JP6583312B2 - Epoxy resin molding material for sealing and electronic component device - Google Patents

Description

  The present invention relates to an epoxy resin molding material for sealing and an electronic component device.

  As electronic devices have become smaller, lighter, and higher performance in recent years, mounting density has been increasing, and electronic component devices have come to be made surface mount packages from conventional pin insertion types. . Surface-mount ICs, LSIs, etc. are thin and small packages to increase the mounting density and reduce the mounting height, increasing the area occupied by the device package, and the package thickness is extremely high It has become thinner. Furthermore, these packages have different mounting methods from conventional pin insertion type packages, and surface mount type packages are becoming mainstream.

  That is, when the electronic component device is attached to the wiring board, the conventional pin insertion type package is soldered from the back side of the wiring board after the pins are inserted into the wiring board, so that the package is not directly exposed to high temperature. However, in the surface mount type package, the entire electronic component device is processed by a solder bath, a reflow device or the like, so that the package is directly exposed to a soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the moisture absorption moisture expands rapidly during soldering, and the generated vapor pressure acts as a peeling stress, causing peeling between the element and lead frame inserts and the sealing material. In addition, this causes package cracks and poor electrical characteristics. For this reason, development of the sealing material excellent in solder heat resistance (reflow resistance) is desired.

  In order to meet these demands, various studies have been made from the epoxy resin side, which is the main material, but only by improving the epoxy resin side, the heat resistance decreases due to low moisture absorption, and the adhesiveness is reduced. A decrease in curability associated with the improvement occurred, and it was difficult to balance physical properties. Accordingly, various epoxy resin modifiers have been studied from the above technical background, and silane coupling agents have been studied, focusing on improving adhesion to inserts such as element lead frames as one example. . Specifically, an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent (for example, see Patent Document 1), and a sulfur atom-containing silane coupling agent for the purpose of further improving adhesion (for example, Patent Document 2). Reference) is under consideration.

JP-A-11-147939 JP 2000-103940 A

  However, when an epoxy group-containing silane coupling agent or an amino group-containing silane coupling agent is used, the effect of improving adhesiveness may not be sufficient. In particular, the amino group-containing silane coupling agent described in Patent Document 1 has high reactivity, and when used in an epoxy resin molding material for sealing, fluidity decreases and the silane coupling agent itself gels. There is a problem in handling. Further, when a sulfur atom-containing silane coupling agent is used, the effect of improving the adhesion with noble metals such as silver (Ag) and gold (Au) is not sufficient, and the effect of improving the reflow resistance is also insufficient.

  As described above, an epoxy resin molding material for sealing that sufficiently satisfies fluidity has not been obtained. The present invention has been made in view of such circumstances, and an object of the present invention is to provide an epoxy resin molding material for sealing excellent in fluidity, and an electronic component device including an element sealed thereby.

  The present invention relates to an epoxy resin molding material for sealing containing a silane compound containing a hydrocarbon group having a specific structure, and an electronic component device including an element sealed with the epoxy resin molding material for sealing. More specifically, it is as follows.

  The present invention relates to an epoxy resin molding material for sealing containing (1) (A) an epoxy resin, (B) a curing agent, and (C) a silane compound represented by the following general formula (I).

(In General Formula (I), R ¹ and R ² each independently represents a hydrocarbon group having 2 to 5 carbon atoms, R ³ represents a hydrocarbon group having 1 or 2 carbon atoms, and p is 2 or 3 is shown.)

In the silane compound represented by (2) (C) general formula (I), R ¹ and R ² are each independently a linear or branched carbon atom having 2 to 5 carbon atoms. It is related with the epoxy resin molding material for sealing as described in said (1) which is a hydrogen group.

In the silane compound represented by (3) (C) general formula (I), R ¹ and R ² are each independently a branched hydrocarbon group having 3 to 5 carbon atoms. It is related with the epoxy resin molding material for sealing as described in said (1) or (2).

  The present invention further includes (4) and (D) at least one second silane compound selected from an epoxy group-containing alkoxysilane compound and an arylamino group-containing alkoxysilane compound. It is related with the epoxy resin molding material for sealing of any one item.

  In the present invention, (5) the epoxy group-containing alkoxysilane compound is at least one selected from the group consisting of a compound represented by the following general formula (II) and a compound represented by the general formula (III): It is related with the epoxy resin molding material for sealing as described in (4).

(In the general formula (II), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 6 carbon atoms. P1 represents an integer of 1 to 3, and q1 represents 2 or 3. In formula (III), R ²¹ and R ²² each independently represent a hydrocarbon group having 1 to 6 carbon atoms, p2 represents an integer of 1 to 3, and q2 represents 2 or 3.

  Moreover, this invention is (6) The epoxy resin for sealing as described in said (4) or (5) whose said arylamino group containing alkoxysilane compound is at least 1 sort (s) of the compound shown by the following general formula (IV). It relates to molding materials.

(In General Formula (IV), R ³¹ and R ³² each independently represent a hydrocarbon group having 1 to 6 carbon atoms. P3 represents an integer of 1 to 3, and q3 represents 2 or 3).

  Moreover, this invention relates to an electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing of any one of (7) said (1)-(6).

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin molding material for sealing excellent in fluidity | liquidity and the electronic component apparatus provided with the element sealed by this can be provided.

  In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Further, in this specification, the amount of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.

  The sealing epoxy resin molding material of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) a silane compound represented by the following general formula (I), as necessary. Consists of other components. By including the silane compound represented by the following general formula (I), the fluidity of the sealing epoxy resin molding material is improved.

(In General Formula (I), R ¹ and R ² each independently represents a hydrocarbon group having 2 to 5 carbon atoms, R ³ represents a hydrocarbon group having 1 or 2 carbon atoms, and p is 2 or 3 is shown.)

  The sealing epoxy resin molding material of the present invention is a solid at room temperature and normal pressure. There is no restriction | limiting in the shape of a solid, Any shapes, such as a powder form, a granular form, and a tablet form, may be sufficient.

(C) Silane compound represented by general formula (I) (first silane compound)
The (C) silane compound used in the present invention needs to have a structure represented by the following general formula (I). Hereinafter, the silane compound represented by the general formula (I) may be referred to as a first silane compound.

In general formula (I), R ¹ and R ² each independently represent a hydrocarbon group having 2 to 5 carbon atoms, R ³ represents a hydrocarbon group having 1 or 2 carbon atoms, and p is 2 or 3 Indicates.

In the present invention, when only a silane compound (for example, methyltrimethoxysilane) other than (C) the first silane compound is used as the silane compound, the effect of improving reflow resistance and fluidity is not sufficient. Specifically, when R ¹ or R ² in the general formula (I) such as n-hexyltrimethoxysilane or n-decyltrimethoxysilane is a hydrocarbon group having 6 or more carbon atoms, the chain length of the hydrocarbon group Tends to be long and the curability tends to be greatly reduced. Further, when R ¹ or R ² in the general formula (I) is a methyl group which is a hydrocarbon group having 1 carbon atom, the fluidity tends to be lowered. Furthermore, when R ¹ or R ² in the general formula (I) is a methyl group, the chain length of the hydrocarbon group is short and the reflow resistance tends to be lowered.

Examples of the hydrocarbon group having 2 to 5 carbon atoms represented by R ¹ and R ² in the general formula (I) include an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, and a pentyl group. And linear, branched or cyclic alkyl groups such as cyclopentyl group; alkenyl groups such as vinyl group, propenyl group, butenyl group, and pentenyl group. Among these, from the viewpoint of fluidity, a linear or branched hydrocarbon group having 2 to 5 carbon atoms is preferable, and a linear or branched alkyl group having 2 to 5 carbon atoms is more preferable. Further, from the viewpoints of curability and fluidity, a branched hydrocarbon group having 3 to 5 carbon atoms is preferable, and a branched alkyl group having 3 to 5 carbon atoms is preferable.

  Furthermore, from the viewpoint of improving reflow resistance by reducing hygroscopicity, an alkyl group having a larger number of carbon atoms is preferred. From the viewpoint of curability, a branched alkyl group is preferable to a straight chain, and the smaller the number of carbon atoms, the more preferable. From the viewpoint of fluidity, a branched alkyl group is preferable to a straight chain, the number of carbons is preferably 3 or 4, and a hydrocarbon group having 3 carbons is more preferable.

Examples of the hydrocarbon group having 1 or 2 carbon atoms represented by R ³ in the general formula (I) include a methyl group, an ethyl group, and a vinyl group. From the viewpoint of fluidity and adhesiveness, the carbon number is 1 Alternatively, an alkyl group of 2 (methyl group or ethyl group) is preferable, and a methyl group is more preferable from the viewpoint of availability.

  About the value shown by p in the said general formula (I), 2 is preferable from a viewpoint of reflow resistance and fluidity | liquidity. On the other hand, 3 is preferable from the viewpoint of curability, and can be properly used according to the required characteristics.

Such a (C) first silane compound is available as a reagent from Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., etc., and industrially, Z-made by Toray Dow Corning Co., Ltd. 6265, Z-2306, Organic Synthetic Chemical Industry Co., Ltd. DIPDMS, IBIPDMS, DIBDMS, etc. are commercially available.
These (C) 1st silane compounds may be used individually by 1 type, or may be used in combination of 2 or more type.

  The content of (C) the first silane compound relative to the total amount of (A) epoxy resin in the sealing epoxy resin molding material is not particularly limited as long as the effects of the present invention are not impaired. From the viewpoint of moldability and adhesiveness, the total content of (C) the first silane compound with respect to the total amount of (A) epoxy resin is preferably 0.5% by mass to 20% by mass, and 1.5% by mass to 15%. % By mass is more preferable, and 2% by mass to 12% by mass is even more preferable. (C) When the total content of the first silane compound is 0.5% by mass or more, the fluidity tends to be further improved. Moreover, there exists a tendency which can suppress generation | occurrence | production of molding defects, such as a void, as it is 20 mass% or less. Furthermore, among the above preferable ranges, the water absorption tends to decrease as the content increases, and the reflow resistance tends to improve.

(D) Second silane compound The epoxy resin molding material for sealing includes (D) an epoxy group-containing alkoxysilane compound and an arylamino group-containing alkoxysilane compound as silane compounds other than the (C) first silane compound. It is preferable to contain at least one second silane compound selected from: By further containing the second silane compound, the reflow resistance is improved. In particular, the addition of the second silane compound has an effect of improving the reflow resistance even when moisture is absorbed.

  The structure of the epoxy group-containing alkoxysilane compound in the present invention is not particularly limited as long as it is a silane compound having an epoxy group. For example, it is preferably at least one selected from the group consisting of a compound represented by the following general formula (II) and a compound represented by (III).

In General Formula (II), R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 6 carbon atoms. p1 represents an integer of 1 to 3, and q1 represents 2 or 3.

In the general formula (III), R ²¹ and R ²² each independently represent a hydrocarbon group having 1 to 6 carbon atoms. p2 represents an integer of 1 to 3, and q2 represents 2 or 3.

  The structure of the arylamino group-containing alkoxysilane compound is not particularly limited as long as it is an alkoxysilane compound in which an aryl group adjacent to the amino group is present. Examples of the arylamino group include a phenylamino group that is unsubstituted or substituted with a hydroxy group or a hydrocarbon group, an N-methyl-N-phenylamino group, a group having an anilide structure, and the like.

  The arylamino group-containing alkoxysilane compound used in the present invention preferably has a structure represented by the following general formula (IV).

In the general formula (IV), R ³¹ and R ³² each independently represent a hydrocarbon group having 1 to 6 carbon atoms. p3 represents an integer of 1 to 3, and q3 represents 2 or 3.

  In the present invention, as the second silane compound, only an epoxy group-containing alkoxysilane compound is used, or only an arylamino group-containing alkoxysilane compound is used, or an epoxy group-containing alkoxysilane compound and an arylamino group are contained. An alkoxysilane compound may be used in combination.

  In general, since an epoxy group-containing alkoxysilane compound reacts with an amino group, it is difficult to consider using an amino group-containing compound in combination with an epoxy group-containing alkoxysilane compound. However, even when the arylamino group-containing alkoxysilane compound is mixed with the epoxy group-containing alkoxysilane compound, a decrease in storage stability of the mixture is suppressed, and an increase in viscosity and gelation of the mixture are suppressed. . And each function of an arylamino group containing alkoxysilane compound and an epoxy group containing alkoxysilane compound is exhibited, and it becomes the epoxy resin molding material for sealing which is excellent by reflow resistance.

  The reason for this is not clear, but it can be considered that the presence of the aryl group adjacent to the amino group inhibits the reactivity of the hydrogen atom of the amino group and suppresses the reaction with the epoxy group.

As the hydrocarbon group having 1 to 6 carbon atoms represented by R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ and R ³² in the general formula (II), general formula (III) and general formula (IV) Includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group; and a phenyl group.

As the hydrocarbon group having 1 to 6 carbon atoms represented by R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ and R ³² , an alkyl group having 1 to 4 carbon atoms is particularly preferred from the viewpoint of fluidity and adhesiveness. It is preferable that a methyl group or an ethyl group is more preferable, and a methyl group is still more preferable from the viewpoint of easy availability.

  As p1 to p3 in the general formulas (II), (III) and (IV), 2 or 3 is preferable from the viewpoint of fluidity and adhesiveness, and 3 is more preferable from the viewpoint of availability. As q1 and q3 in the general formulas (II) and (IV), 3 is preferable from the viewpoint of the storage stability and availability of the silane compound. Moreover, as q2 in the said general formula (III), 2 is preferable from a viewpoint of the storage stability and availability of a silane compound.

  Among the second silane compounds, from the viewpoint of reflow resistance, the compound represented by the general formula (II) or (III) is preferable, and from the viewpoint of the balance of fluidity, curability and reflow resistance. The compound represented by the general formula (IV) is preferable.

  Such second silane compounds are Z-6040 (3-glycidoxypropyltrimethoxysilane), Z-6041 (3-glycidoxypropyltriethoxysilane), Z-6042 (made by Toray Dow Corning Co., Ltd.). 3-glycidoxypropylmethyldiethoxysilane), Z-6043 (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane), Z-6044 (3-glycidoxypropylmethyldimethoxysilane), Z-6883 It can be obtained as a commercial product such as (3-anilinopropyltrimethoxysilane).

  These second silane compounds may be used alone or in combination of two or more. When two or more epoxy group-containing silane compounds are used, only the compound represented by the above general formula (II), only the compound represented by the above general formula (III), and only the compound represented by the above general formula (IV). Or a compound represented by the above general formula (II), a compound represented by the above general formula (III), and a compound represented by the above general formula (IV) may be used in combination.

  In the present invention, when the second silane compound is used, the content is not particularly limited as long as the effects of the present invention are not impaired. When the total amount of (C) the first silane compound and (D) the second silane compound relative to the total amount of (A) epoxy resin in the epoxy resin molding material for sealing is “C + D content”, The C + D content is preferably 3% by mass to 20% by mass, more preferably 6% by mass to 16% by mass, and still more preferably 8% by mass to 12% by mass from the viewpoints of moldability and adhesiveness. There exists a tendency for fluidity | liquidity to improve that a C + D content rate is 3 mass% or more. Moreover, there exists a tendency which can suppress generation | occurrence | production of shaping | molding defects, such as a void, as C + D content rate is 20 mass% or less. Furthermore, among the above preferable ranges, the water absorption tends to decrease as the content increases, and the reflow resistance tends to improve.

Further, the total amount of (C) the first silane compound relative to the total amount of (C) the first silane compound and (D) the second silane compound in the epoxy resin molding material for sealing is “C content”. In the case, the C content is not particularly limited as long as the effects of the present invention are not impaired. Among these, from the viewpoints of reflow resistance and each property balance, the C content is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 20% by mass to 60% by mass. .
Further, within this range, the higher the C content, the lower the water absorption rate. Moreover, reflow resistance and fluidity | liquidity can be improved simultaneously and fully as C content rate is 20 to 80 mass%.

Also, the second silane compound as (D), when used in combination an epoxy group-containing alkoxysilane compound (D ₁₎ and an arylamino group-containing alkoxysilane compound (D _2), first the encapsulating epoxy resin molding material When the total amount of the epoxy group-containing alkoxysilane compound (D ₁ ) relative to the total amount of the two silane compounds (D) is “D ₁ content rate”, the D ₁ content rate is particularly limited unless the effects of the present invention are impaired. There is no limit. Among these, from the viewpoint of reflow resistance and balance of each property, the D ₁ content is preferably 20% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 85% by mass or less, and further more preferably 40% by mass or more and 80% by mass or less. preferable.

  The blending method of (C) the silane compound and (D) the second silane compound in producing the sealing epoxy resin molding material is not particularly limited. For example, you may mix | blend each independently, and you may mix | blend (C) silane compound and (D) 2nd silane compound which were mixed beforehand. Furthermore, when mix | blending each independently, the order in particular is not restrict | limited.

(A) Epoxy resin If the epoxy resin used in this invention is generally used for the epoxy resin molding material for sealing, there will be no restriction | limiting in particular. Of these, one containing two or more epoxy groups in one molecule is preferable. Specifically, phenol novolac type epoxy resins, ortho cresol novolak type epoxy resins, phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and α-naphthol, β-naphthol, dihydroxynaphthalene, etc. Epoxidation of a novolak resin obtained by condensation or cocondensation of at least one phenolic compound selected from the group consisting of naphthol compounds and compounds having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst A novolak epoxy resin obtained by condensation or cocondensation of the above-described phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane type epoxy resin obtained by epoxidizing rephenylmethane type phenol resin; epoxy resin which is diglycidyl ether such as alkyl-substituted, aromatic ring-substituted or unsubstituted bisphenol A, bisphenol F, bisphenol S, biphenol, thiodiphenol 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; glycidyl obtained by reaction of polyamine such as diaminodiphenylmethane and isocyanuric acid and epichlorohydrin Amine-type epoxy resin; dicyclopentadiene-type epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and phenols; naphthalene-type epoxy resin having a naphthalene ring Xylene resin: Phenol aralkyl resin synthesized from at least one of phenolic compound and naphthol compound and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, phenol aralkyl type epoxy resin obtained by epoxidizing naphthol aralkyl resin, naphthol aralkyl Aralkyl epoxy resins such as epoxy resins; Trimethylolpropane epoxy resins; Terpene-modified epoxy resins; Linear aliphatic epoxy resins obtained by oxidizing olefinic bonds with peracids such as peracetic acid; Alicyclic epoxy resins, etc. Is mentioned. These may be used alone or in combination of two or more.

Among these, the epoxy resin is a biphenyl type epoxy resin that is diglycidyl ether of alkyl-substituted, aromatic-ring-substituted or unsubstituted biphenol (for example, trade name: YX- manufactured by Mitsubishi Chemical Corporation) from the viewpoint of compatibility between fluidity and curability. 4000, YL-6121H). Further, from the viewpoint of curability, it is preferable to contain a novolac type epoxy resin (for example, trade name: ESCN-190 manufactured by Sumitomo Chemical Co., Ltd.). Moreover, it is preferable to contain the dicyclopentadiene type epoxy resin (for example, brand name: HP-7200 by DIC Corporation) from a low hygroscopic viewpoint. Moreover, it is preferable to contain the naphthalene type epoxy resin (For example, Nippon Kayaku Co., Ltd. brand name: NC-7300) from a heat resistant and low curvature viewpoint. Further, from the viewpoint of compatibility between fluidity and flame retardancy, bisphenol F type epoxy resin which is diglycidyl ether of alkyl-substituted, aromatic-ring-substituted or unsubstituted bisphenol F (for example, trade name YSLV- manufactured by Nippon Steel Chemical Co., Ltd.) 80XY) is preferably contained. In addition, from the viewpoint of compatibility between fluidity and reflow resistance, a thiodiphenol-type epoxy resin which is a diglycidyl ether of alkyl-substituted, aromatic ring-substituted or unsubstituted thiodiphenol (for example, trade name manufactured by Nippon Steel Chemical Co., Ltd.) : YSLV-120TE). From the viewpoint of both curability and flame retardancy, phenol / aralkyl resin synthesized from alkyl-substituted, aromatic-ring-substituted or unsubstituted phenol compounds and dimethoxyparaxylene or bis (methoxymethyl) biphenyl is epoxidized. It preferably contains an aralkyl type epoxy resin (for example, trade names NC-2000L, NC-3000S, CER-3000L manufactured by Nippon Kayaku Co., Ltd.). From the viewpoint of both storage stability and flame retardancy, a naphthol / aralkyl type epoxy resin obtained by epoxidizing a naphthol / aralkyl resin synthesized from an alkyl-substituted, aromatic ring-substituted or unsubstituted naphthol compound and dimethoxyparaxylene (for example, And Nippon Steel Chemical Co., Ltd. trade names ESN-375 and ESN-175). Further, from the viewpoint of improving curability and Tg, a triphenylmethane type epoxy resin synthesized from phenol and salicylaldehyde (for example, trade name: EPPN-502H manufactured by Nippon Kayaku Co., Ltd.) is preferable.
In addition to the above, from the viewpoint of low warpage, dihydroanthracene type epoxy resin (for example, trade name: YX-8800 manufactured by Mitsubishi Chemical Corporation) which is diglycidyl ether of alkyl-substituted, aromatic-ring-substituted or unsubstituted anthracene is preferable. From the viewpoint of the balance between reflow resistance, curability and fluidity, a methoxynaphthalene type epoxy resin (such as DIC Corporation trade name HP-5000) is preferable.
These suitably used epoxy resins may be referred to as specific epoxy resins.

  When the sealing epoxy resin molding material contains the specific epoxy resin, the content of the specific epoxy resin is preferably 20% by mass or more based on the total amount of the epoxy resin in order to exert its performance, and 30% by mass. % Or more is more preferable, and 50 mass% or more is still more preferable.

  The epoxy equivalent of the epoxy resin is not particularly limited. Among these, from the viewpoint of balance of various properties such as moldability, reflow resistance and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.

  The softening point or melting point of the epoxy resin is not particularly limited. Among them, from the viewpoint of moldability and reflow resistance, the softening point or melting point is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability when producing an epoxy resin molding material for sealing, it is 50 ° C. to 130 ° C. It is more preferable.

  From the viewpoint of moldability and reflow resistance, the content of the epoxy resin in the sealing epoxy resin molding material is preferably 3.5% by mass to 12.5% by mass, and 5.0% by mass to 9%. More preferably, it is 5 mass%.

(B) Curing agent The epoxy resin molding material for sealing contains at least one curing agent. If the said hardening | curing agent is generally used for the epoxy resin molding material for sealing, there will be no restriction | limiting in particular. For example, selected from the group consisting of phenol compounds such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, thiodiphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene. A novolak-type phenol resin obtained by condensing or co-condensing at least one phenolic compound with formaldehyde or acetaldehyde under an acidic catalyst; an acidic catalyst comprising a phenol compound and an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde Triphenylmethane type phenolic resin obtained by condensation or cocondensation under pressure; at least one selected from the group consisting of phenols and naphthols, and dimethoxyparaxylene Or phenol / aralkyl resins synthesized from bis (methoxymethyl) biphenyl; aralkyl-type phenol resins such as naphthol / aralkyl resins; copolymer type in which a phenol novolac structure and a phenol / aralkyl structure are randomly, block, or alternately repeated Examples include phenol-aralkyl resins; paraxylylene-modified phenol resins; metaxylylene-modified phenol resins; melamine-modified phenol resins; terpene-modified phenol resins; dicyclopentadiene-modified phenol resins; cyclopentadiene-modified phenol resins; These may be used alone or in combination of two or more.

  Among them, from the viewpoint of fluidity, flame retardancy, and reflow resistance, phenol aralkyl resins (for example, trade name MEH-7785 manufactured by Meiwa Kasei Co., Ltd., trade name: XLC manufactured by Mitsui Chemicals, Inc.) and naphthol aralkyl resin ( For example, at least one selected from the group consisting of Nippon Steel Chemical Co., Ltd. trade names SN-475 and SN-170) is preferable. Further, from the viewpoint of low hygroscopicity, dicyclopentadiene-modified phenolic resin (for example, trade name: DPP manufactured by Shin Nippon Petrochemical Co., Ltd.) is preferable. Further, from the viewpoint of curability, a novolak type phenol resin (for example, trade name: H-4 manufactured by Meiwa Kasei Co., Ltd.) is preferable. The curing agent preferably contains at least one of these phenol resins.

  The curing agent is at least one phenol resin selected from the group consisting of phenol-aralkyl resins, naphthol-aralkyl resins, dicyclopentadiene-modified phenol resins, and novolac-type phenol resins (hereinafter also referred to as “specific phenol resins”). It is preferable to contain.

Among the curing agents contained in the sealing epoxy resin molding material, the phenol / aralkyl resin and the naphthol / aralkyl resin are partially mixed with a polymerizable monomer such as acenaphthylene from the viewpoint of flame retardancy. Preferably it is. Although acenaphthylene can be obtained by dehydrogenating acenaphthene, a commercially available product may be used. Moreover, it can also be used as a polymer of acenaphthylene or a polymer of acenaphthylene and other aromatic olefins instead of acenaphthylene. Examples of a method for obtaining a polymer of acenaphthylene or a polymer of acenaphthylene and another aromatic olefin include radical polymerization, cationic polymerization, and anionic polymerization. In the polymerization, a conventionally known catalyst can be used, but it can also be carried out only by heat without using a catalyst. In this case, the polymerization temperature is preferably 80 ° C to 160 ° C, and more preferably 90 ° C to 150 ° C. The softening point of the resulting polymer of acenaphthylene or the polymer of acenaphthylene and another aromatic olefin is preferably 60 ° C to 150 ° C, more preferably 70 ° C to 130 ° C.
When the polymer has a softening point of 60 ° C. or higher, seepage during molding tends to be suppressed and moldability tends to be improved. Moreover, it exists in the tendency for compatibility with an epoxy resin and a hardening | curing agent to improve that it is 150 degrees C or less.

Examples of other aromatic olefins copolymerized with acenaphthylene include styrene, α-methylstyrene, indene, benzothiophene, benzofuran, vinylnaphthalene, vinylbiphenyl, and alkyl-substituted products thereof. In addition to the above-mentioned aromatic olefins, aliphatic olefins can be used in combination as long as the effects of the present invention are not hindered. Examples of the aliphatic olefin include (meth) acrylic acid and esters thereof, maleic anhydride, itaconic anhydride, fumaric acid, esters thereof and the like.
The amount of these aliphatic olefins to be used is preferably 20% by mass or less, more preferably 9% by mass or less, based on the total amount of the polymerization monomer used for the preliminary mixing with the phenol / aralkyl resin and naphthol / aralkyl resin.

As a method of premixing part or all of the curing agent with acenaphthylene, the curing agent and acenaphthylene are finely pulverized and mixed in a solid state with a mixer or the like, or both components are uniformly dissolved in a solvent that dissolves them. After that, the method can be performed by a method of removing the solvent, a method of melt-mixing both at a temperature equal to or higher than the softening point of at least one of the curing agent and acenaphthylene. Among them, the melt mixing method is preferable because a uniform mixture is obtained and impurities are less mixed.
The premix (acenaphthylene-modified curing agent) is produced by the above method. The melt mixing is not particularly limited as long as the temperature is at least the softening point of at least one of the curing agent and acenaphthylene. 100 degreeC-250 degreeC is preferable, and 120 degreeC-200 degreeC is more preferable. Further, in the melt mixing, there is no limitation on the mixing time as long as both are mixed uniformly. Among these, 1 hour to 20 hours are preferable, and 2 hours to 15 hours are more preferable. When the curing agent and acenaphthylene are premixed, the acenaphthylene may polymerize or react with the curing agent during mixing.

  When the sealing epoxy resin molding material contains a specific phenol resin selected from the group consisting of the phenol-aralkyl resin, naphthol-aralkyl resin, dicyclopentadiene-modified phenol resin, and novolak-type phenol resin exemplified above. The content of the specific phenol resin is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent, from the viewpoint of more effectively exhibiting the performance.

  Any one of the specific phenol resins may be used alone, or two or more of them may be used in combination. When two or more of the specific phenol resins are used in combination, the content is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more in the total amount of the curing agent. .

The hydroxyl equivalent of the curing agent is not particularly limited. Among these, from the viewpoint of balance of various properties such as formability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.
The softening point or melting point of the curing agent is not particularly limited. Among these, from the viewpoint of moldability and reflow resistance, the softening point or melting point is preferably 40 ° C to 180 ° C, and from the viewpoint of handleability during the production of an epoxy resin molding material for sealing, it is 50 ° C to 130 ° C. It is more preferable.

  In the sealing epoxy resin molding material, the equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the ratio of the number of hydroxyl groups in the curing agent to the epoxy group (number of hydroxyl groups in curing agent / in epoxy resin) The number of epoxy groups is not particularly limited. In order to suppress each unreacted component to be small, it is preferably set in the range of 0.5 to 2.0, more preferably 0.6 to 1.3. Furthermore, in order to obtain the epoxy resin molding material for sealing which is excellent in moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

(E) Curing accelerator It is preferable that the epoxy resin molding material for sealing contains at least one curing accelerator. The curing accelerator is not particularly limited as long as it is generally used in an epoxy resin molding material for sealing. For example, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 5,6-dibutylamino-1,8-diazabicyclo [5.4.0] cycloamidine compounds such as undec-7-ene; these cycloamidine compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3 Quinone compounds such as dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, Compounds having intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane and phenol resin; benzyldimethylamine, triethano Tertiary amine compounds such as ruamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivatives of these tertiary amine compounds, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, Imidazole compounds such as 2-heptadecylimidazole; derivatives of these imidazole compounds; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine; Phosphorus compound having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, quinone compound, diazophenylmethane, phenol resin, etc. to an organic phosphine compound; Tetra-substituted phosphonium tetra-borate such as phenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium ethyl triphenyl borate, tetrabutyl phosphonium tetrabutyl borate; 2-ethyl-4-methylimidazole tetraphenyl borate, N-methylmorpholine tetraphenyl Examples thereof include tetraphenylboron salts such as borates; derivatives of these tetrasubstituted phosphonium / tetrasubstituted borates and tetraphenylboron salts. These may be used alone or in combination of two or more.

  Among these, the curing accelerator is preferably an adduct of a tertiary phosphine and a quinone compound, more preferably an adduct of triphenylphosphine and benzoquinone or an adduct of tributylphosphine and benzoquinone, from the viewpoints of curability and fluidity. . From the viewpoint of storage stability, an adduct of a cycloamidine compound and a phenol resin is preferable, and a novolak-type phenol resin salt of diazabicycloundecene is more preferable (hereinafter also referred to as “specific curing accelerator”).

  The content of these specific curing accelerators is preferably 60% by mass or more and more preferably 80% by mass or more in the total amount of the curing accelerator.

  There is no restriction | limiting in particular as a tertiary phosphine used for the said adduct of a tertiary phosphine and a quinone compound. For example, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, tris ( 4-butylphenyl) phosphine, tris (isopropylphenyl) phosphine, tris (tert-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2,6-dimethylphenyl) phosphine, tris (2,4 , 6-trimethylphenyl) phosphine, tris (2,6-dimethyl-4-ethoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phos Tertiary phosphine having an aryl group such as fins and the like. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferable.

  Moreover, there is no restriction | limiting in particular as a quinone compound used for the adduct of a tertiary phosphine and a quinone compound. For example, o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone and the like can be mentioned. From the viewpoint of moisture resistance and storage stability, p-benzoquinone is preferred.

The content of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved. When the epoxy resin molding material for sealing contains a curing accelerator, the total content of the curing accelerator is 0.1 mass with respect to 100 mass parts of the total amount of (A) epoxy resin and (B) curing agent. Part to 10 parts by weight is preferable, and 0.3 part to 5 parts by weight is more preferable. When it is 0.1 part by mass or more, it can be cured in a shorter time. Moreover, when it is 10 mass parts or less, it will be suppressed that a cure rate becomes quick too much, and there exists a tendency for a better molded article to be obtained.

(F) Inorganic filler It is preferable that the said epoxy resin molding material for sealing contains at least 1 sort (s) of an inorganic filler. By including the inorganic filler, hygroscopicity reduction, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement are more effectively achieved. The inorganic filler is not particularly limited as long as it is generally used for an epoxy resin molding material for sealing. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, Examples thereof include powders such as titania, beads formed by spheroidizing these, and glass fibers. These may be used alone or in combination of two or more. Among these, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient. Alumina is preferred from the viewpoint of high thermal conductivity. Furthermore, the shape of the inorganic filler is preferably a spherical shape from the viewpoint of fluidity during molding and mold wear suppression.
As the inorganic filler, spherical fused silica is particularly preferable from the viewpoint of a balance between cost and performance.

The average particle diameter of the inorganic filler is not particularly limited. Among these, from the viewpoint of moldability, the thickness is preferably 5 μm to 50 μm, and more preferably 10 μm to 30 μm. In addition, the average particle diameter of an inorganic filler is measured as a volume average particle diameter using a laser diffraction scattering system particle size distribution measuring apparatus.
The specific surface area of the inorganic filler is not particularly limited. Among them from the viewpoints of moldability and ^strength, is preferably 0.5m ² / g~12m 2 / ^g, and more preferably 1m ² / g~5m 2 / g. The specific surface area of the inorganic filler is measured from the nitrogen adsorption ability at 77K according to JIS Z 8830.

  The content of the inorganic filler is not particularly limited as long as the present invention is achieved. Above all, from the viewpoint of flame retardancy improvement, moldability improvement, moisture absorption reduction, linear expansion coefficient reduction and strength improvement, the total content of the inorganic filler when the epoxy resin molding material for sealing contains an inorganic filler, 70 mass%-95 mass% is preferable in the epoxy resin molding material for sealing, and 85 mass%-95 mass% is more preferable from a viewpoint of a hygroscopic reduction and a linear expansion coefficient reduction. There exists a tendency for a flame retardance and reflow resistance to improve that the content rate of an inorganic filler is 70 mass% or more. Moreover, there exists a tendency which is excellent in fluidity | liquidity in it being 95 mass% or less.

(G) Other additives (third silane compound)
The sealing epoxy resin molding material may contain the (C) silane compound and (D) the second silane from the viewpoint of improving the adhesion between the resin component in the molding material and the inorganic filler. A third silane compound other than the compound may be included. Examples of the third silane compound include various silane compounds such as mercaptosilane, aminosilane, alkylsilane, ureidosilane, and vinylsilane. The third silane compound excludes (C) the first silane compound and (D) the silane compound overlapping the second silane compound.

  Examples of the third silane compound include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxy Silane compounds having an unsaturated bond such as propyltriethoxysilane and vinyltriacetoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysila , Bis (triethoxysilylpropyl) tetrasulfide-containing silane compounds; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxy Amino group-containing silane compounds such as silane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine; isocyanates such as isocyanatepropyltrimethoxysilane and isocyanatepropyltriethoxysilane Group-containing silane compounds: methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethyl Xysilane, diphenyldiethoxysilane, diphenylsilanediol, triphenylmethoxysilane, triphenylethoxysilane, triphenylsilanol, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, N-β- (N-vinylbenzylamino) Ethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, 2-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl-N -(1,3-dimethyl-butylidene) propylamine, N- (3-triethoxysilylpropyl) phenylimine, 3- (3- (triethoxysilyl) propylamino) -N, N-dimethyl Silane compounds such as lopionamide, N-triethoxysilylpropyl-β-alanine methyl ester, 3- (triethoxysilylpropyl) dihydro-3,5-furandione, bis (trimethoxysilyl) benzene; 1H-imidazole, Imidazole compounds such as 2-alkylimidazole, 2,4-dialkylimidazole and 4-vinylimidazole, and γ-glycidoxypropylalkoxysilane such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane An imidazole-based silane compound that is a reaction product of One of these may be used alone, or two or more may be used in combination.

  When the sealing epoxy resin molding material contains a third silane compound, from the viewpoint of moldability and adhesiveness, the total content of the third silane compound relative to the total amount of (A) epoxy resin is 0.06 mass. % To 2% by mass is preferable, 0.1% to 0.75% by mass is more preferable, and 0.2% to 0.7% by mass is still more preferable. There exists a tendency for adhesiveness to improve more as the total content rate of a 3rd silane compound is 0.06 mass% or more. Moreover, there exists a tendency which can suppress generation | occurrence | production of shaping | molding defects, such as a void, as the total content rate of a 3rd silane compound is 2 mass% or less.

(Coupling agents other than silane compounds)
The sealing epoxy resin molding material may contain a conventionally known coupling agent other than the silane compound from the viewpoint of improving the adhesion between the resin component and the inorganic component in the molding material. Examples of the coupling agent include titanate coupling agents, aluminum chelates, and aluminum / zirconium compounds. These may be used alone or in combination of two or more.

  Moreover, when the said epoxy resin molding material for sealing contains coupling agents other than a silane compound, the total content rate is 0.00 with respect to the total amount of (A) epoxy resin from a viewpoint of a moldability and adhesiveness. 06 mass%-2 mass% are preferable, 0.1 mass%-0.75 mass% are more preferable, 0.2 mass%-0.7 mass% are still more preferable. There exists a tendency for adhesiveness to improve more that the total content rate of coupling agents other than a silane compound is 0.06 mass% or more. Moreover, there exists a tendency which can suppress generation | occurrence | production of shaping | molding defects, such as a void, as the total content rate of coupling agents other than a silane compound is 2 mass% or less.

(Anion exchanger)
The sealing epoxy resin molding material may contain an anion exchanger as required. By including an anion exchanger, it is possible to improve the moisture resistance and high-temperature storage characteristics of the sealed element. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. Examples thereof include hydrotalcites and hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium and bismuth. These may be used alone or in combination of two or more. Among these, hydrotalcite represented by the following composition formula (V) is preferable.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (V)
In the formula (V), 0 <X ≦ 0.5, and m represents a positive number.

  When the sealing epoxy resin molding material contains an anion exchanger, the content of the anion exchanger is not particularly limited as long as it is a sufficient amount for capturing anions such as halogen ions. Especially, 0.1 mass part-30 mass parts are preferable, and, as for the content rate of the anion exchanger with respect to 100 mass parts of (A) epoxy resins, 1 mass part-5 mass parts are more preferable.

(Adhesion promoter)
The epoxy resin molding material for sealing of the present invention may contain an adhesion promoter as necessary. Adhesion can be further improved by including an adhesion promoter. Adhesion promoters include derivatives such as imidazole, triazole, tetrazole, triazine, anthranilic acid, gallic acid, malonic acid, malic acid, maleic acid, aminophenol, quinoline, etc. and their derivatives, aliphatic acid amide compounds, dithiocarbamic acid Examples thereof include salts and thiadiazole derivatives. These may be used alone or in combination of two or more.

(Release agent)
The sealing epoxy resin molding material may contain a release agent as necessary. Examples of the mold release agent include oxidized or non-oxidized polyolefin. Specific examples of the oxidized or non-oxidized polyolefin include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000, such as trade name H4, PE, and PED series manufactured by Hoechst Co., Ltd.

  The oxidized or non-oxidized polyolefin as the release agent is preferably contained in an amount of 0.01 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the (A) epoxy resin. It is more preferable. There exists a tendency for favorable mold release property to be acquired as it is 0.01 mass part or more. Moreover, there exists a tendency for adhesiveness to improve that it is 10 mass parts or less.

  Examples of other mold release agents other than oxidized or non-oxidized polyolefin include carnauba wax, montanic acid ester, montanic acid, and stearic acid. These may be used alone or in combination of two or more. When other release agents are used in addition to the oxidized or non-oxidized polyolefin, the total amount of the release agent is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (A), 0.5 mass part-3 mass parts are more preferable.

(Flame retardants)
The epoxy resin molding material for sealing can contain a conventionally known flame retardant as necessary. By including a flame retardant, the flame retardancy of the molding material is improved. Flame retardants include brominated epoxy resins; inorganic substances such as antimony trioxide, red phosphorus, aluminum hydroxide, magnesium hydroxide, and zinc oxide; red phosphorus and phosphate esters coated with thermosetting resins such as phenolic resins Phosphorus compounds such as melamine, melamine derivatives, melamine-modified phenol resins, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives; phosphorus and nitrogen-containing compounds such as cyclophosphazene; aluminum hydroxide, hydroxylation Compounds containing metal elements such as magnesium, zinc oxide, zinc stannate, zinc borate, iron oxide, molybdenum oxide, zinc molybdate, dicyclopentadienyl iron, and composite metal hydroxide represented by the following composition formula (VI) Etc.

^{_{p (M 1 a O b)}} · q (M 2 c O d) · m (H 2 O) (VI)
In formula (VI), M ¹ and M ² represent different metal elements, and a, b, c, d, p, q and m each independently represent a positive number.

M ¹ and M ² in the composition formula (VI) are not particularly limited as long as they are different metal elements. From the viewpoint of flame retardancy, M ¹ is selected from metal elements belonging to the third period metal element, group IIA alkaline earth metal element, group IVB, group IIB, group VIII, group IB, group IIIA and group IVA M ² is preferably selected from Group IIIB to IIB transition metal elements, M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, and M ² is iron. More preferably, it is selected from cobalt, nickel, copper and zinc.

From the viewpoint of fluidity, it is preferable that M ¹ is magnesium and M ² is zinc or nickel. The molar ratio of p and q is not particularly limited. It is preferable that p / q is 1/99 to 1/1. A, b, c and d are appropriately selected according to M ¹ and M ² . The metal element is classified into a long-period periodic table in which the typical element is the A group and the transition element is the B group (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987). (Reduced plate 30th printing).

  These flame retardants may be used alone or in combination of two or more. When the sealing epoxy resin molding material contains a flame retardant, the content of the flame retardant is not particularly limited. Among them, the content of the flame retardant with respect to 100 parts by mass of (A) epoxy resin is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 15 parts by mass.

(Colorants etc.)
The sealing epoxy resin molding material may contain a colorant such as carbon black, organic dye, organic pigment, titanium oxide, red lead, bengara and the like. Further, as other additives, polyphenylene ether, thermoplastic resins such as indene oligomers which are copolymer resins of indenes such as indene and alkylindene and styrenes and phenols such as styrene and alkylstyrene, silicone oil And a stress relaxation agent such as silicone rubber powder can be included as necessary.

<Method for preparing epoxy resin molding material for sealing>
The method for preparing the sealing epoxy resin molding material of the present invention is not particularly limited, and any method may be used as long as various components constituting the sealing epoxy resin molding material can be uniformly dispersed and mixed. As a general method, there can be mentioned a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, and then cooled and pulverized. Specifically, a predetermined amount of the above-mentioned components are uniformly stirred and mixed, and obtained by a method such as kneading, cooling, and pulverizing with a kneader, roll, extruder, or the like that has been heated to 70 ° C. to 140 ° C. in advance. be able to. Moreover, it is easy to use if the epoxy resin molding material for sealing is made into a tablet with a size and mass suitable for molding conditions.

<Electronic component device>
The electronic component device according to the present invention includes an element sealed with the sealing epoxy resin molding material, and includes other components as necessary.
As an electronic component device having an element sealed with the sealing epoxy resin molding material, a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, etc., a support member such as a semiconductor chip, transistor, diode An electronic component device in which an active element such as a thyristor, an element such as a passive element such as a capacitor, a resistor, or a coil is mounted and a necessary portion is sealed with the above-described epoxy resin molding material for sealing. Specifically, as such an electronic component device, 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 sealing epoxy resin DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead) package), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package) and other general resin-encapsulated ICs, and semiconductor chips connected to the tape carrier by bumps are sealed with the above-mentioned encapsulating epoxy resin molding material Stopping TCP (Tape Carrier Package), wiring on wiring boards and glass, wire bonding, flip chip bonding, soldering COB (Chip On Board) formed by sealing active elements such as semiconductor chips, transistors, diodes, and thyristors and / or passive elements such as capacitors, resistors, and coils connected with the above-mentioned epoxy resin molding material for sealing. ) After mounting the device on the surface of the module, hybrid IC, multi-chip module, organic substrate on which the wiring board connection terminal is formed on the back surface, connecting the device 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) formed by sealing an element with the sealing epoxy resin molding material. Moreover, the epoxy resin molding material for sealing can also be used effectively for a printed circuit board.

  As a method for sealing an element using the sealing epoxy resin molding material, 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. The conditions for sealing the element can be appropriately selected according to the configuration of the sealing epoxy resin molding material.

  EXAMPLES Next, although an Example demonstrates this invention concretely, the scope of the present invention is not limited to these Examples. Unless otherwise specified, “part” and “%” are based on mass.

[Preparation of epoxy resin molding material for sealing]
(Examples 1-13, Comparative Examples 1-7)
The following components are blended in parts by mass shown in Tables 1 to 3 below, and roll kneading is performed under conditions of a kneading temperature of 80 ° C. and a kneading time of 10 minutes. Each epoxy resin molding material was prepared. In addition, the blank in a table | surface represents an unblended.

(A) The following was used as an epoxy resin.
Epoxy resin 1: epoxy equivalent 241 with a softening point of 96 ° C. Biphenylene skeleton-containing phenol aralkyl type epoxy resin (trade name CER-3000L, manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 2: Epoxy resin having an epoxy equivalent of 251 and a softening point of 60 degrees (trade name HP-5000, manufactured by DIC Corporation)

(B) As the curing agent, the following was used.
Curing agent 1: phenol aralkyl resin having a hydroxyl group equivalent of 176 and a softening point of 70 ° C. (trade name: Millex XLC, manufactured by Mitsui Chemicals, Inc.)
Curing agent 2: novolak type phenol resin having a hydroxyl group equivalent of 106 and a softening point of 64 ° C. (trade name H-4, manufactured by Meiwa Kasei Co., Ltd.)

(C) The following was used as the first silane compound.
First silane compound-1: n-propyltrimethoxysilane First silane compound-2: isobutyltrimethoxysilane First silane compound-3: diisobutyldimethoxysilane First silane compound-4: isobutyl Isopropyldimethoxysilane / first silane compound-5: diisopropyldimethoxysilane

(D) The following was used as the second silane compound.
Second silane compound-1: γ-glycidoxypropyltrimethoxysilane Second silane compound-2: γ-anilinopropyltrimethoxysilane

The following were used as silane compounds other than the first and second silane compounds.
Silane compounds other than the first and second-1: methyltrimethoxysilane. Silane compounds other than the first and second. Dimethoxydimethylsilane. Silane compounds other than the first and second. -3: Hexyltrimethoxysilane.

(E) As the curing accelerator, a betaine-type adduct of triphenylphosphine and p-benzoquinone was used.
(F)) As the inorganic filler, spherical fused silica having an average particle diameter of 17.5 μm and a specific surface area of 3.8 m ² / g was used.

  As other additive components, carnauba wax (manufactured by Clariant Japan Co., Ltd.) and carbon black (manufactured by Mitsubishi Chemical Corporation) were used.

[Evaluation of epoxy resin molding material for sealing]
The properties of the sealing epoxy resin molding materials prepared in Examples 1 to 13 and Comparative Examples 1 to 7 were evaluated by the following property tests (1) to (6). The evaluation results are shown in Tables 1 to 3 below. 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 unless otherwise specified. Further, post-curing was performed at 180 ° C. for 5 hours.

(1) Spiral flow Using a spiral flow measurement mold in accordance with EMMI-1-66, the sealing epoxy molding material was molded under the above conditions, and the flow distance (cm) was determined.

(2) Hardness under heat The epoxy resin molding material for sealing is molded into a disc having a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, a Shore D hardness meter (HD-1120 (type D )).

(3) 260 ° C. shear adhesive strength Under the above conditions, the epoxy resin molding material for sealing was molded into a silver-plated copper plate with a bottom diameter of 4 mm, a top diameter of 3 mm, and a height of 4 mm, post-cured, and Daisy Japan Co., Ltd. Using a series 4000 manufactured by the company, the shear adhesive strength (MPa) was determined at a shear rate of 50 μm / s while maintaining the temperature of the copper plate at 260 ° C.

(4) Water absorption rate The disk molded in the above (2) is post-cured under the above conditions, left for 168 hours under the conditions of 85 ° C. and 60% RH, and the mass change before and after being left is measured. (Mass%) = (disc weight after being left−disc weight before being left) / disc weight before being left × 100.

(5) Reflow resistance 80 mm flat package (QFP) with external dimensions of 20 mm x 14 mm x 2 mm mounted with 8 mm x 10 mm x 0.4 mm silicon chip (lead frame material: copper alloy, die pad top surface and lead tip silver plating Processed product) was molded under the above conditions using an epoxy resin molding material for sealing and post-cured.
The obtained package is humidified for 168 hours under the conditions of 85 ° C. and 85% RH, and then subjected to a reflow treatment at a predetermined temperature (245 ° C., 255 ° C., 265 ° C.) for 10 seconds to check for cracks outside the package. The number of packages in which either cracks or peeling occurred with respect to the number of test packages of 10 were observed with an ultrasonic flaw detector (HYE-FOCUS manufactured by Hitachi Construction Machinery Co., Ltd.). The total was evaluated.

(6) Flame retardancy Using a mold that molds a 1/16 inch (about 1.6 mm) thick test piece, the epoxy resin molding material for sealing is molded under the above conditions and post-cured. did. The obtained test piece was evaluated for flame retardancy according to the UL-94 test method.

  From Tables 1 to 3, Comparative Examples 1 to 7 using (C) the first silane compound and (C) a silane compound different from the first silane compound are inferior in fluidity and reflow resistance.

On the other hand, when the Example and comparative example which are the same resin compositions except having mix | blended (C) 1st silane compound are compared with a comparative example, it turns out that fluidity | liquidity is favorable in an Example. In particular, in Examples 2 to 13 in which (C) the second silane compound is used in addition to (C) the first silane compound, it can be seen that the reflow resistance is superior.
Moreover, it turns out that the fluidity | liquidity has improved more in the Example using the 1st silane compound-2, 3, 4, 5 which has a C3-C5 branched chain hydrocarbon group.

Claims (5)

(A) An epoxy resin, (B) a curing agent, a silane compound represented by the following (C) general formula (I), and (F) an inorganic filler, and the content of the inorganic filler is 70 wt% to 95% by mass is, the (a) wherein the total amount of the epoxy resin (C) the total content of the first silane compound is 1.0 wt% to 7.5 wt%, further (D) An epoxy resin molding material for sealing containing at least one second silane compound selected from a compound represented by the general formula (III) and an arylamino group-containing alkoxysilane compound .

(In general formula (I), R ¹ and R ² each independently represent a hydrocarbon group having 2 to 5 carbon atoms, R ³ represents a hydrocarbon group having 1 or 2 carbon atoms, and p represents 2 Show.)

(In general formula (III), R ²¹ and R ²² each independently represent a hydrocarbon group having 1 to 6 carbon atoms. P2 represents an integer of 1 to 3, and q2 represents 2 or 3.) The silane compound represented by (C) the general formula (I), wherein R ¹ and R ² are each independently a linear or branched hydrocarbon group having 2 to 5 carbon atoms. The epoxy resin molding material for sealing as described. The silane compound represented by (C) the general formula (I), wherein R ¹ and R ² are each independently a branched hydrocarbon group having 3 to 5 carbon atoms. The epoxy resin molding material for sealing as described. The epoxy resin molding material for sealing according to any one of claims 1 to 3, wherein the arylamino group-containing alkoxysilane compound is at least one compound represented by the following general formula (IV).

(In General Formula (IV), R ³¹ and R ³² each independently represent a hydrocarbon group having 1 to 6 carbon atoms. P3 represents an integer of 1 to 3, and q3 represents 2 or 3). An electronic component apparatus provided with the element sealed with the epoxy resin molding material for sealing of any one of Claims 1-4 .