JP6384555B2 - Solid sealing resin composition for compression molding and semiconductor device - Google Patents

Description

    The present invention relates to a solid sealing resin composition for compression molding and a semiconductor device.

  Conventionally, in the field of element sealing of electronic component devices such as transistors and ICs, resin sealing has been the mainstream in terms of productivity and cost, and epoxy resin molding materials have been widely used. This is because the epoxy resin is balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts. In recent years, high-density mounting of electronic components on printed wiring boards has been progressing. As a result, surface mount packages have become mainstream from conventional pin insertion packages.

  Surface-mount ICs, LSIs, etc. are thin and small packages in order to increase the mounting density and reduce the mounting height, and the volume occupied by the device package increases, resulting in a very thick package. It has become thinner. In addition, due to the increased functionality and capacity of the elements, the chip area is increased and the number of pins is increased, and further, the pad pitch is reduced and the pad size is reduced by increasing the number of pads (electrodes), so-called narrow pad pitch. Progress is also being made. In addition, in order to cope with further reduction in size and weight, CSP (Quad Flat Package), SOP (Small Outline Package), and other forms of packages are easy to cope with higher pin count and CSP capable of higher density mounting. (Chip Size Package) and BGA (Ball Grid Array). In recent years, these packages have been developed with new structures such as a face-down type, a stacked (stacked) type, a flip chip type, and a wafer level type in order to realize high speed and multiple functions. Since the wafer level type has almost the same package size and chip size, it has succeeded in reducing the size of the package.

  On the other hand, since the area where the bumps can be mounted is limited to the area of the chip, it is difficult to further integrate the package. In recent years, a package called FO-WLP (Fan Out Wafer Level Package) has been proposed as a new package (see FIG. 1). In this package manufacturing method, a technique is employed in which a chip is temporarily fixed on a carrier using a temporary fixing tape, and the upper portion thereof is sealed by compression molding. The reason why compression molding is adopted for the production of FO-WLP is that FO-WLP requires large-scale batch sealing and is difficult to fill by transfer molding, which is a general resin sealing method.

Therefore, in order to produce such a semiconductor device, it is customary to use compression molding with a low resin flow rate. In the package obtained by these, the sealing material layer and the rewiring layer exist also in the peripheral region other than directly under the chip where the conventional WL-CSP could not mount the bump, so that there is a region where the bump can be mounted. Expanded and succeeded in further high integration (see Fig. 2).
However, since the heat resistance of the temporary fixing tape used at this time is low, molding at 175 ° C., which is a general sealing temperature, cannot be performed, and molding at a low temperature of 130 ° C. or less is required.

  In order to solve this problem, molding with a liquid sealing material using a latent highly active catalyst is now common (see, for example, Patent Document 1 and Non-Patent Documents 1 to 3).

WO 09/142065 pamphlet

Embedded Wafer Level Packages with Laterally Placed and Vertically Stacked Thin Dies (ECTC 2009. 1537-1545) Embedded Wafer Level Ball Grid Array (FO-WLP) (ECTC 2006.1-5) Wafer Level Embedding Technology for 3D Wafer Level Embedded Package (ECTC 2009 1289-1296)

However, the liquid sealing material currently used cannot be said to have sufficient storage stability of the sealing material itself, and due to problems such as an increase in viscosity, storage stability of about 24 h at room temperature (25 ° C.) In some cases, the storage stability of only about 6 months was stored even in a freezer at -20 ° C or lower.
On the other hand, in the case of a solid sealing material, a long sealing time may be required for molding at a low temperature from the viewpoint of catalytic activity. In the case of the sealing method for a package as described above, a sealing time of not more than 600 seconds at 130 ° C. or less is required. However, in the case of the conventional solid sealing material, the reactivity at such a low temperature is low, and it tends to become uncured, and it may be difficult to take out from the mold.
In addition, it is possible to improve the reactivity at low temperatures by using a highly active catalyst, but in that case, the reaction proceeds during storage because of high reaction activity even at room temperature (25 ° C.) or during low temperature storage. In some cases, long-term storage stability deteriorated.

Therefore, when it is used as a sealing material for FO-WLP, it has sufficient reactivity at low temperatures, while long-term storage stability as a sealing material is required.
The present invention provides a solid molding resin composition for compression molding, which has excellent reactivity even at low temperatures, has excellent long-term storage stability, and is suitable for sealing a semiconductor device for FO-WLP, and a solid sealing resin composition for compression molding. An object of the present invention is to provide a semiconductor device.

  As a result of intensive studies to solve the above-mentioned problems, the inventors have found that the above object can be achieved by selecting a specific curing accelerator, and have completed the present invention.

That is, the present invention relates to the following.
<1> A solid encapsulating resin composition for compression molding comprising (A) an epoxy resin, (B) a curing agent, and (C) an addition reaction product of a phosphine compound and a quinone compound.

<2> Measured by differential scanning calorimetry, the time required for the reaction rate of the (A) epoxy resin and (B) curing agent to reach 40% is within 400 seconds when the reaction temperature is 130 ° C., Or the solid sealing resin composition for compression molding as described in said <1> which is within 600 second in the case of the reaction temperature of 120 degreeC.

<3> The solid sealing resin composition for compression molding according to <1> or <2>, wherein the fluidity after 48 hours at 25 ° C. is 90% or more with respect to the fluidity before the passage.

<4> The addition reaction product of the (C) phosphine compound and the quinone compound is an addition reaction product of a phosphine compound represented by the following general formula (I) and a quinone compound represented by the following general formula (II). The solid sealing resin composition for compression molding according to any one of 1> to <3>.

(R ¹ , R ² and R ^{3 in} formula (I) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. In addition, R ^{4 to} R ⁶ in formula (II) are each Independently, it represents a hydrogen atom or a monovalent substituent having 1 to 18 carbon atoms, and R ⁴ and R ⁵ may be bonded to each other to form a ring.

<5> (D) The compression filler according to any one of <1> to <4>, further including an inorganic filler, the content of which is 55% by volume to 90% by volume in the total volume. Solid encapsulating resin composition.

<6> A semiconductor device having a semiconductor element sealed with the solid sealing resin composition for compression molding according to any one of <1> to <5>.

  According to the present invention, a solid encapsulating resin composition for compression molding, which has excellent reactivity even at low temperatures, has excellent long-term storage stability, and is suitable for sealing a semiconductor device for FO-WLP, and thereby It has become possible to provide a semiconductor device to be formed.

It is a schematic sectional drawing which shows a part of manufacturing process of FO-WLP. It is a schematic sectional drawing which shows an example of FO-WLP.

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. . In the present specification, numerical ranges indicated using “to” indicate ranges including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. Further, when referring to the amount of each component in the composition in the present specification, when there are a plurality of substances corresponding to each component in the composition, the plurality of the components present in the composition unless otherwise specified. It means the total amount of substance.

The solid molding resin composition for compression molding of the present invention (hereinafter also simply referred to as “resin composition”) comprises (A) an epoxy resin, (B) a curing agent, and (C) an addition of a phosphine compound and a quinone compound. And other components as necessary.
With such a configuration, it has excellent reactivity even at a low temperature, has excellent long-term storage stability, and is suitable for sealing a semiconductor device for FO-WLP.
The compression-molding solid encapsulating resin composition is solid at room temperature (25 ° C.).

The resin composition has a reaction temperature of 130 ° C., the reaction rate between the epoxy resin and the curing agent contained in the resin composition reaches 40% within 400 seconds, or the reaction temperature of 120 ° C. It is preferable that the time to reach 40% is within 600 seconds.
The reaction rate between the epoxy resin and the curing agent contained in the resin composition can be generally measured by DSC (differential scanning calorimetry) or the like. A specific measurement method will be described later.

  If the reaction rate reaches 30% within 400 seconds at a reaction temperature of 130 ° C. or 600 seconds at a reaction temperature of 120 ° C., it is sufficient in terms of releasability from the mold, but handling after resin sealing From the standpoint of sex, the reaction rate preferably reaches 40%, more preferably 50%.

In order for the reaction rate to satisfy the above-described conditions, for example, a method in which the resin composition is used as a curing accelerator and includes at least one selected from addition products of a phosphine compound and a quinone compound is exemplified. it can.
Details of the addition reaction product of the phosphine compound and the quinone compound will be described later.

(life)
From the viewpoint of long-term storage stability, the solid encapsulating resin composition for compression molding of the present invention has fluidity with respect to the fluidity of the resin composition before progress even after 48 hours at room temperature (25 ° C.). Therefore, it is preferably 90% or more, and more preferably 95% or more. More specifically, after preparing the solid sealing resin composition for compression molding, 48 hours at room temperature (25 ° C.) after measurement of the fluidity with respect to the fluidity of the resin composition measured within 24 hours. It is preferable that the fluidity ratio measured after being left to stand is 90% or more.
In addition, generally the fluidity | liquidity of a resin composition can be evaluated by a disk flow etc. Specifically, the fluidity of the resin composition can be measured based on the disc flow.

  In order for the fluidity of the resin composition to satisfy the above-mentioned conditions, for example, a method comprising a resin composition containing at least one selected from an addition reaction product of a phosphine compound and a quinone compound as a curing accelerator. Can be mentioned.

(A) Epoxy resin If the epoxy resin used in this invention is generally used for the resin composition for sealing, there will be no restriction | limiting in particular. Specifically, phenol novolac type epoxy resins, ortho cresol novolac type epoxy resins, phenol resins such as epoxy resins having a triphenylmethane skeleton, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, and the like At least one selected from the group consisting 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 or the like in an acidic catalyst A novolak-type epoxy resin obtained by epoxidizing a novolak resin obtained by cocondensation; bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or non-substituted Epoxy resins that are diglycidyl ethers such as substituted biphenols; stilbene type epoxy resins, hydroquinone type epoxy resins; glycidyl ester type epoxy resins obtained by reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; diaminodiphenylmethane; Glycidylamine type epoxy resin obtained by reaction of polyamine such as isocyanuric acid and epichlorohydrin; Epoxidation product of co-condensation resin of dicyclopentadiene and phenol; Epoxy resin having naphthalene ring; Phenol aralkyl resin, Naphthol aralkyl resin Epoxidized aralkyl type phenol resin such as trimethylolpropane type epoxy resin; terpene modified epoxy resin; linear fat obtained by oxidizing olefinic bond with peracid such as peracetic acid Epoxy resins; alicyclic epoxy resins; sulfur atom-containing epoxy resins.
These may be used alone or in combination of two or more.

Among these, from the viewpoint of filling property and reflow resistance, the epoxy resin is a biphenyl type epoxy resin which is a diglycidyl ether of alkyl-substituted or unsubstituted biphenol, a bisphenol F type epoxy resin which is a diglycidyl ether of biphenol F, and stilbene. At least one selected from the group consisting of a type epoxy resin and a sulfur atom-containing epoxy resin is preferable, and it is more preferable to include at least a bisphenol F type epoxy resin and to increase the ratio.
The epoxy resin is preferably a novolak type epoxy resin from the viewpoint of curability, a dicyclopentadiene type epoxy resin is preferable from the viewpoint of low hygroscopicity, and a naphthalene type epoxy resin from the viewpoint of heat resistance and low warpage. Triphenylmethane type epoxy resin is preferable, and it is preferable to contain at least one of these epoxy resins.

  Examples of the biphenyl type epoxy resin include an epoxy resin represented by the following general formula (III). Moreover, as a bisphenol F type epoxy resin, the epoxy resin etc. which are shown with the following general formula (IV) are mentioned. Examples of the stilbene type epoxy resin include an epoxy resin represented by the following general formula (V), and examples of the sulfur atom-containing epoxy resin include an epoxy resin represented by the following general formula (VI).

Here, R < ¹ > -R < ⁸ > shows a hydrogen atom or a C1-C10 substituted or unsubstituted monovalent hydrocarbon group each independently. n represents an integer of 0 to 3.
The monovalent hydrocarbon groups of the substituted or unsubstituted 1 to 10 carbon atoms in R ¹ to R ^8, include methyl group or the like.

Here, R < ¹ > -R < ⁸ > is respectively independently a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10 aryl group, or a C6-C10. An aralkyl group is shown. n represents an integer of 0 to 3.

Here, R ^{1 to} R ⁸ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms. n represents an integer of 0 to 10.
Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms in R ^{1 to} R ⁸ include a methyl group.

Here, R < ¹ > -R < ⁸ > shows a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, or a substituted or unsubstituted C1-C10 alkoxy group each independently. n represents an integer of 0 to 3.
The monovalent hydrocarbon groups of the substituted or unsubstituted 1 to 10 carbon atoms in R ¹ to R ^8, include methyl group or the like.

  Examples of the biphenyl type epoxy resin represented by the general formula (III) include 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3. , 3 ', 5,5'-tetramethylbiphenyl as the main component, epichlorohydrin and 4,4'-biphenol or 4,4'-(3,3 ', 5,5'-tetramethyl) biphenol An epoxy resin obtained by reacting is used. Among these, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is preferable.

Examples of the bisphenol F-type epoxy resin represented by the general formula (IV) include, for example, R ¹ , R ³ , R ⁶ and R ⁸ are methyl groups, and R ² , R ⁴ , R ⁵ and R ⁷ are hydrogen atoms. Yes, YSLV-80XY (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) having n = 0 as a main component is available as a commercial product.

  The stilbene type epoxy resin represented by the general formula (V) can be obtained by reacting a stilbene phenol as a raw material with epichlorohydrin in the presence of a basic substance. Examples of the raw material stilbene phenols include 3-t-butyl-4,4′-dihydroxy-3 ′, 5,5′-trimethylstilbene, 3-t-butyl-4,4′-dihydroxy- 3 ', 5', 6-trimethylstilbene, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl- 5,5'-dimethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, etc., among which 3-t-butyl-4,4 ' -Dihydroxy-3 ', 5,5'-trimethylstilbene and 4,4'-dihydroxy-3,3', 5,5'-tetramethylstilbene are preferred. These stilbene type phenols may be used alone or in combination of two or more.

Among the sulfur atom-containing epoxy resins represented by the above general formula (VI), R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, and R ¹ , R ⁴ , R ⁵ and R 8 are alkyl groups. A resin is preferable, and an epoxy resin in which R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are t-butyl groups, and R ⁴ and R ⁵ are methyl groups is more preferable. As such a compound, YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd.) and the like are commercially available.

  These epoxy resins may be used alone or in combination of two or more, but the content is 40 mass in total with respect to the total amount of the epoxy resin in order to exhibit its performance. % Or more, preferably 60% by mass or more, and more preferably 80% by mass or more.

  As a novolak-type epoxy resin, the epoxy resin etc. which are shown by the following general formula (VII) are mentioned, for example.

  Here, each R independently represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. n represents an integer of 0 to 10.

The novolak-type epoxy resin represented by the general formula (VII) can be easily obtained by reacting novolak-type phenol resin with epichlorohydrin. Especially, as R in general formula (VII), as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group etc., a C1-C10 alkyl group, a methoxy group, an ethoxy group C1-C10 alkoxy groups, such as a propoxy group and a butoxy group, are preferable, and a hydrogen atom or a methyl group is more preferable.
n is preferably an integer of 0 to 3.
Among the novolak type epoxy resins represented by the general formula (VII), orthocresol novolak type epoxy resins are preferable.
In the case of using a novolac type epoxy resin, the blending amount thereof is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.

  Examples of the dicyclopentadiene type epoxy resin include an epoxy resin represented by the following general formula (VIII).

Here, each R ¹ independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. R ² independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 0 to 10, and m represents an integer of 0 to 6.

R ¹ in the above formula (VIII) is, for example, a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, or a t-butyl group, a vinyl group, an allyl group, or a butenyl group. And a substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms such as an alkenyl group, a halogenated alkyl group, an amino group-substituted alkyl group, and a mercapto group-substituted alkyl group. Of these, an alkyl group such as a methyl group or an ethyl group and a hydrogen atom are preferable, and a methyl group and a hydrogen atom are more preferable.
Examples of R ² include alkyl groups such as methyl, ethyl, propyl, butyl, isopropyl, and t-butyl groups, alkenyl groups such as vinyl, allyl, and butenyl groups, halogenated alkyl groups, and amino groups. Examples thereof include substituted or unsubstituted monovalent hydrocarbon groups having 1 to 5 carbon atoms such as a group-substituted alkyl group and a mercapto group-substituted alkyl group.
m is an integer of 0 to 6, and is preferably 0.

  When a dicyclopentadiene type epoxy resin is used, its blending amount is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total amount of the epoxy resin in order to exhibit its performance.

  Examples of the naphthalene type epoxy resin include an epoxy resin represented by the following general formula (IX), and examples of the triphenylmethane type epoxy resin include an epoxy resin represented by the following general formula (X). It is done.

Here, R ^{1 to} R ³ each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms. p represents 1 or 0, and l and m are each an integer of 0 to 11, wherein (l + m) is an integer of 1 to 11 and (l + p) is an integer of 1 to 12. i represents an integer of 0 to 3, j represents an integer of 0 to 2, and k represents an integer of 0 to 4, respectively.
Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms in R ^{1 to} R ³ include a methyl group.

  The naphthalene type epoxy resin represented by the general formula (IX) includes a random copolymer containing 1 constituent unit and m constituent units at random, an alternating copolymer containing alternating units, and a copolymer containing regularly. Examples thereof include block copolymers which are included in a combined or block form, and any one of these may be used alone, or two or more may be used in combination.

Here, each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. n shows the integer of 1-10.
A methyl group etc. are mentioned as a C1-C10 substituted or unsubstituted monovalent hydrocarbon group in R.

  The naphthalene type epoxy resin and the triphenylmethane type epoxy resin may be used either alone or in combination, but the content is based on the total amount of the epoxy resin in order to exhibit its performance. In total, the content is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more.

(B) Curing agent The curing agent used in the present invention is not particularly limited as long as it is generally used in a solid molding resin composition for compression molding. Specifically, selected from the group consisting of phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc. At least one selected from the group consisting of phenols and naphthols, obtained by condensing or co-condensing a compound having an aldehyde group such as formaldehyde, benzaldehyde, and salicylaldehyde with an acidic catalyst. Phenol / aralkyl resins synthesized from seeds and dimethoxyparaxylene or bis (methoxymethyl) biphenyl; aralkyl-type phenol resins such as naphthol / aralkyl resins; phenols and naphthols Examples thereof include dichloropentadiene type phenol novolac resins synthesized by copolymerization from at least one selected from the group consisting of tolls and cyclopentadiene; dichloropentadiene type phenol resins such as naphthol novolac resins; terpene-modified phenol resins.
These may be used alone or in combination of two or more.

Among these, biphenyl type phenol resins are preferable from the viewpoint of flame retardancy. From the viewpoint of reflow resistance and curability, aralkyl type phenol resins are preferred. From the viewpoint of low hygroscopicity, a dicyclopentadiene type phenol resin is preferred. From the viewpoints of heat resistance, low expansion rate and low warpage, triphenylmethane type phenol resin is preferred. From the viewpoint of curability, a novolac type phenol resin is preferable.
More preferably, the curing agent contains at least one selected from these phenol resins.

  Examples of the biphenyl type phenol resin include a phenol resin represented by the following general formula (XI).

R ^{1 to} R ⁹ in the formula (XI) are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or other alkyl group having 1 to 10 carbon atoms, or a methoxy group. , Alkoxy groups having 1 to 10 carbon atoms such as ethoxy group, propoxy group and butoxy group, aryl groups having 6 to 10 carbon atoms such as phenyl group, tolyl group and xylyl group, or carbon numbers such as benzyl group and phenethyl group 6-10 aralkyl groups are shown. Of these, a hydrogen atom and a methyl group are preferable. n represents an integer of 0 to 10.

Examples of the biphenyl type phenol resin represented by the general formula (XI) include compounds in which R ^{1 to} R ⁹ are all hydrogen atoms, and in particular, from the viewpoint of melt viscosity, 50 is a condensate having n of 1 or more. A mixture of condensates containing at least mass% is preferred. As such a compound, MEH-7851 (trade name, manufactured by Meiwa Kasei Co., Ltd.) is commercially available.
When using a biphenyl type phenol resin, the content is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 80% by mass or more with respect to the total amount of the curing agent in order to exhibit its performance. Further preferred.

Examples of the aralkyl type phenol resin include phenol / aralkyl resin, naphthol / aralkyl resin, and the like. Among them, a phenol / aralkyl resin represented by the following general formula (XII) is preferable, and a phenol / aralkyl resin in which R in the general formula (XII) is a hydrogen atom and the average value of n is 0 to 8 is more preferable. Specific examples include p-xylylene type phenol / aralkyl resins, m-xylylene type phenol / aralkyl resins, and the like.
When using these aralkyl type phenol resins, the content is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit the performance.

Here, each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 0 to 10.
A methyl group etc. are mentioned as a C1-C10 substituted or unsubstituted monovalent hydrocarbon group in R.

  Examples of the dicyclopentadiene type phenol resin include a phenol resin represented by the following general formula (XIII).

Here, R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. R ² independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 0 to 10, and m represents an integer of 0 to 6.
Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms in R ¹ and R ² include a methyl group.

  When a dicyclopentadiene type phenol resin is used, the content is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit its performance.

  Examples of the triphenylmethane type phenol resin include a phenol resin represented by the following general formula (XIV).

Here, each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 0 to 10.
A methyl group etc. are mentioned as a C1-C10 substituted or unsubstituted monovalent hydrocarbon group in R.
When using a triphenylmethane type phenol resin, the content is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit its performance.

  Examples of the novolak type phenol resin include phenol novolak resin, cresol novolak resin, naphthol novolak resin and the like, and phenol novolak resin is preferable. In the case of using a novolac type phenol resin, the content is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total amount of the curing agent in order to exhibit its performance.

  The biphenyl type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin and novolac type phenol resin may be used alone or in combination of two or more. Also good. In particular, the inclusion of a biphenyl type phenol resin or an aralkyl type phenol resin is preferable because the contact angle can be reduced. Moreover, it is preferable that the content rate of each phenol resin shall be 60 mass% or more in total with respect to the hardening agent whole quantity, and 80 mass% or more is more preferable.

  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 number of epoxy groups in the epoxy resin (number of hydroxyl groups in curing agent / number of epoxy groups in epoxy resin) is particularly There is no limit. In order to suppress each unreacted component to be small, it is preferably set in the range of 0.5 to 2, and more preferably 0.6 to 1.3. In order to obtain a solid molding resin composition for compression molding excellent in moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

(C) Addition reaction product of phosphine compound and quinone compound In the solid molding resin composition for compression molding of the present invention, the addition reaction product of (C) phosphine compound and quinone compound is represented by the following general formula (I). The phosphine compound is preferably an addition reaction product of a quinone compound represented by the following general formula (II). In addition, the (C) addition reaction product of a phosphine compound and a quinone compound is generally blended as a curing accelerator.

Here, each ^R 1, ^{R 2} and ^{R 3} in the formula (I) independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R ^{4 to} R ⁶ in formula (II) each independently represent a hydrogen atom or a monovalent substituent having 1 to 18 carbon atoms, and R ⁴ and R ⁵ are bonded to each other to form a cyclic structure. May be.

R ¹ , R ² and R ^{3 in the} general formula (I) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. There is no restriction | limiting in particular as a C1-C12 hydrocarbon group, A C1-C12 substituted or unsubstituted aliphatic hydrocarbon group, a C1-C12 substituted or unsubstituted alicyclic hydrocarbon group And a substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms.
Furthermore, the hydrocarbon group preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms.
In addition, the carbon number in the said C1-C12 hydrocarbon group does not include the carbon number of a substituent.

The substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms includes a substituted or unsubstituted chain aliphatic hydrocarbon group having 1 to 12 carbon atoms and a substituted or unsubstituted fat having 1 to 12 carbon atoms. A cyclic hydrocarbon group is mentioned.
Examples of the substituted or unsubstituted chain aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and pentyl group Chain alkyl groups such as hexyl group, octyl group, decyl group and dodecyl group; aryl group-substituted alkyl groups such as benzyl group; alkoxy groups such as methoxy-substituted alkyl group, ethoxy-substituted alkyl group and butoxy-group-substituted alkyl group A substituted alkyl group; an amino group-substituted alkyl group substituted with an amino group such as a dimethylamino group and a diethylamino group; and a hydroxyl group-substituted alkyl group.

  Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, an aryl group, Examples include those substituted with a hydroxyl group, an amino group, a halogen and the like.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 12 carbon atoms include aryl groups such as phenyl group and naphthyl group; tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, t-butylphenyl Groups and alkyl group-substituted aryl groups such as dimethylnaphthyl group; alkoxy group-substituted aryl groups such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group and methoxynaphthyl group; dimethylaminophenyl group and diethylaminophenyl group An amino group-substituted aryl group such as a hydroxyl group-substituted aryl group such as a hydroxyphenyl group and a dihydroxyphenyl group; an aryloxy group such as a phenoxy group and a crezoxy group; a substituted aryl group substituted with a phenylthio group, a tolylthio group, a diphenylamino group, And this Amino group, halogen or the like, and the like obtained by substituting a.

Among these, as R ¹ , R ² and R ³ in the general formula (I), from the viewpoint of the reaction rate, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 12 carbon atoms and a substituted or substituted group having 1 to 12 carbon atoms can be used. An unsubstituted aromatic hydrocarbon group is preferred, a substituted or unsubstituted chain aliphatic hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 1 to 6 carbon atoms, and carbon A substituted or unsubstituted aromatic hydrocarbon group having 1 to 8 carbon atoms is more preferable, a chain alkyl group having 1 to 3 carbon atoms, an aryl-substituted alkyl group having 1 to 7 carbon atoms, an unsubstituted alkyl group having 1 to 6 carbon atoms. An alicyclic hydrocarbon group and an aryl group having 1 to 6 carbon atoms are more preferable.

R ^{4 to} R ⁶ in the above general formula (II) represent a hydrogen atom or a monovalent substituent having 1 to 18 carbon atoms, but are not particularly limited as a monovalent substituent having 1 to 18 carbon atoms. . C1-C18 substituted or unsubstituted aliphatic hydrocarbon group, C1-C18 substituted or unsubstituted alkyloxy group, C1-C18 substituted or unsubstituted alkylthio group, C1-C1 18 substituted or unsubstituted alicyclic hydrocarbon groups, 1 to 18 carbon atoms substituted or unsubstituted aromatic hydrocarbon groups, 1 to 18 carbon atoms substituted or unsubstituted aryloxy groups, 1 to carbon atoms 18 substituted or unsubstituted arylthio groups and the like can be mentioned.
The carbon number in the monovalent substituent having 1 to 18 carbon atoms does not include the carbon number of the substituent.

  Examples of the substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. Alkyl groups such as hexyl group, octyl group, decyl group and dodecyl group; allyl group; alkyl groups substituted with alkoxy groups such as methoxy group, ethoxy group, propoxyl group, n-butoxy group and tert-butoxy group; Alkyl groups substituted with alkylamino groups such as dimethylamino group and diethylamino group; alkyl groups substituted with alkylthio groups such as methylthio group, ethylthio group, butylthio group and dodecylthio group; amino group-substituted alkyl groups, hydroxyl group-substituted alkyl groups And a substituted alkyl group such as an aryl group-substituted alkyl group.

  Examples of the substituted or unsubstituted alkyloxy group having 1 to 18 carbon atoms include alkoxy groups such as methoxy group, ethoxy group, propoxyl group, n-butoxy group and tert-butoxy group; amino group-substituted alkoxy group, hydroxyl group-substituted alkoxy Groups, substituted alkoxy groups such as aryl group-substituted alkoxy groups, and the like.

  Examples of the substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms include a methylthio group, an ethylthio group, a butylthio group, and a dodecylthio group.

  Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 1 to 18 carbon atoms include, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, and the like, and an alkyl group, an alkoxy group, Examples include those substituted with an aryl group, a hydroxyl group, an amino group, halogen, and the like.

  Examples of the substituted or unsubstituted aromatic hydrocarbon group having 1 to 18 carbon atoms include aryl groups such as phenyl group and tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, and t-butylphenyl group. Alkyl group-substituted aryl group, alkoxy group-substituted aryl group such as methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, t-butoxyphenyl group, aryloxy group such as phenoxy group, crezoxy group, phenylthio group, tolylthio group, diphenylamino Examples thereof include an aryl group substituted with a group and the like, and an aryl group substituted with an amino group, halogen and the like.

Examples of the substituted or unsubstituted aryloxy group having 1 to 18 carbon atoms include phenoxy group and crezoxy group.
Examples of the substituted or unsubstituted arylthio group having 1 to 18 carbon atoms include a phenylthio group and a tolylthio group.

Among them, R ^{4 to} R ⁶ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, substituted or unsubstituted Are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group, more preferably a hydrogen atom and a substituted or unsubstituted alkyl group. .

  The molar ratio of the phosphine compound to the quinone compound (phosphine compound / quinone compound) in the addition reaction product of the (C) phosphine compound and quinone compound is preferably 0.5 to 2, preferably 1 to 1.5. More preferably

The addition reaction product of the (C) phosphine compound and the quinone compound can be prepared by a conventional method. For example, it can be obtained by mixing a phosphine compound and a quinone compound in a solvent to cause an addition reaction. The solvent is not particularly limited as long as at least a part of the phosphine compound and the quinone compound can be dissolved, and can be appropriately selected from commonly used solvents. The reaction temperature of the addition reaction can be, for example, 0 to 150 ° C., and the reaction time can be 10 minutes to 24 hours.
Moreover, a commercially available compound may be used for the addition reaction product of the (C) phosphine compound and the quinone compound.

  The content of the addition reaction product of the (C) phosphine compound and the quinone compound in the compression-molding solid encapsulating resin composition is 0. 0 in the compression-molding solid encapsulating resin composition from the viewpoint of curing time. It can be set to 3-0.05 mass%, and it is preferable that it is 0.2-0.1 mass%.

  The content of the addition reaction product of the (C) phosphine compound and the quinone compound in the compression-molding solid encapsulating resin composition is 5 to 0.5 mass with respect to the epoxy resin from the viewpoint of curing time. %, And more preferably 3 to 1% by mass.

Furthermore, the solid molding resin composition for compression molding comprises an addition reaction product having a molar ratio of 1: 1 between the phosphine compound represented by the general formula (I) and the quinone compound represented by the general formula (II). It is preferable to contain 5 to 0.1% by mass in the total mass of the resin composition.
More preferably, it is represented by the general formula (I), and R ^{1 to} R ³ are a chain alkyl group having 1 to 7 carbon atoms, an aryl-substituted alkyl group having 1 to 8 carbon atoms, and an unsubstituted group having 1 to 8 carbon atoms. And a phosphine compound that is an alicyclic hydrocarbon group or an aryl group having 1 to 7 carbon atoms, and represented by the general formula (II), wherein R ^{4 to} R ⁶ are a hydrogen atom or a substituted or unsubstituted alkyl group. An addition reaction product having a molar ratio of 1: 1 of a certain quinone compound is included in the total mass of the resin composition in an amount of 5 to 0.1% by mass.
More preferably, it is represented by the general formula (I), and R ^{1 to} R ³ are a chain alkyl group having 1 to 4 carbon atoms, an aryl-substituted alkyl group having 1 to 7 carbon atoms, and an unsubstituted group having 1 to 6 carbon atoms. A phosphine compound that is an alicyclic hydrocarbon group or an aryl group having 1 to 6 carbon atoms and the general formula (II), wherein R ^{4 to} R ⁶ are in a molar ratio of the hydrogen atom quinone compound of 1: 1. It is to contain 5 to 0.1% by mass of the addition reaction product in the total mass of the resin composition.

(D) Inorganic filler It is preferable that the solid sealing resin composition for compression molding of the present invention further contains at least one inorganic filler. The inorganic filler used in the present invention is preferably contained in the compression-molding solid encapsulating resin composition for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement. Inorganic fillers include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Examples thereof include powders such as spinel, mullite, titania, beads formed by spheroidizing these, and glass fibers.
Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate.
These inorganic fillers may be used alone or in combination of two or more. Of these, fused silica is preferable from the viewpoint of filling property and linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity, and the shape of the inorganic filler is preferably spherical from the viewpoint of filling property and mold wear.

It is preferable that the content rate of an inorganic filler is 55 volume%-90 volume% with respect to the solid sealing resin composition for compression molding from a viewpoint of a filling property and reliability. 60 volume%-90 volume% are more preferable, and 70 volume%-85 volume% are especially preferable.
When it is 55% by volume or more, reflow resistance tends to be improved, and when it is 90% by volume or less, filling property tends to be improved.

(E) Coupling agent (D) When an inorganic filler is used, the solid encapsulating resin composition for compression molding of the present invention contains a coupling agent in order to increase the adhesion between the resin component and the inorganic filler. It is preferable to further blend at least one kind. As a coupling agent, there is no restriction | limiting in particular by what is generally used for the solid sealing resin composition for compression molding. For example, silane compounds having at least one amino group selected from primary, secondary and tertiary amino groups, various silane compounds such as epoxy silane, mercapto silane, alkyl silane, ureido silane, vinyl silane, titanium compounds, Examples include aluminum chelates and aluminum / zirconium compounds.

Illustrative examples include silane coupling agents having unsaturated bonds such as vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, β- Silane coupling agents having an epoxy group such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-mercaptopropyltrimethoxysilane Γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ- Nilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxysilane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxy Silane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N-ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) aminopropyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltri Ethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N Diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropylmethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxy Silane and silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) ) Titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (Dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate, isopropyltri (dioctylphosphate) ) Titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis (Dioctyl phosphite) titanate coupling agents such as titanate; These may be used alone or in combination of two or more.
Of these, a silane coupling agent having an epoxy group is preferable from the viewpoint of filling properties.

When the compression-molding solid encapsulating resin composition contains a coupling agent, the total content of the coupling agent is 0.037% by mass to 4.75% by mass in the compression-molding solid encapsulating resin composition. It is preferable that it is 0.05 mass%-3 mass%, and it is further more preferable that it is 0.1 mass%-2.5 mass%.
There exists a tendency for adhesiveness with a flame | frame to improve that it is 0.037 mass% or more. There exists a tendency for the moldability of a package to improve that it is 4.75 mass% or less.

(Coupling agent coverage)
When using a coupling agent in this invention, it is preferable that the coverage of the coupling agent to an inorganic filler shall be 0.3-1.0, More preferably, it is 0.4-0.9, More preferably, it is 0. It is convenient to set it in the range of 0.5 to 0.8.
If the coverage of the coupling agent is 1.0 or less, bubbles due to volatile matter generated during molding tend to be reduced, and the generation of voids in the thin portion tends to be suppressed. Moreover, since the adhesive force of resin and an inorganic filler falls that the coverage of a coupling agent is 0.3 or more, there exists a tendency for the strength of a molded product to fall.
The coupling agent coverage X is defined as in the formula (xxx).
(Xxx) X (%) = (S _c / S _f ) × 100
S _c and S _f represent the total minimum coating area of all coupling agents and the total surface area of all fillers in the resin composition, respectively, and are defined by the (yyy) formula and the (zzz) formula.
_{(Yyy) S c = A 1} × W 1 + A 2 + × W 2 + ... + A n × M n (n is used a coupling agent number seeds)
(Zzzz) S _f = B ₁ × W ₁ + B ₂ × W ₂ +... + B ₁ × W ₁ (l is the number of fillers used)
Here, A and M represent the minimum coating area of each coupling agent and the amount of use thereof, and B and W represent the specific surface area of each inorganic filler and the amount of use thereof, respectively.

(Coupling agent coverage control method)
If the minimum coating area and specific surface area of each coupling agent and inorganic filler to be used are known, the cup with the desired coupling agent coverage can be obtained from the formula (xxx), (yyy) and (zzz). It is possible to calculate the usage amount of the ring agent and the inorganic filler.

(Flame retardants)
Various flame retardants may be further added to the present invention from the viewpoint of flame retardancy. The flame retardant is generally used in solid molding resin compositions for compression molding and is not particularly limited. For example, brominated epoxy such as diglycidyl etherified tetrabromobisphenol A or brominated phenol novolac epoxy resin. resin. Phosphorus compounds such as antimony oxide, red phosphorus and the above-mentioned phosphate esters, melamine, melamine cyanurate, nitrogen-containing compounds such as melamine-modified phenol resin and guanamine-modified phenol resin, phosphorus / nitrogen-containing compounds such as cyclophosphazene, zinc oxide, Examples thereof include metal compounds such as iron oxide, molybdenum oxide, ferrocene, the above aluminum hydroxide, magnesium hydroxide, and composite metal hydroxide.
Non-halogen and non-antimony flame retardants are preferred from the viewpoint of environmental problems in recent years and high temperature storage properties. Among these, phosphate esters are preferable from the viewpoint of filling properties, and composite metal hydroxides are preferable from the viewpoints of safety and moisture resistance.

The composite metal hydroxide is preferably a compound represented by the following composition formula (XX).
p (M ¹ aOb) · q (M ² cOd) · r (M ³ cOd) · m (H ₂ O) (XX)
(Here, M ¹ , M ² and M ³ represent different metal elements, a, b, c, d, p, q and m are positive numbers, and r is 0 or a positive number.)
Especially, the compound whose r in the said composition formula (XX) is 0, ie, the compound shown by the following composition formula (XXa), is further more preferable.
m (M ¹ aOb) · n (M ² cOd) · l (H ₂ O) (XXa)
(Here, M1 and M2 represent different metal elements, and a, b, c, d, m, n, and l represent positive numbers.)

M ¹ and M ^{2 in the} composition formulas (XX) and (XXa) are not particularly limited as long as they are different metal elements, but from the viewpoint of flame retardancy, M ¹ and M ² should not be the same. M ¹ is selected from metal elements of the third period, Group IIA alkaline earth metal elements, Group IVB, Group IIB, Group VIII, Group IB, Group IIIA and Group IVA, and M ² is IIIB to IIB is preferably selected from transition metal elements of group, magnesium M ^1, calcium, aluminum, chosen tin, titanium, iron, cobalt, nickel, copper and zinc, M ² is iron, cobalt, nickel, copper and zinc More preferably, it is chosen from. From the viewpoint of fluidity, M ¹ is preferably magnesium and M ² is preferably zinc or nickel, more preferably M ¹ is magnesium and M ² is zinc.
The molar ratio of p, q, and r in the above composition formula (XX) is not particularly limited as long as the effect of the present invention can be obtained, but r = 0, and the molar ratio p / q of p and q is 99/1 to Preferably it is 50/50. That is, the molar ratio m / n of m and n in the composition formula (XXa) is preferably 99/1 to 50/50.
In addition, the classification of metal elements is a long-period type periodic rate table in which the typical element is the A subgroup and the transition element is the B subgroup (Source: Kyoritsu Shuppan Co., Ltd., “Chemical Dictionary 4”, February 15, 1987) (Reduced plate 30th printing).

The shape of the composite metal hydroxide is not particularly limited, but from the viewpoint of fluidity and filling properties, a polyhedral shape having an appropriate thickness is preferable to a flat plate shape. Compared to metal hydroxides, complex metal hydroxides tend to give polyhedral crystals.
Although there is no restriction | limiting in particular in the compounding quantity of a composite metal hydroxide, 0.5 mass%-20 mass% are preferable with respect to the solid sealing resin composition for compression molding, and 0.7 mass%-15 mass% are more. Preferably, 1.4 mass%-12 mass% are more preferable.
When it is 0.5% by mass or more, flame retardancy tends to be sufficient, and when it is 20% by mass or less, filling property and reflow resistance tend to be improved.

Moreover, an anion exchanger can also be added to the solid encapsulating resin composition for compression molding of the present invention from the viewpoint of improving the moisture resistance and high temperature storage characteristics of a semiconductor element such as an IC. The anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. For example, hydrotalcites, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, bismuth, etc. These may be used alone or in combination of two or more. Of these, hydrotalcite represented by the following composition formula (XXI) is preferable.
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (XXI)
(0 <X ≦ 0.5, m is a positive number)

  Further, in the solid sealing resin composition for compression molding of the present invention, as other additives, a release agent such as higher fatty acid, higher fatty acid metal salt, ester wax, polyolefin wax, polyethylene, polyethylene oxide and the like, carbon A colorant such as black, a stress relaxation agent such as silicone oil and silicone rubber powder, and the like can be blended as necessary.

(Preparation and usage)
The solid encapsulating resin composition for compression molding of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed, but as a general method, a raw material having a predetermined blending amount is mixed. Examples thereof include a method in which the mixture is sufficiently mixed by, etc., then mixed or melt-kneaded by a mixing roll, an extruder, a raking machine, a planetary mixer, etc., then cooled, and defoamed and pulverized as necessary. Moreover, you may tablet by the dimension and mass which meet molding conditions as needed.
As a method of sealing a semiconductor device using the solid molding resin composition for compression molding of the present invention as a sealing material, a low-pressure transfer molding method is generally used, but an injection molding method, a compression molding method, etc. are also used. Can be mentioned. A dispensing method, a casting method, a printing method, or the like may be used. Compression molding is preferable from the viewpoint of collective sealing.

(Semiconductor device)
Next, the semiconductor device of the present invention will be described. Moreover, the suitable use and usage method of the solid sealing resin composition for compression molding of this invention are demonstrated through description of this semiconductor device.
Examples of the semiconductor device of the present invention include a package for FO-WLP manufactured by compression molding with a sealing resin composition. Here, the solid sealing resin composition for compression molding of the present invention is used as the sealing resin composition.

  As such a semiconductor device, for example, BGA (Ball Grid Array), CSP (Chip Size Package), MCP (Multi Chip Package), etc., in which the semiconductor chip mounting side is sealed with a solid molding resin composition for compression molding. Can also be used. In addition, even if these semiconductor devices are a stacked type package in which two or more elements are stacked on a mounting substrate, two or more elements are solid molded resin for compression molding at a time. It may be a collective mold type package sealed with a composition.

A preferred embodiment of the semiconductor device of the present invention will be described with reference to FIG. The semiconductor device of the present invention is not limited to these.
FIG. 1 shows an example of manufacturing a semiconductor manufacturing apparatus in FO-WLP. The diced chip 3 is affixed to the carrier 1 using a temporary fixing tape 2. By applying a solid molding resin composition for compression molding to the chip 3 by compression molding and thermosetting, a molded body in which the chip 3 is coated with the sealing material 4 can be obtained.
From the viewpoint of heat resistance of the temporary fixing tape 2 used at this time, in the compression molding using the solid sealing resin composition for compression molding, it is preferably molded at 150 ° C. or less, more preferably 140 ° C. or less. From the viewpoint of warpage, it is particularly preferably 130 ° C. or lower.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In addition, evaluation of each solid sealing resin composition for compression molding was performed based on the evaluation method demonstrated later unless it mentions specially.

(Examples 1-6, Comparative Examples 1-3)
Example 1 Each material was premixed (dry blended) so as to have the composition shown in Tables 1 and 2, then kneaded with a biaxial roll having a roll surface temperature of about 80 ° C. for 15 minutes, and then cooled and crushed. To 6 and Comparative Examples 1 to 3 were produced. In addition, the composition in a table | surface was shown by the mass part. Moreover, the blank in a table | surface shows having not mix | blended.

(A) Epoxy resin The following was used as an epoxy resin.
-(Epoxy resin 1): Nippon Kayaku Co., Ltd. product name NC-3000 (epoxy equivalent 280) as a biphenylene type epoxy resin
・ (Epoxy resin 2): Mitsubishi Chemical Corporation product name YX-4000 (epoxy equivalent 192, melting point 67 ° C.) as biphenyl skeleton type epoxy resin
-(Epoxy resin 3): As a triphenylmethane type epoxy resin, Mitsubishi Chemical Corporation product name 1032H60 (epoxy equivalent 170, melting point 60)

(B) Curing agent In addition, the following were used as (B) curing agent: (Curing agent 1): phenolic polycondensate having a hydroxyl group equivalent of 199 and a softening point of 80 ° C. (product name HE200C-10, Air Water Chemical Company) )
(Curing agent 2): Triphenol polycondensate having a hydroxyl group equivalent of 175 and a softening point of 70 ° C. (product name HE910-10, Air Water Water Chemical)

(C) Curing accelerator (C) As the curing accelerator, the following was used.
-(Curing Accelerator 1): Addition product of triphenylphosphine and 1,4-benzoquinone-(Curing Accelerator 2): Addition reaction product of tributylphosphine and methyl-1,4-benzoquinone-(Curing accelerator 3) : Adduct of tricyclohexylphosphine and 1,4-benzoquinone (Curing accelerator 4): Adduct of tri-p-methylbenzylphosphine and 1,4-benzoquinone (Curing accelerator 5): Triisobutylphosphine and 1, An adduct of 4-benzoquinone was used.
The curing accelerators 1 to 5 are addition reaction products having a molar ratio of 1: 1 between the phosphine compound and the quinone compound.
(Curing Accelerator A): Triphenylphosphine (Curing Accelerator B): 2-Ethyl 4-methylimidazole (2E4MZ manufactured by Shikoku Chemicals Co., Ltd.)
-(Curing Accelerator C): 2-Phenyl 4-methylimidazole (2P4MZ manufactured by Shikoku Chemicals Co., Ltd.)

(D) Inorganic filler (D) As an inorganic filler, spherical fused silica having a volume average particle diameter of 14.5 μm and a specific surface area of 2.8 m ² / g was used.

(E) Coupling agent The following was used as a coupling agent.
(Coupling agent 1): γ-glycidoxypropyltrimethoxysilane (epoxysilane) (trade name A-187 manufactured by Toray Dow Silicone Co., Ltd.)
(Coupling agent 2): Secondary aminosilane (trade name Y-9669 manufactured by Toray Dow Silicone Co., Ltd.)
(Coupling agent 3): Silane ester (trade name KBM-202SS manufactured by Shin-Etsu Chemical Co., Ltd.)
(Coupling agent 4): Mercaptosilane (trade name KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.)

  As another additive, carbon black (trade name MA-600MJ-S manufactured by Mitsubishi Chemical Corporation) was used in parts by mass shown in Tables 1-2.

  Evaluation of each produced solid sealing resin composition for compression molding was performed based on the evaluation method shown below.

(Geltime)
The gel time is measured by placing a fixed amount (0.5 g) of a resin composition on an iron plate heated to 175 ° C., stirring with a spatula, and measuring the time (seconds) until it loses fluidity and solidifies. evaluated.

(Reaction rate)
The resin composition was measured by DSC (Differential Scanning Calorimetry) method, and the reaction rate of the resin composition at 130 ° C. for 400 seconds and 120 ° C. for 600 seconds was determined. The reaction rate was measured as follows.
2-10 mg of the resin compositions obtained in Examples and Comparative Examples were weighed into an aluminum measuring container, and the temperature rising rate was 20 ° C. using a Perkin Elmer DSC (Differential Scanning Calorimeter) “Pyris 1” (trade name). The temperature was increased to 30 to 300 ° C./min and the calorific value was measured, and this was defined as the initial calorific value.
Subsequently, the resin composition was heated under conditions of 130 ° C. for 400 seconds or 120 ° C. for 600 seconds to obtain a resin composition in a state where heat treatment was performed. For the resin composition after the heat treatment, the calorific value was similarly measured, and this was defined as the calorific value after heating. The reaction rate (%) was calculated from the obtained calorific value by the following formula.
Reaction rate (%) = [(initial heating value−heating value after heating) / (initial heating value)] × 100

(Fluidity; life)
Using a mold temperature of 180 ° C. and an iron plate of 8 kg, 5 g of the produced resin composition was compression molded under the condition of a curing time of 90 seconds, and the average value of the major axis and minor axis of the resin composition molded into a disk shape was measured. The initial value of the disk flow was used.
Furthermore, the produced resin composition was treated for 48 hours in a constant temperature bath at 25 ° C. The disk flow measurement of the resin composition treated with time was performed in the same manner as described above. The fluidity was determined by the ratio of the measured values before and after the treatment. The case where the measured value of the disk flow is the same as the initial value is 100%.

As shown in Table 2, Comparative Example 1, which does not contain an addition reaction product of (C) phosphine compound and quinone compound as a curing accelerator, has a low reaction rate at 130 ° C. or 120 ° C., and Comparative Example It can be seen that 2 and 3 have low fluidity (life) and a problem in long-term storage stability.
On the other hand, all of Examples 1 to 6 have a high reaction rate at 130 ° C. or 120 ° C. (40% or more), a large fluidity (life) (90% or more), and long-term storage stability. It turns out that it is excellent.
The solid sealing resin composition for compression molding of the present invention is a resin composition that exhibits high reactivity at low temperatures required for low temperature molding, and has excellent long-term storage stability, and for FO-WLP packages. It is suitable and its industrial value is great.

1: carrier, 2: temporary fixing tape, 3: chip, 4: sealing material, 5: bump, 6: rewiring layer.

Claims (8)

  (A) An epoxy resin, (B) a curing agent, and (C) an addition reaction product of a phosphine compound and a quinone compound, and a compression molding solid for use in compression molding with a molding temperature of 130 ° C. or lower. Sealing resin composition.   (A) an epoxy resin, (B) a curing agent, (C) an addition reaction product of a phosphine compound and a quinone compound, and measured by differential scanning calorimetry, the (A) epoxy resin and (B) The time required for the reaction rate with the curing agent to reach 40% is within 400 seconds when the reaction temperature is 130 ° C, or within 600 seconds when the reaction temperature is 120 ° C, and the molding temperature is 130 ° C or less. A solid sealing resin composition for compression molding for use in compression molding.   The solid sealing resin composition for compression molding according to claim 1 or 2, which is used for sealing a semiconductor device for FO-WLP.   The solid sealing resin composition for compression molding according to any one of claims 1 to 3, wherein the fluidity after 48 hours at 25 ° C is 90% or more with respect to the fluidity before the passage. . The (C) addition reaction product of a phosphine compound and a quinone compound is an addition reaction product of a phosphine compound represented by the following general formula (I) and a quinone compound represented by the following general formula (II): Item 5. The solid encapsulating resin composition for compression molding according to any one of Items 4.

(Here, R ¹ , R ² and R ³ in formula (I) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. Moreover, R ^{4 to} R in formula (II) ⁶ each independently represents a hydrogen atom or a monovalent substituent having 1 to 18 carbon atoms, and R ⁴ and R ⁵ may be bonded to each other to form a ring.)   The solid sealing resin for compression molding according to any one of claims 1 to 5, further comprising (D) an inorganic filler, the content of which is 55% by volume to 90% by volume in the total volume. Composition. The semiconductor device for FO-WLP which has the semiconductor element sealed with the solid sealing resin composition for compression molding of any one of Claims 1-6. The manufacturing of a semiconductor device provided with the process of sealing a semiconductor element by the compression molding whose molding temperature is 130 degrees C or less with the solid sealing resin composition for compression molding of any one of Claims 1-6. Way .