JP6551499B2 - Semiconductor molding resin material for compression molding and semiconductor device - Google Patents

Description

  The present invention relates to a semiconductor molding resin material 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, cost, etc., and epoxy resin has been widely used as a semiconductor sealing resin material. This is because epoxy resins are balanced in various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts. In recent years, high density mounting of electronic components on printed wiring boards has been advanced. Along with this, the semiconductor device has mainly become a surface mount type package from a conventional pin insertion type package.

  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 thin. 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. Is also in progress. Also, in order to correspond to further reduction in size and weight, the form of the package is also from a quad flat package (QFP) or a small outline package (SOP) to a CSP which can easily cope with the increase in the number of pins and can be mounted in higher density. (Chip Size Package) and BGA (Ball Grid Array).

  Along with the multi-functionality of the package, the built-in wire has become thinner, and it has become difficult to mold due to the generation of wire flow in normal transfer molding. Compression molding has been developed to solve these problems. Currently, compression molding is used not only for BGA type packages but also for FO (Fan Out) type packages. At present, among them, it is often used in FO-WLP (Fan Out Wafer Level Package). At present, it is mainly produced using a liquid sealing material to produce FO-WLP. In the case of a liquid sealing material, since the unit price of the resin is high, the cost of the package is high and the unit price of the package is high.

Moreover, in the case of this compression molding, since large-size collective sealing is performed, warpage after molding is a problem. In addition, after the rewiring process, which is a feature of this package after molding, the warping behavior changes when it receives various thermal histories, which makes handling to other processes difficult. There is a concern.
Therefore, in the case of using a conventional liquid sealing material (see, for example, Patent Document 1), a process for reducing the warpage is required. Further, after molding, various heat treatments such as rewiring material curing and reflow for bump mounting are performed before mounting in the manufacturing process of the package. At that time, in the case of the liquid sealing material, the warpage behavior is largely changed, which may adversely affect other processes. Therefore, it is required that the warpage be small in each process. At present, in order to solve the problem, solidification of the sealing material is being studied (see, for example, Non-Patent Document 1).
Usually, in compression molding, when supplying a solid sealing material, it is common to supply powder. However, in the case of this package, a molding machine is present in the clean room in consideration of the subsequent steps. For this reason, it is known that when supplied as powder, fine powder generated from the sealing material adversely affects other processes.

For this problem, it is conceivable to use a granulated sealant (see, for example, Patent Literature 2 and Patent Literature 3).
In addition, as a method different from granulation, a method of performing compression molding in a pellet form or a sheet form has also been proposed (see, for example, Patent Document 4). In this case, a material having excellent formability has already been developed by using a thin sheet molding having a thickness of 3 mm or less.

WO 09/142065 pamphlet JP 2008-303367 A JP, 2008-303368, A JP, 2006-216899, A

Wafer Level Embedding Technology for 3D Wafer Level Embedded Package (ECTC 2009 1289-1296)

However, the above-described granulated sealing material can not completely remove the fine powder generated at the time of material conveyance. In addition, in compression molding, when the material is supplied as powder, air in the material is not sufficiently removed, and there is a possibility that the air may be voided after molding.
Moreover, in the manufacturing process of the semiconductor device which performs compression molding in a pellet form or a sheet form, it is necessary to shape | mold epoxy sealing resin at low temperature. For this reason, when molding is performed using a sheet molded product having a thickness of 3 mm or less, the thermal history does not work well with the epoxy sealing resin at the stage of molding, and the resin may not melt. is there. As a result, there are drawbacks that cause chip breakage and damage to the mold.

  In the present invention, it is possible to stabilize warpage behavior after molding and heat treatment, to significantly reduce the generation of fine powder, and to suppress generation of defects such as voids and chip breakage and damage to the mold during compression molding. It is an object of the present invention to provide a semiconductor encapsulation resin material for compression molding that has been made possible and a semiconductor device formed thereby.

  As a result of intensive studies to solve the above problems, the inventors have made warpage in each process by molding into a pellet or sheet while optimizing the resin composition of the semiconductor sealing resin material. It has been found that the behavior is stabilized and the generation of fine powder can be suppressed, and defects such as voids in compression molding, chip cracking, and damage to a mold can be suppressed, and the present invention has been completed.

That is, the present invention relates to the following items.
<1> A pellet or sheet containing (A) epoxy resin, (B) curing agent, and (C) filler, the content of the (C) filler is 85 mass% or more, and a thickness of 3 mm to 10 mm It is a semiconductor molding resin material for compression molding which is a shaped molded body.
<2> The semiconductor encapsulation resin material for compression molding according to <1>, wherein the (A) epoxy resin contains a compound represented by the following general formula (I).

(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 1 to 10.)
It is a semiconductor sealing resin material for compression molding as described in <1> or <2> in which the <3> above-mentioned (B) hardening | curing agent contains the compound shown by following General formula (II).

(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 1 to 10.)
<4> The molded body according to any one of <1> to <3>, wherein a glass transition temperature when the molded body is cured at a molding temperature of 175 ° C. or lower and a post-molding heat treatment temperature of 150 ° C. or lower is 150 ° C. or higher. It is a semiconductor encapsulation resin material for compression molding.

The <5> above-mentioned (C) filler is a semiconductor sealing resin material for compression molding as described in any one of <1>-<4> which is a particle group which can pass the sieve of 55 micrometers of openings.
It is a semiconductor device provided with the element sealed by the semiconductor sealing resin material for compression molding as described in any one of <6><1>-<5>.

  According to the present invention, warpage behavior after molding and heat treatment is stabilized, generation of fine powder is significantly reduced, and defects such as voids in compression molding, chip cracking, and damage to the mold can be suppressed. Become.

It is sectional drawing at the time of the compression molding of FO type package (semiconductor device) sealed using the semiconductor sealing resin material (sealing material) of this invention, and is a schematic cross section which shows a part of manufacturing process of FO type package FIG. It is sectional drawing of the FO type package which is an example of one Embodiment of the semiconductor device of this invention.

  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, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

[Semiconductor sealing resin material for compression molding]
The semiconductor molding resin material for compression molding of the present invention (hereinafter, also simply referred to as "semiconductor sealing resin material") contains (A) an epoxy resin, (B) a curing agent, and (C) a filler, (C) The content of a filler is 85 mass% or more, and it is a pellet-like or sheet-like compact having a thickness of 3 mm to 10 mm. The semiconductor sealing resin material is solid at room temperature (25 ° C.). With this configuration, the warping behavior after molding and heat treatment is stabilized, the generation of fine powder can be greatly reduced, chip cracking and damage to the mold can be suppressed, and the FO package semiconductor device Suitable for sealing of

  That is, since the semiconductor sealing resin material has a smaller thermal shrinkage than the liquid sealing material, the fluctuation of the warping behavior which becomes a problem when a conventional liquid sealing material is used in compression molding is relatively small. Furthermore, in the present invention, by adding the filler (C) to the resin material so as to have a certain concentration or more, it is possible to reduce warping after molding and significantly lower warpage in each step after molding. Can be improved. In addition, by selecting the concentration range of the filler (C) and molding the sealing material into a pellet shape or sheet shape with a thickness of 3 mm to 10 mm, as a conventional compression molding solid sealing material while suppressing warpage Generation of fine powder, defects such as voids, chip cracks, and damage to the mold, which are problems when supplying powder or thin film sheets, can be significantly reduced.

(C) Filler The semiconductor encapsulating resin material contains at least one kind of (C) filler having a constant concentration in order to absorb moisture, reduce the linear expansion coefficient, improve thermal conductivity, and improve strength.
Examples of the filler (C) include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steer. Powders such as tight, spinel, mullite, and titania or beads obtained by spheronizing them, glass fibers and the like can be mentioned. Examples of the filler (C) include aluminum hydroxide, magnesium hydroxide, zinc borate and zinc molybdate, which have a flame retardant effect. Among these, fused silica is preferable from the viewpoint of filling properties and reduction of linear expansion coefficient. Alumina is preferred from the viewpoint of high thermal conductivity.
The (C) filler may be used alone or in combination of two or more.
The shape of the filler (C) is preferably a spherical shape from the viewpoint of filling properties and mold wear.

The content of the (C) filler is 85% by mass or more in the total mass of the semiconductor sealing resin material from the viewpoint of the filling property and the reliability. By increasing the content of the (C) filler, warpage after molding can be reduced. When the content of the (C) filler is less than 85% by mass, warpage can not be sufficiently suppressed. The content of the (C) filler is preferably 85% by mass to 95% by mass. 88 mass% or more is more preferable in order to suppress the curvature after shaping | molding more. When the content is 95% by mass or less, the packing property is excellent, and the material can be easily produced.
The content rate of the (C) filler in the semiconductor sealing resin material total mass is measured as follows. First, the total mass of the semiconductor encapsulating resin material is measured, the semiconductor encapsulating resin material is baked at 400 ° C. for 2 hours and then at 700 ° C. for 3 hours to evaporate the resin component, and the mass of the remaining (C) filler is determined. By measuring, the ratio of the mass of the (C) filler to the total mass of the semiconductor encapsulation resin material is taken as the content of the (C) filler.

The semiconductor encapsulating resin material may open a hole by a laser in a molded product. Therefore, it is preferable that the (C) filler be controlled to a predetermined roughness by classification treatment from the viewpoint of the easiness of making holes by laser.
As a method of obtaining the above-mentioned (C) filler, whether it is wet or dry, sieving may be performed using a commonly used sieving machine, classifier or the like. Examples of the apparatus to be used include an air type, an electrostatic type, a sonic vibration type, and an electromagnetic vibration type.

As the (C) filler, those which can pass through a sieve having an opening of 55 μm of the sieve to be used (the coarse particles have been removed) are preferable. By passing through a sieve having an opening of 55 μm, the filling property is further improved. It is more preferable to be able to pass through a sieve with a finer mesh (for example, 30 μm), in consideration of the case where the miniaturization of the holes progresses.
It is desirable that the classification accuracy is less than 1% when a certain opening is passed through and then the opening is passed again.

(A) Epoxy Resin The (A) epoxy resin used in the present invention is not particularly limited as long as it is generally used for semiconductor sealing resin materials. 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 Condensation of at least one selected from the group consisting of naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene with a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde in an acidic catalyst Novolak type epoxy resin obtained by epoxidizing a novolak resin obtained by co-condensation or bisphenol; 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, Glycidyl amine type epoxy resin obtained by reaction of epichlorohydrin with polyamine such as isocyanuric acid; Epoxide compound of co-condensed resin of dicyclopentadiene and phenols; 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 olefin bond with peracid such as peracetic acid Family epoxy resins; alicyclic epoxy resins; sulfur atom-containing epoxy resin; dihydroanthracene type epoxy resins.
These may be used alone or in combination of two or more.

  The (A) epoxy resin preferably contains at least one compound (triphenylmethane type epoxy resin) represented by the following general formula (I). When the compound is contained in the semiconductor sealing resin material, heat resistance and low warpage can be imparted to the resin material, and the warpage behavior can be stabilized.

Here, each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Moreover, n shows the integer of 1-10.
The carbon number of the monovalent hydrocarbon group is set to 1 to 10 in order to obtain the effects of the present invention. From the viewpoint of heat resistance and low warpage, 1 to 7 is preferable, and 1 to 4 is more preferable.
Examples of the monovalent hydrocarbon group for R in the general formula (I) include an alkyl group and an alkenyl group. Among them, an alkyl group is preferable.
As a substituent in the said monovalent hydrocarbon group, a halogen atom, an amino group, a mercapto group etc. are mentioned.

  Examples of R in the general formula (I) include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t-butyl group, a vinyl group, an allyl group, and a butenyl group. Alkenyl group, a halogenated alkyl group, an amino group substituted alkyl group, a mercapto group substituted alkyl group and the like. Of these, an alkyl group such as a methyl group or an ethyl group and a hydrogen atom are preferable.

  The epoxy equivalent of the triphenylmethane type epoxy resin represented by the general formula (I) is not particularly limited. Among these, from the viewpoint of stabilizing the warping behavior, it is preferably 150 to 200, and more preferably 155 to 180.

  The triphenylmethane type epoxy resins may be used alone or in combination of two or more. The content is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more in the total mass of the epoxy resin (A) in order to exhibit its performance. More preferable.

The (A) epoxy resin is, as an epoxy resin other than the above compound, a biphenyl type epoxy resin which is a diglycidyl ether of an alkyl-substituted or unsubstituted biphenol from the viewpoint of filling property and reflow resistance, and a diglycidyl ether of bisphenol F It is preferable to contain at least one selected from the group consisting of a bisphenol F-type epoxy resin, a stilbene-type epoxy resin, and a sulfur atom-containing epoxy resin. Among these, it is more preferable to include at least one selected from the group consisting of biphenyl type epoxy resins and sulfur atom-containing epoxy resins. Any of the above-mentioned biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin and sulfur atom-containing epoxy resin may be used alone or in combination of two or more.
The epoxy resin (A) is preferably a novolak epoxy resin from the viewpoint of curability, a dicyclopentadiene epoxy resin from the viewpoint of low hygroscopicity, and a naphthalene from the viewpoint of heat resistance and low warpage. Type epoxy resin is preferred. The (A) epoxy resin preferably also contains at least one of these novolak type epoxy resins, dicyclopentadiene type epoxy resins and naphthalene type epoxy resins.
Further, the (A) epoxy resin is preferably an epoxidized aralkyl type phenol resin from the viewpoint of adhesion, and is preferably a dihydroanthracene type epoxy resin from the viewpoint of curability and adhesion. It is also preferable that the (A) epoxy resin contains at least one of an epoxy compound of the aralkyl type phenol resin and a dihydroanthracene type epoxy resin.

  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. Moreover, as a stilbene type epoxy resin, the epoxy resin etc. which are shown with the following general formula (V) are mentioned. Moreover, as a sulfur atom containing epoxy resin, the epoxy resin etc. which are shown with the following general formula (VI) are mentioned.

Here, R ^{1 to} R ⁸ each independently represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. n shows the integer of 0-3.
Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms in R ^{1 to} R ⁸ include an alkyl group.

Here, R ^{1 to} R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl having 6 to 10 carbon atoms. Indicates a group. n shows the integer of 0-3.
Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms in R ^{1 to} R ⁸ include an alkyl group.

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 shows the integer of 0-10.
Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms in R ^{1 to} R ⁸ include an alkyl group.

Here, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms. n shows the integer of 0-3.
Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms in R ^{1 to} R ⁸ include an alkyl group.

  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 of Nippon Steel Chemical Co., Ltd.) having n = 0 as a main component is commercially available.

  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 and the like, 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), an epoxy resin wherein 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 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 (made by Nippon Steel Chemical Co., Ltd.) etc. is available as a commercial item.

  Any of the aforementioned biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin and sulfur atom-containing epoxy resin may be used alone or in combination of two or more. The content is preferably 40% by mass or more, more preferably 60% by mass or more, and more preferably 80% by mass or more in the total mass of the epoxy resin (A) in order to exhibit its performance. More preferable.

  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 novolac epoxy resin represented by the above general formula (VII) can be easily obtained by reacting epichlorohydrin with novolac phenol resin. Among them, as R in the general formula (VII), a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or the like, an alkyl group having 1 to 10 carbon atoms, 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 novolac epoxy resins represented by the above general formula (VII), ortho-cresol novolac epoxy resins are preferable.
In the case of using a novolac type epoxy resin, the content is preferably 20% by mass or more, more preferably 30% by mass or more in the total mass of the epoxy resin (A) in order to exhibit its performance.

  As a dicyclopentadiene type epoxy resin, the epoxy resin etc. which are shown by following General formula (VIII) are mentioned, for example.

Here, R ¹ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² represents a substituted or unsubstituted monovalent hydrocarbon having 1 to 10 carbon atoms. Indicates a group. 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. Among them, 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 an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and a t-butyl group, an alkenyl group such as a vinyl group, an allyl group, and a butenyl group, a halogenated alkyl group, and an amino group. A substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms such as a group-substituted alkyl group or a mercapto group-substituted alkyl group can be mentioned. Among these, m is preferably 0.

  In the case of using a dicyclopentadiene type epoxy resin, the content is preferably 20% by mass or more, more preferably 30% by mass or more in the total mass of the epoxy resin (A) in order to exhibit its performance. .

  As a naphthalene type epoxy resin, the epoxy resin etc. which are shown by following General formula (IX) are mentioned, for example.

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 an alkyl 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.

  A naphthalene type epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more type. The content is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more in the total mass of the epoxy resin (A) in order to exhibit its performance. More preferable.

  As the epoxy compound of the aralkyl type phenol resin, an epoxy compound of a phenol / aralkyl resin is preferable. As the epoxidized product of the phenol / aralkyl resin, a biphenylene type epoxy resin containing a biphenylene skeleton represented by the following general formula (X) is preferable.

Here, in the general formula (X), R ^{1 to} R ⁸ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. R < ⁹ > shows a C1-C12 valent hydrocarbon group each independently. i represents an integer of 0 to 3, and n represents an integer of 0 to 10.
The biphenylene type epoxy resin represented by the above general formula (X) reacts epichlorohydrin with a phenol / aralkyl resin synthesized from alkyl-substituted, aromatic ring-substituted or unsubstituted phenol and bis (methoxymethyl) biphenyl by a known method Can be obtained.

Examples of the monovalent hydrocarbon group represented by R ^{1 to} R ⁹ in the general formula (X) 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 pentyl. Group, hexyl group, octyl group, decyl group, dodecyl group and other chain alkyl groups; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopentenyl group, cyclohexenyl group and other cyclic alkyl groups; benzyl group, phenethyl group, etc. Aryl group-substituted alkyl group; alkoxy group-substituted alkyl group such as methoxy group-substituted alkyl group, ethoxy group-substituted alkyl group, butoxy group-substituted alkyl group; amino group-substituted alkyl group such as aminoalkyl group, dimethylaminoalkyl group, diethylaminoalkyl group Hydroxyl group-substituted alkyl group; phenyl group, naphthyl group, biphenyl group Unsubstituted aryl group; alkyl group-substituted aryl group such as tolyl group, dimethylphenyl group, ethylphenyl group, butylphenyl group, tert-butylphenyl group, dimethylnaphthyl group and the like; methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, Examples include alkoxy group-substituted aryl groups such as tert-butoxyphenyl group and methoxynaphthyl group; amino group-substituted aryl groups such as dimethylamino group and diethylamino group; hydroxyl group-substituted aryl groups. Among them, methyl group is preferable. R ^{1 to} R ⁸ are also preferably a hydrogen atom, and i is preferably 0.
Further, n in the general formula (X) is more preferably 6 or less on average.
Such an epoxy resin is available as a commercial product under the trade name NC-3000 manufactured by Nippon Kayaku Co., Ltd.

  When the semiconductor encapsulating resin material contains an epoxidized product of the phenol / aralkyl resin, the content is preferably 20% by mass or more, and 30% by mass in the total mass of the epoxy resin in order to exhibit its performance. The above is more preferred, and more preferably 50% by mass or more.

  Moreover, in the said semiconductor sealing resin material, the dihydroanthracene type | mold epoxy resin shown by the following structural formula (XV) can also be used as (A) epoxy resin.

Formula (XV) ^{R 1} and ^{R 2} in each independently represents a hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms having 1 to 12 carbon atoms. n shows the integer of 0-4. m shows the integer of 0-2.

  As the dihydroanthracene type epoxy resin represented by the general formula (XV), YX-8800 (trade name, manufactured by Mitsubishi Chemical Corporation) and the like are available.

  In the case where the semiconductor encapsulating resin material contains the dihydroanthracene type epoxy resin represented by the general formula (XV), in order for the epoxy resin to exhibit performance from each viewpoint, the content is determined based on the total amount of the epoxy resin. The amount is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more.

Biphenyl type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, biphenylene type epoxy resin and dihydroanthracene type epoxy The resin is preferably blended with the (A) epoxy resin in combination with the triphenylmethane type epoxy resin. The combined use of these epoxy resins and the compound represented by the general formula (I) can stabilize the warping behavior more effectively.
The (A) epoxy resin may be a biphenyl type epoxy resin, a bisphenol F type epoxy resin, a stilbene type epoxy resin, a sulfur atom-containing epoxy resin, a novolac type epoxy resin, a dicyclopentadiene type resin instead of a triphenylmethane type epoxy resin. It is also preferable that it is at least one selected from the group consisting of an epoxy resin, a naphthalene type epoxy resin, a biphenylene type epoxy resin and a dihydroanthracene type epoxy resin, and a biphenyl type epoxy resin, a sulfur atom containing epoxy resin, a novolac type epoxy resin, More preferably, it is at least one selected from the group consisting of dicyclopentadiene type epoxy resins, biphenylene type epoxy resins and dihydroanthracene type epoxy resins.

  The epoxy equivalent of the epoxy resin other than the triphenylmethane type epoxy resin represented by the above general formula (I) is not particularly limited. Among these, from the viewpoint of stabilizing the warping behavior, 150 to 300 is preferable, and 155 to 280 is more preferable.

  The content rate of the (A) epoxy resin contained in the semiconductor encapsulation resin material is not particularly limited. Especially, it is preferable that they are 3 mass%-15 mass% in the total mass of a semiconductor sealing resin material, and it is more preferable that they are 5 mass%-10 mass%.

(B) Curing Agent The (B) curing agent used in the present invention is not particularly limited as long as it is generally used for semiconductor sealing resin materials. Specifically, at least selected from the group consisting of phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol, and naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene. Novolak-type phenolic resin obtained by condensation or co-condensation of one compound with a compound having an aldehyde group such as formaldehyde, benzaldehyde or salicylaldehyde under an acidic catalyst; at least one member selected from the group consisting of phenols and naphthols Phenol aralkyl resins synthesized from dimethoxyparaxylene or bis (methoxymethyl) biphenyl; aralkyl phenol resins such as naphthol aralkyl resins; phenols and naphtho And dicyclopentadiene type phenolic resins such as dichloropentadiene type phenol novolac resin and naphthol novolac resin synthesized by copolymerization with at least one selected from the group consisting of cyclopentadiene and terpene-modified phenolic resin.
These may be used alone or in combination of two or more.

  The (B) curing agent preferably contains at least one compound (triphenylmethane type phenol resin) represented by the following general formula (II). When the compound is contained in the semiconductor sealing resin material, the cured product of the resin material has a high glass transition temperature, and the warpage behavior is stabilized.

Here, each R independently represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Moreover, n shows the integer of 1-10.
Examples of the monovalent hydrocarbon group for R in the general formula (II) include an alkyl group, an alkoxy group, an aryl group, and an aralkyl group in order to reduce warpage. Among them, an alkyl group is preferable.
From the viewpoint of high glass transition temperature, for example, in the case of an alkyl group, an alkoxy group and the like, the carbon number of the monovalent hydrocarbon group is preferably 1 to 10, and more preferably 1 to 6. 6-10 are preferable in an aryl group, an aralkyl group, etc.
Examples of the substituent in the monovalent hydrocarbon group include an amino group, a mercapto group, an alkenyl group and an alkyl group.

Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms in R in the general formula (II) include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, and an isobutyl group. C 1-10 alkyl groups having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, butoxy and the like, and an aryl group having 6 to 10 carbon atoms such as phenyl, tolyl and xylyl groups And aralkyl groups having 6 to 10 carbon atoms such as benzyl group and phenethyl group.
R in the general formula (I) is specifically a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, methoxy group, ethoxy group, propoxy group, butoxy group, phenyl It is preferable to be selected from the group consisting of a group, tolyl group, xylyl group, benzyl group and phenethyl group, and in particular, a hydrogen atom or a methyl group is more preferable.

  In the semiconductor encapsulating resin material, the compound represented by the general formula (II) is preferably used in combination with the compound represented by the general formula (I). Thereby, since the resin material with the high glass transition temperature of hardened | cured material can be obtained and more excellent heat resistance is provided, the more outstanding curvature reduction effect is acquired.

  The hydroxyl equivalent of the triphenylmethane type phenol resin represented by the above general formula (II) is not particularly limited. Among these, from the viewpoint of stabilizing the warping behavior, it is preferably 70 to 150, and more preferably 80 to 120.

  The said semiconductor sealing resin material is replaced with a triphenylmethane type phenol resin as (B) hardening | curing agent, and novolak type phenol resins other than a biphenyl type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, and a triphenylmethane type. It is also preferable to include at least one selected from the group consisting of resins.

  The (B) curing agent preferably contains at least one biphenyl type phenol resin as a curing agent other than the triphenylmethane type phenol resin from the viewpoint of flame retardancy. Moreover, an aralkyl type phenol resin is preferable from a viewpoint of reflow resistance and curability. From the viewpoint of low hygroscopicity, dicyclopentadiene type phenol resin is preferable. From the viewpoint of curability, a novolac type phenol resin is preferable. The (B) curing agent preferably contains at least one selected from these phenolic resins.

  As a biphenyl type phenol resin, the phenol resin etc. which are shown by following General formula (XI) are mentioned, for example.

R ^{1 to} R ⁹ in the above general formula (XI) are each independently an alkyl group having 1 to 10 carbon atoms such as hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isopropyl group and isobutyl group, methoxy Group, ethoxy group, propoxy group, butoxy group, etc., C1-C10 alkoxy group, phenyl group, tolyl group, xylyl group, etc. aryl group, or benzyl group, phenethyl group, etc. 6 to 10 are aralkyl groups. Among them, a hydrogen atom and a methyl group are preferable. n shows the integer of 0-10.

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% by mass of a condensate having n of 1 or more. Mixtures of condensates containing at least% are preferred. As such a compound, MEH-7851 (trade name of Meiwa Kasei Co., Ltd.) is commercially available.
In the case of using a biphenyl type phenol resin, the content is preferably 30% by mass or more, more preferably 50% by mass or more, in the total mass of the (B) curing agent, in order to exhibit its performance. The mass% or more is more preferable.

As an aralkyl type phenol resin, a phenol * aralkyl resin, a naphthol * aralkyl resin etc. are mentioned. Among them, phenol-aralkyl resins represented by the following general formula (XII) are preferable, and phenol-aralkyl resins in which R in the following general formula (XII) is a hydrogen atom and the average value of n is 0 to 8 are more preferable. Specific examples include p-xylylene type phenol / aralkyl resins, m-xylylene type phenol / aralkyl resins, and the like.
When these aralkyl type phenol resins are used, the content is preferably 30% by mass or more, and more preferably 50% by mass or more in the total mass of the curing agent (B) in order to exert its performance.

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 0-10.
Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms for R include an alkyl group and the like.

  As a dicyclopentadiene type phenol resin, the phenol resin etc. which are shown by following General formula (XIII) are mentioned.

Here, R ¹ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² represents a substituted or unsubstituted monovalent hydrocarbon having 1 to 10 carbon atoms. Indicates a group. 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 an alkyl group.

  When using a dicyclopentadiene type phenol resin, the content is preferably 30% by mass or more, and more preferably 50% by mass or more in the total mass of the (B) curing agent in order to exhibit its performance.

  Examples of the novolak type phenol resin other than the triphenylmethane type phenol resin include a phenol novolak resin, a cresol novolak resin, a naphthol novolak resin (naphthalene type phenol resin), and the like. Among them, the phenol novolak resin and the naphthol novolak resin are 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 in the total mass of the (B) curing agent in order to exhibit its performance.

  Any one of these biphenyl type phenol resins, aralkyl type phenol resins, dicyclopentadiene type phenol resins and novolac type phenol resins may be used alone or in combination of two or more. In particular, by including a biphenyl type phenol resin or an aralkyl type phenol resin, the contact angle can be reduced, which is preferable. Further, the content of each phenol resin is preferably 60% by mass or more, more preferably 80% by mass or more in the total mass of the (B) curing agent.

  The hydroxyl equivalent of the phenol resin other than the triphenylmethane-type phenol resin in the curing agent (B) is not particularly limited. Among these, from the viewpoint of stabilizing the warping behavior, it is preferably 50 to 150, and more preferably 75 to 125.

The above biphenyl type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin and novolac type phenol resin are combined with the triphenylmethane type phenol resin represented by the above general formula (II) to form the (B) curing agent. It is preferable to mix. The combined use of the curing agent and the triphenylmethane-type phenol resin represented by the above general formula (II) can more effectively stabilize the warpage behavior.
The curing agent (B) is at least one selected from the group consisting of a biphenyl type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin and a novolac type phenol resin instead of the triphenylmethane type phenol resin. It is also preferred that it be.

  Equivalent ratio of (A) epoxy resin and (B) curing agent, that is, ratio of number of hydroxyl groups in curing agent to number of epoxy groups in epoxy resin (number of hydroxyl groups in curing agent / number of epoxy groups in epoxy resin) There is no particular restriction. It is preferable to set in the range of 0.5-2 in order to suppress each unreacted content to a low amount, and 0.6-1.3 is more preferable. In order to obtain a semiconductor encapsulating resin material excellent in moldability and reflow resistance, it is more preferably set in the range of 0.8 to 1.2.

(Curing accelerator)
The semiconductor encapsulating resin material preferably further contains at least one curing accelerator from the viewpoint of curability.
The curing accelerator is not particularly limited as long as it is generally used as a semiconductor sealing resin material. For example, 1,8-diaza-bicyclo [5.4.0] undec-7-ene, 1,5-diaza-bicyclo [4.3.0] nonene, 5,6-dibutylamino-1,8-diaza And cycloamidine compounds such as bicyclo [5.4.0] undec-7-ene; maleic acid anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, and the like. , 3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, etc. Compounds having an internal polarization formed by addition of compounds having a π bond such as quinone compounds, diazophenylmethane and phenol resin; benzyldimethylamine, trieta Tertiary amines such as triamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol and derivatives thereof; imidazoles such as 2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole and derivatives thereof Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine; maleic anhydride, quinone compound, diazophenylmethane, phenol Phosphorus compounds having an intramolecular polarization formed by addition of compounds having a π bond such as resins; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate 2-ethyl-4-methylimidazole tetraphenyl borate, tetraphenyl boron salts such as N- methylmorpholine tetraphenylborate; derivatives thereof. These may be used alone or in combination of two or more. Among these, an adduct of an organic phosphine and a quinone compound is preferable from the viewpoint of filling property and reflow resistance.

  When the said semiconductor sealing resin material contains a hardening accelerator, the content rate will not be restrict | limited especially if it is the quantity by which the hardening acceleration effect is achieved, but in the semiconductor sealing resin material total mass, it is 0.00. 005% by mass to 2% by mass is preferable, and 0.01% by mass to 0.5% by mass is more preferable. When it is 0.005% by mass or more, the curability in a short time is excellent. When it is 2% by mass or less, a good curing rate can be maintained, and a good molded product can be obtained.

(Coupling agent)
The semiconductor encapsulating resin material preferably further contains at least one coupling agent in order to enhance the adhesion between the above-described various resins used as a blending component and the (C) filler. The coupling agent is not particularly limited as it is generally used for semiconductor sealing resin materials. 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 coupling agents such as silane and γ-mercaptopropylmethyldimethoxysilane; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) Tananate, isopropyltri (N-aminoethyl-aminoethyl) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis ( Dioctyl pyrophosphate) Oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylic isostearoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tri (dioctyl phosphate) Titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis Tityl phosphite) titanate coupling agents such as titanate; and the like. 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 semiconductor sealing resin material includes a coupling agent, the total content of the coupling agent is preferably 0.037% by mass to 4.75% by mass in the semiconductor sealing resin material. It is more preferable that it is 05 mass%-3 mass%, and it is further more preferable that it is 0.1 mass%-2.5 mass%. If the content is 0.037% by mass or more, adhesion to the frame tends to be improved. If the content is 4.75% by mass or less, the moldability of the package tends to be improved.

(Coupling agent coverage)
When a coupling agent is used in the present invention, the coverage of the coupling agent on the (C) filler is preferably 0.3 to 1.0, more preferably 0.4 to 0.9, and more preferably Is preferably in the range of 0.5 to 0.8.
When the coverage of the coupling agent is 1.0 or less, air bubbles due to volatile components generated at the time of molding may be reduced, and the generation of voids in the thin-walled part may tend to be suppressed. Moreover, since the adhesive force of resin and said (C) filler falls that the coverage of a coupling agent is 0.3 or more, there exists a tendency for molded article intensity 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 the number of coupling agent types used)
(Zzz) S _f = B ₁ × W ₁ + B ₂ × W ₂ + ... + B _l × W _l (l is the number of filler materials used)

Here, A and M respectively represent the minimum coverage area of each coupling agent and the amount thereof used, and B and W each represent the specific surface area of the (C) filler and the amount thereof used.
The minimum coating area of the coupling agent is an area per unit weight of the coupling agent when it is assumed that the coupling agent covers the filler as a monomolecular film, and is represented by the following (zza) equation.
Minimum covering area (m ² /g)=(6.02×10 ²³ × 13 × 10 ⁻²⁰ ) / molecular weight of coupling agent ... (zza)

(Method of controlling coupling agent coverage)
If the minimum coating area and specific surface area of each coupling agent to be used and the (C) filler are known, from the formula (xxx), formula (yyy) and formula (zzz), It is possible to calculate the used amount of the coupling agent and the filler (C).

(Flame retardants)
The semiconductor sealing resin material may further contain at least one of various flame retardants from the viewpoint of flame retardancy.
The flame retardant is not particularly limited and is generally used for semiconductor encapsulating resin materials. For example, brominated epoxy resins such as diglycidyl etherified tetrabromobisphenol A and brominated phenol novolac epoxy resins. 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-mentioned aluminum hydroxide, magnesium hydroxide and composite metal hydroxide.
From the viewpoint of recent environmental problems and high-temperature storage characteristics, non-halogen and non-antimony flame retardants are preferable. Among them, phosphoric acid esters are preferable from the viewpoint of filling property, and composite metal hydroxides are preferable from the viewpoint 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, and a, b, c, d, p, q and m are positive numbers, and r is 0 or a positive number.
Among these, a compound where r in the composition formula (XX) is 0, that is, a compound represented by the following composition formula (XXa) is more preferable.
m (M ¹ aOb) · n (M ² cOd) · l (H ₂ O) (XXa)
Here, M ¹ and M ² indicate different metal elements, and a, b, c, d, m, n and l indicate 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. From the viewpoint of flame retardancy, M ¹ is a metal element of the third period, an alkaline earth metal element of group IIA, a group IVB, a group IIB, a group VIII, a group IB, so that M ¹ and M ² are not identical. It is preferably selected from metal elements belonging to Group IIIA and Group IVA, and M ² is preferably selected from transition metal elements of Groups IIIB to IIB, and M ¹ is magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, More preferably, it is selected from copper and zinc, and M ² is selected from iron, cobalt, nickel, copper and zinc. From the viewpoint of flowability, M ¹ is preferably magnesium, M ² is zinc or nickel, and more preferably M ¹ is magnesium and M ² is zinc.

The molar ratio of p, q, and r in the composition formula (XX) is not particularly limited as long as the effects of the present invention can be obtained, but r = 0, and the molar ratio p / q of p and q is 99/1 to It is preferably 50/50. That is, the molar ratio m / n of m and n in the above composition formula (XXa) is preferably 99/1 to 50/50.
In addition, the classification of the metal element is a periodic table with a long period type in which the typical element is A group and the transition element is B group (source: published by Kyoritsu Publishing Co., Ltd. “Chemical Dictionary 4” February 15, 1987 This was done on the basis of a 30th reprint of the day printing plate.

The shape of the composite metal hydroxide is not particularly limited. From the viewpoint of fluidity and filling properties, a polyhedral shape having an appropriate thickness is preferable to a flat plate shape. The composite metal hydroxide is easy to obtain polyhedral crystals as compared with the metal hydroxide.
When the semiconductor sealing resin material contains a composite metal hydroxide, the content is not particularly limited. It is preferable that it is 0.5 mass%-20 mass% in semiconductor encapsulation resin material total mass, It is more preferable that it is 0.7 mass%-15 mass%, 1.4 mass%-12 mass% Further preferred. 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.

(Others)
Moreover, the said semiconductor sealing resin material can also contain an anion exchanger from a viewpoint of improving the moisture resistance of semiconductor elements, such as IC, and high-temperature leaving characteristics.
There is no restriction | limiting in particular as said anion exchanger, A conventionally well-known thing can be used. For example, hydrotalcites and hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, bismuth and the like can be mentioned. These can be used alone or in combination of two or more. Among 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)

  The above-mentioned semiconductor sealing resin material includes, as other additives, higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylene, release agents such as polyethylene polyethylene, colorants such as carbon black, silicone oil, Stress relaxation agents such as silicone rubber powder can be contained as required.

(Mold of semiconductor sealing resin material)
The semiconductor sealing resin material is formed into a pellet or sheet having a predetermined thickness after the concentration of the filler (C) is set to a predetermined level or more as described above. Thereby, generation | occurrence | production of fine powder can be suppressed significantly. As a result, it is possible to reduce the occurrence of package conveyance failure due to the fine powder scattered from the sealing material being solidified on the conveyance path or adhering to the conveyance device.
The molded body may be in the form of a pellet or sheet having a predetermined thickness, and scales other than thickness (for example, capacity, surface area, surface area, etc.), plane and cross-sectional shapes are not particularly limited. Absent. Generally, it is appropriately selected according to the mold of the apparatus used when molding. Here, "pellet-like" means one formed into a mass of any shape so that the semiconductor sealing resin material can be easily processed as a sealing material. The “sheet-like” means that the above-mentioned semiconductor sealing resin material is formed into a single layer or a laminate of two or more layers.

  The thickness of the semiconductor sealing resin material represents the maximum value of the thickness of the molded body when the molded body is in a pellet form, and represents the average value in the case of a sheet form. The thickness of the semiconductor encapsulation resin material can be measured by a caliper or a micrometer. In this case, the allowable error is ± 1 mm as a general error range as an error range of measurement with a caliper.

  The thickness of the semiconductor sealing resin material is set to 3 mm to 10 mm from the viewpoint of the depth of the cavity of the molding machine. If it is less than 3 mm, the pellet or sheet in the cavity is less likely to have a thermal history, and the resin may be molded at a hard stage, which may damage the chip. If it exceeds 10 mm, it may hit the upper mold of the mold before the resin melts, and the mold may be damaged. From the viewpoint of damage to the mold and heat history, it is preferably 4 mm to 7 mm.

The method for molding the semiconductor encapsulating resin material into a pellet or a sheet is not particularly limited. For example, a method in which the semiconductor encapsulating resin material is melt-extruded and molded at a predetermined heating temperature using a commonly used molding machine, while heating. The method of injection molding etc. are mentioned.
In the molding, conditions such as heating temperature are not particularly limited. For example, the molding temperature (mold temperature) is preferably in the range of 100 ° C. to 175 ° C., and more preferably 150 ° C. or less from the viewpoint of low warpage.
Further, after molding, the cured product of the obtained semiconductor sealing resin material may be further subjected to post-molding heat treatment (after cure).

(Glass-transition temperature)
With respect to the cured semiconductor encapsulating resin material (cured product) obtained by molding the semiconductor encapsulating resin material under normal conditions of a molding temperature (mold temperature) of 175 ° C. or less, a heating temperature of 150 ° C. The glass transition temperature of the cured product is preferably 150 ° C. or more from the viewpoint of warpage suppression when heat treatment after forming (after cure) is further performed below. At 150 ° C. or higher, warping can be satisfactorily suppressed after molding or heat treatment. The glass transition temperature of the cured semiconductor encapsulating resin material is more preferably 160 ° C. or higher.

  In order for the glass transition temperature of the cured product to satisfy the above condition, for example, the semiconductor sealing resin material includes at least one compound represented by the general formula (I) and the general formula (II). And the method of comprising including at least 1 sort (s) of the compound shown by these.

  As a method for measuring the glass transition temperature, a TMA method (differential expansion method) can be used. For example, the linear expansion curve of a test piece having a size of 19 mm × 3 mm × 3 mm cut out from each cured product before and after after-curing is measured by a method of measuring under a condition of a heating rate of 5 ° C./min. The glass transition temperature is determined based on the inflection point of the linear expansion coefficient. Furthermore, from the linear expansion curve, the linear expansion coefficient at a predetermined temperature in the temperature range (glass range) below the glass transition temperature is read. Usually, the linear expansion coefficient at 40 ° C. is the linear expansion coefficient in the glass region. The measurement of the linear expansion curve is performed, for example, using TMASS6000 manufactured by Seiko Instruments Inc.

(Preparation method of use)
The semiconductor encapsulation resin material can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, a raw material of a predetermined blending amount is sufficiently mixed by a mixer, etc., then mixed or melt-kneaded by a mixing roll, an extruder, a raking machine, a planetary mixer, etc., then cooled and removed as necessary. A foam, the method of grind | pulverizing etc. can be mentioned.
As a method for sealing a semiconductor device using the semiconductor sealing resin material as a sealing material, a low-pressure transfer molding method is generally used, and an injection molding method, a compression molding method, and the like are also included. A dispensing method, a casting method, a printing method or the like may be used. Compression molding is preferred from the viewpoint of collective sealing.

(Semiconductor device)
Subsequently, the semiconductor device of the present invention will be described. Moreover, the preferable application and usage method of the semiconductor sealing resin material of this invention are demonstrated through description of this semiconductor device.
The semiconductor device of the present invention includes, for example, an FO type package manufactured by compression molding using a semiconductor sealing resin material as shown in FIG. Here, as a semiconductor sealing resin material, the semiconductor sealing resin material of this invention is used. In the semiconductor device of the FO type package shown in FIG. 2, the chip 3 is disposed on the rewiring layer 6, and the chip 3 is sealed with a sealing material 4 which is a thermosetting product of the semiconductor sealing resin material of the present invention. ing. The bumps 6 are disposed on the surface of the redistribution layer 6 opposite to the surface on which the chips 3 are disposed, and the chips 3 and the wiring board are electrically connected via the bumps 6.

  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 semiconductor sealing resin material can be used. It is. In addition, even if these semiconductor devices are stacked type packages in which two or more elements are stacked on a mounting substrate, two or more elements are sealed with a semiconductor sealing resin material at a time. It may be a stopped mold package. By using the semiconductor sealing resin material as a sealing material for such a semiconductor device, it is possible to ensure a stable warping behavior after molding or after heat treatment, and to greatly reduce the generation of fine powder.

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 semiconductor sealing resin material on the chip 3 by compression molding and thermosetting it, a molded body in which the chip 3 is covered 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 compression molding using a semiconductor sealing resin material, it is preferably sealed (molded) at less than 175 ° C., more preferably 150 ° C. or less, From the viewpoint of reducing warpage, 130 ° C. or less is more preferable.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, evaluation of each semiconductor sealing resin material and a semiconductor device was performed based on the evaluation method demonstrated later, unless it mentions specially.

<Manufacturing of semiconductor encapsulation resin materials>
(Examples 1-14, Comparative Examples 1-12)
Using the materials described below as (A) epoxy resin, (B) curing agent, (C) filler, and (D) other additives so that the formulations shown in Tables 1 to 4 are used, each material is premixed. After (dry blending), the mixture is further kneaded for 15 minutes with a biaxial roll at a roll surface temperature of 90 ° C. to 110 ° C. and then cooled and crushed, and 5.5 mm in thickness at a molding temperature of 25 ° C. in a 43 mm diameter mold. Tablet (pellet-like) molding was performed, and each semiconductor sealing resin material of Examples 1-14 and Comparative Examples 1-12 was manufactured.
In addition, each composition in Tables 1-4 was shown by the mass part. Moreover, "-" in Tables 1-4 indicates that it is not blended.

(A) Epoxy resin The following was used as an epoxy resin.
-(Epoxy resin 1): Triphenylmethane type epoxy resin, product name 1032H60 manufactured by Mitsubishi Chemical Corporation (epoxy equivalent 170, melting point 60 ° C)
· (Epoxy resin 2): Product name NC-3000 (Epoxy equivalent weight 280) manufactured by Nippon Kayaku Co., Ltd. as a biphenylene type epoxy resin,
· (Epoxy resin 3): Product name YX-8800 (epoxy equivalent 178) manufactured by Mitsubishi Chemical Corporation as a dihydroanthracene type epoxy resin
-(Epoxy resin 4): Product name ESCN-190 (epoxy equivalent 200) manufactured by Sumitomo Chemical Co., Ltd. as an ortho-cresol novolak type resin
· (Epoxy resin 5): As a sulfur atom-containing epoxy resin, product name YSLV-120TE (epoxy equivalent 242) manufactured by Nippon Steel Corp.
-(Epoxy resin 6): Product name YX-4000 (Epoxy equivalent 192, melting point 67 ° C) manufactured by Mitsubishi Chemical Corporation as a biphenyl type epoxy resin.
(Epoxy resin 7): Product name HP-7200 (epoxy equivalent 264) manufactured by Dainippon Ink & Chemicals, Inc. as a dicyclopentadiene type epoxy resin

(B) Hardener (B) The following was used as a hardener.
· (Curing agent 1): Product name MEH-7500 (hydroxy group equivalent 104) manufactured by Meiwa Kasei Co., Ltd. as a triphenylmethane-type phenol resin
· (Curing agent 2): Product name SN-395 (hydroxyl equivalent 105) manufactured by Nippon Steel Chemical Co., Ltd. as a naphthalene type phenolic resin
· (Curing agent 3): product name HE200C-10 manufactured by Air Water Chemical Co., Ltd. as a biphenylene type phenolic resin
-(Curing agent 4): Product name HP-850N (hydroxyl equivalent 108) manufactured by Hitachi Chemical Co., Ltd. as a phenol novolac type phenolic resin
(Curing agent 5): Product name MEH-7800 (hydroxyl equivalent 97) manufactured by Meiwa Kasei Co., Ltd. as a phenol resin

(C) Filler As the (C) filler, spherical fused silica (average particle size of 14.1 μm, specific surface area of 3.5 m ² / g) that passed through a sieve having an opening of 53 μm was used.
(D) Other additives The following were used as (D) other additives.
· (Hardening accelerator 1): Adduct of triisobutylphosphine and 1,4-benzoquinone · (Coupling agent 1): Secondary aminosilane (made by Toray Dow Silicone Co., Ltd., product name Y-9669) was used.
・ (Carbon black): Mitsubishi Chemical Corporation, product name MA-600MJ-S

(Example 15)
Example 15 (Example 15) in the same manner as Example 3 except that after the tablet (pellet-like) molding in Example 3 was further heat-treated at 60.degree. C., the surface fine powder was fixed to the tablet (pellet-like). 3) was produced.

(Examples 16 to 17)
The (C) filler used in Example 1 is replaced with the following, and the composition is as shown in Table 2, and the other components are the same as in Example 1 except for the semiconductor encapsulating resin material of Example 16 and 17. Manufactured.
In Example 16, (C) spherical fused silica (average particle size 11.3 μm, specific surface area 3.3 m ² / g) that passed through a sieve with an opening of 30 μm was used as the filler.
In Example 17, spherical fused silica (average particle size 10.5 μm, specific surface area 3.5 m ² / g) that passed through a sieve having an opening of 20 μm was used as the filler (C).
As other additives, carbon black (manufactured by Mitsubishi Chemical Co., Ltd., product name MA-600MJ-S) was used so as to obtain the formulations shown in Table 2, respectively.
Other than that was carried out similarly to Example 1, and tablet (pellet-shaped) shaping | molding was performed, and the semiconductor sealing resin material was manufactured.

(Comparative example 13)
The curing accelerator used in Example 1 (A) epoxy resin, (B) curing agent, (C) filler, and D) other additives was replaced with the following, and (A) epoxy resin and (B) Curing agent, (C) Filler and coupling agent are pre-mixed with three rolls, then the remaining materials shown in Table 4 are added to the mixture, and mixed using a rough machine. In the same manner as Example 1, Comparative Example 13 which is a liquid semiconductor sealing resin material was produced.

(A) Epoxy resin (Epoxy resin 8): Product name SB-403S (epoxy equivalent 181) manufactured by Nippon Kayaku Co., Ltd. as a bisphenol F type epoxy resin

(B) Curing agent · (hardening agent 6): Product name MT-500 (acid anhydride equivalent 164) manufactured by Shin Nippon Rika Co., Ltd. as methyl tetrahydroxy anhydride.
(C) Filler As the (C) filler, spherical fused silica (average particle diameter 29.7 μm, specific surface area 1.7 m ² / g) that passed through a sieve having an opening of 53 μm was used.
(D) Other additives The following were used as the curing accelerator (the coupling agent and carbon black are the same as in Example 1).
・ (Curing Accelerator 2): Asahi Kasei Chemicals Corporation as microcapsule type imidazole

(Comparative Example 14)
While replacing the (C) filler used in Example 1 with the one used in Comparative Example 13 and mixing the respective materials as in Comparative Example 13, (A) epoxy resin, (B) curing agent and (C) filler And the coupling agent are premixed with three rolls, then the remaining materials shown in Table 5 are added thereto, mixed using a milling machine, and after cooling and pulverizing each kneaded material, the diameter is 90 mm. Comparative Example 14 which is a semiconductor sealing resin material was produced in the same manner as in Example 1 except that it was molded into a sheet having a thickness of 0.8 mm at a molding temperature of 80 ° C. using a metal mold.

(Comparative Example 15)
In the same manner as in Example 1, each kneaded material was cooled and pulverized so as to have the composition shown in Table 5, and then formed into a tablet (pellet shape) to a thickness of 11 mm at a molding temperature of 80 ° C. with a mold having a diameter of 30 mm. Except that, Comparative Example 15 as a semiconductor sealing resin material was produced in the same manner as Example 1.

(Comparative example 16)
After cooling and pulverizing each of the kneaded materials so as to obtain the composition shown in Table 5 in the same manner as in Example 1, the particle size of the obtained powdery semiconductor sealing resin material is sieved with a hand sieve. Comparative Example 16 which is a classified semiconductor encapsulating resin material was produced in the same manner as in Example 1 except that fine powder of 0.5 mm or less and coarse particles of 1 mm or more were respectively removed.

(Comparative Example 17)
After cooling and pulverizing each of the kneaded materials so as to obtain the compounding as shown in Table 5 in the same manner as in Example 1, Example 1 and Example 1 were repeated except that the obtained semiconductor sealing resin material was granulated by centrifugal milling. Similarly, the comparative example 17 which is a granular semiconductor sealing resin material was produced.

  The produced semiconductor sealing resin materials of Examples 1 to 17 and Comparative Examples 1 to 17 were evaluated by the following tests. The evaluation results are shown in Tables 1 to 5.

〔Evaluation method〕
(Glass-transition temperature)
In the measurement of the glass transition temperature after curing the semiconductor encapsulation resin material of the present invention, the semiconductor encapsulation resin material is molded at a temperature of 175 ° C. for 90 seconds, and then heat treated at 150 ° C. for 1 hour It carried out using the molded article for transition temperature measurement.

(Warpage after molding)
A method for measuring warpage will be described with reference to FIG. The molding temperature is set to 125 ° C., and the semiconductor sealing resin material is molded into a disk shape of 8 inches in 300 seconds, and then heat treatment is performed at 150 ° C. for 1 hour. Thereafter, the carrier and the temporary tacking tape are removed on a hot plate at 180 ° C., and the resulting molded article is placed on a table with the convexed surface facing down on the table and the end of the molded article The height from the table was measured with a ruler, and the measured value was taken as the warp after molding.
In the case of evaluation of the curvature after shaping | molding, the case where the curvature after the heat processing after the said shaping | molding exceeded 2 mm was made into "x". In addition, evaluation of warpage after the heat treatment is warpage after treating the molded article after peeling off the carrier and the temporary tacking tape at 200 ° C. for 1 hour in a nitrogen atmosphere, and 10 at 260 ° C. which is a reflow condition. Warpage after each second treatment was measured with a ruler, and in any case, warpage exceeding 2 mm was regarded as "x".
In addition, when the warpage exceeded 1.5 mm and 2 mm or less, “Δ”, when it exceeded 1 mm and 1.5 mm or less, “◯”, and when it was 1 mm or less, “◎”.

  As shown in Examples 1 to 17, it was found that the semiconductor encapsulating resin material of the present invention showed excellent characteristics with little warping and molding defects after molding and after heat treatment after molding.

(Chip breakage, damage to mold and generation of fine powder)
The semiconductor sealing resin material of Examples 1 to 17 and Comparative Examples 14 to 17 formed into various shapes was used as a sealing material, and the semiconductor device was sealed by compression molding. Then, the influence on the molded and sealed semiconductor device was examined.
As a result, in Comparative Example 14 in which the semiconductor encapsulating resin material was formed into a thin sheet, chip cracking was observed, and in Comparative Example 15 in which the semiconductor sealing resin material was formed into a thick tablet (pellet shape), the mold was damaged during molding. Was recognized. This is considered to be a defect that occurs because the heat history of the resin material is not good during molding, and the resin is not sufficiently melted.
In Comparative Example 16, which was not formed into pellets or sheets and classified, generation of fine powder and voids were observed, and in Comparative Example 17, which was granulated, voids were observed. As described above, when the sealing material is supplied as powder, the air in the material is not sufficiently removed, which suggests that defects such as voids occur after molding.
On the other hand, in Examples 1 to 17, no defects such as generation of voids, chip breakage, or damage to the mold occurred.

  From the above, the semiconductor encapsulating resin material of the present invention for FO type packaging is more stable than various conventional materials and is much less expensive than the liquid semiconductor encapsulating resin material. It is advantageous in that it can Moreover, in the present invention, by making the supply form a pellet or sheet, the generation of fine powder is greatly reduced, and defects due to voids, chip cracking and damage to the mold can be suppressed, and its industrial value is It is large.

  1: Carrier, 2: Temporary tacking tape, 3: Chip, 4: Sealant, 5: Bump, 6: Rewiring layer

Claims (5)

(A) An epoxy resin, (B) a curing agent, and (C) a filler, wherein the content of the (C) filler is 85% by mass or more, and is formed into a pellet or sheet having a thickness of 3 mm to 10 mm. a body, used at 0.99 ° C. or less of the molding temperature,
The (A) epoxy resin contains a compound represented by the following general formula (I),
Wherein the molded body molding temperature 175 ° C. or less, a glass transition temperature of the semiconductor sealing resin material for compression molding Ru der 0.99 ° C. or more when cured at a molding after heat treatment temperature 0.99 ° C. or less.



(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 1 to 10.) The semiconductor encapsulation resin material for compression molding according to claim 1 , wherein the curing agent (B) contains a compound represented by the following general formula (II).

(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 1 to 10.) 3. The semiconductor molding resin material for compression molding according to claim 1, wherein a glass transition temperature when the molded body is cured at a molding temperature of 175 ° C. or less and a post-molding heat treatment temperature of 150 ° C. or less is 160 ° C. or more. . The semiconductor sealing resin material for compression molding according to any one of claims 1 to 3 , wherein the (C) filler is a particle group capable of passing through a sieve having an opening of 55 µm. The semiconductor device provided with the element sealed by the semiconductor sealing resin material for compression molding of any one of Claims 1-4 .