy) cyclohexane (manufactured by NOF Corporation, trade name Perhexa C-40 (purity 40%) was prepared. In addition, the compounds represented by structural formulas (III) to (V) in the component (E) The mixing ratio (weight ratio) is 1: 1: 1.

  An oxidized polyethylene wax was prepared as a release agent, carbon black as a colorant, and triphenylphosphine oxide as a flame retardant.

  Next, each material prepared above is blended in parts by weight shown in Tables 1 and 2, respectively, and roll kneading is performed under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. An epoxy resin molding material for sealing was produced.

The epoxy resin molding materials for sealing of each Example and each Comparative Example prepared above 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. Post-curing was performed at 175 ° C. for 6 hours.

(1) Spiral flow (indicator of fluidity / fillability)
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) Glass transition point According to JIS K7197, the cured product obtained by the above molding and post-curing was used as a test piece, and the glass transition point was determined by TMA (Thermal Mechanical Analysis). The test piece size was 4 × 4 × 20 mm, the measurement temperature region during measurement was 250 ° C. from room temperature (25 ° C.), and the temperature increase rate was 5 ° C./min. The glass transition point was calculated | required from the intersection of the line extended from a 40-80 degreeC area | region, and the line extended from 200-240 degreeC.

(3) Flame retardance According to 94UL standard, the test piece thickness after post-curing was tested at 1/8 inch to determine the combustibility.

(4) Dielectric constant and dielectric loss tangent Based on JISK6911, the dielectric constant and dielectric loss tangent in frequency 1MHz were calculated | required. The measurement apparatus used was “4275A MULTI-FREQENCY LCR METER” manufactured by HEWLETT PACKARD.

  As shown in Tables 3 and 4, Comparative Examples 1 to 5 that do not contain the component (E) have a short spiral flow (high fluidity) and a large dielectric loss tangent value. It is clear that Comparative Examples 2, 3 and 5 containing the component (D3) and the component (D4) as the coupling agent are also inferior in flame retardancy. Moreover, even if it contains (E) component, it is clear that the comparative example 6 which does not contain "the hardening | curing agent 1" as (B) component is also inferior in a flame retardance.

  On the other hand, Examples 1 to 8 including the component (B) and the component (E) are excellent in fluidity and achieve a high glass transition point, and have an electronic component device such as flame retardancy and low dielectric constant / low dielectric loss tangent. It can be seen that the characteristics related to reliability are also excellent. Moreover, it is clear that Examples 2 to 4 and 6 to 8 including the component (D3) and the component (D4) as the component (D) are particularly excellent in fluidity.

Claims (4)

(A) epoxy resin, (B) phenolic curing agent represented by the following general formula (I), (C) inorganic filler, (D) silane coupling agent and (E) represented by the following general formula (II) An epoxy resin molding material for sealing, comprising a compound to be formed.

(In general formula (I), n represents 0 or a positive integer. The hydrogen atom bonded to each benzene ring may be substituted with a hydrocarbon group.)

(In general formula (II), R represents a hydrocarbon skeleton which may have a substituent, R ¹ represents a hydrogen atom, a methyl group, or an ethyl group, m is 1 to 4, and n is an integer of 2 or more. To express.)   The epoxy resin molding material for sealing according to claim 1, wherein the component (D) is a silane coupling agent having an unsaturated bond.   The epoxy resin molding material for sealing according to claim 1 or 2, which does not contain a halogen flame retardant and an antimony flame retardant.   The electronic component apparatus provided with the element sealed using the epoxy resin molding material for sealing of any one of Claims 1-3.