CN1768112A - Epoxy resin molding material for sealing and semiconductor device - Google Patents

Abstract

The present invention provides a resin composition for sealing a semiconductor, which is an epoxy resin molding material for sealing a semiconductor package, comprising an epoxy resin, (B) a curing agent and (C) an inorganic filler as essential components, wherein the inorganic filler (C) has a flat particle diameter of 12 [ mu ] m or less and a specific surface area of 3.0m²(ii) a ratio of/g or more.

Description

Epoxy resin molding material for sealing and semiconductor device

This application is based on Japanese patent applications previously filed by the same applicant, namely Japanese Patent Application No. 2003-103346 (application date April 7, 2003), Japanese Patent Application No. 2003-103357 (application date April 7, 2003), Special Application No. 2003-103435 (application date April 7, 2003), Special Application No. 2003-103438 (application date April 7, 2003) and Special Application No. 2003-103443 (application date April 7, 2003) , the specification of which is hereby incorporated by reference.

technical field

The present invention relates to an epoxy resin molding material for sealing and a semiconductor device.

More specifically, the present invention relates to an epoxy resin molding material for encapsulation having excellent filling properties suitable for an underfill for flip-chip mounting. Further, the present invention relates to a flip-chip-mounted semiconductor device sealed with the epoxy resin molding material for sealing, which has few molding defects such as voids and is excellent in reliability such as reflow resistance and moisture resistance.

Background technique

In the field of element sealing of electronic components such as transistors and ICs, resin sealing has been the mainstream, and epoxy resin molding materials have been widely used due to productivity and cost considerations. This is because epoxy resin has a good balance of various properties such as electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.

In recent years, with the development of high-density mounting of electronic components on printed circuit boards, semiconductor devices have shifted from pin-type packages to surface-mount packages. In addition, surface mount ICs, LSIs, etc. have become thin and small packages in order to increase the mounting density and reduce the mounting height. Therefore, the area occupied by the components in the package increases, and the thickness of the package becomes very thin. In addition, with the multi-functionalization and large-capacity of components, the increase in chip area and multi-pin are promoted, and the increase in the number of pads (electrodes) promotes the reduction of pad spacing and the reduction of pad size. This is the so-called pad pitch narrowing. In addition, in order to respond to further miniaturization and weight reduction, the packaging method is also changing from QFP (small square planar package), SOP (small outline package), etc. to CSP ( chip size package) and BGA (ball grid array package). In recent years, these packaging technologies have developed new structures such as flip chip type, stacked (stacked) type, flip chip type, and wafer level type in order to achieve high speed and multifunctionality.

Flip-chip mounting is a connection technology that replaces the conventional wire bonding method. Soldering bumps are attached to the pads of the semiconductor chip, and the bumps are used to connect to the pads on the circuit board. In addition, after the chips with bumps are aligned on the circuit board, the solder is melted by reflow, and the electrical and mechanical connections are formed through automatic fine-tuning steps. In order to improve various reliability of the devices thus mounted, underfill is injected into the gaps of the chips/boards connected by solder bumps. And in order to completely fill the narrow gap where the solder bumps have been placed without creating voids, etc., the underfill needs to have high fillability.

In order to solve this problem, conventionally, a liquid-type sealing epoxy resin molding material using a solvent or a solvent-free system mainly composed of a bisphenol-type epoxy resin is used, and the capillary phenomenon is used to penetrate into the gap between the chip and the circuit board, and then way of curing.

However, the cost of liquid-type sealing epoxy resin molding materials is high, so in consideration of cost reduction, a new vacuum-type molding technology using solid-type sealing epoxy resin molding materials has been developed for flip chips. bottom padding. However, conventional solid-type molding materials have low fillability, so it is difficult to seal without defects such as voids. For example, in the process of manufacturing next-generation flip-chip semiconductor devices with fine-pitch solder bumps and the like, if epoxy resin is used for conventional solid-type sealing, voids with a diameter of about 0.1 mm will be generated. However, the underfill portion cannot be sufficiently filled. In addition, from the trend of finerization of flip-chip mounted semiconductor devices, that is, reduction in bump height and bump pitch, increase in the number of bumps and flip-chip area along with the increase in the number of inputs and outputs, it will be required in the future Higher fillability.

Therefore, there is a need for an epoxy resin molding material for encapsulation having excellent filling properties suitable for underfills for flip-chip mounting. In addition, there is a need for a flip-chip semiconductor device including fine-pitch solder bumps and the like that is free from molding defects and has good reliability such as reflow resistance and moisture resistance.

However, instead of the conventional lead frame used as an interposer, the semiconductor device in the front-end field established at present is a MAP in which several elements are mounted on an organic substrate or a ceramic substrate, molded at one time using an epoxy resin molding material, and then diced. (Module array package) forming method. This method has gradually become the mainstream of forming methods because it can reduce material costs and improve productivity. At this time, from the viewpoint of high-speed and multi-functionalization of components, instead of Au wires used to connect components and wiring, solder balls are mounted on components, and solder balls are used to connect to pads on circuit boards. A method called flip chip mounting. After the chips with solder balls are aligned on the circuit board, the solder balls are melted by reflow, and electrical and mechanical connections are formed through automatic fine-tuning steps.

However, the reliability of flip-chip mounting is significantly reduced because the surface of the component and the solder ball are in contact with the air. Therefore, how to combine with the above-mentioned MAP molding method to improve reliability, realize miniaturization and speed up of semiconductors, and improve productivity.

In terms of combined flip-chip mounting and MAP molding, there are problems such as substrate warpage after molding and package warpage after single-chip dicing. In addition, substrate warpage will significantly hinder the process of dicing into individual semiconductor chips after forming and the process of mounting solder bumps. In addition, package warpage will cause poor connection when mounted on a circuit board due to lack of flatness.

In order to solve this problem, the technology that has been used to seal the surface of the component and the solder ball part, that is, the method of filling a liquid resin called an underfill, has been studied. However, the cost of liquid resin is higher than that of epoxy resin molding materials, and the substrate is easy to warp after the resin is cured. Therefore, it cannot support the sealing of large-sized substrates for the purpose of improving productivity, so the applicability of epoxy resin molding materials that are low-cost and excellent in dimensional stability has begun to be studied.

A new vacuum molding technology using a solid-type sealing epoxy resin molding material for flip chip underfill has been developed. However, conventional solid molding materials use a method in which the amount of filler is less than that of epoxy resin molding materials for SMD in order to improve filling properties. Therefore, when the epoxy resin molding materials are cured, the substrate and package are likely to warp due to shrinkage.

Therefore, there is a need for an epoxy resin molding material for sealing that can maintain proper fillability when used as an underfill for flip-chip mounting, and can reduce warpage of the substrate and package after sealing, and has no molding defects such as voids after sealing. It is a flip-chip mounted semiconductor device with excellent reliability such as reflow resistance and moisture resistance.

A first aspect of the present invention is to provide an epoxy resin molding material for sealing suitable for sealing a flip-chip mounting type semiconductor device having fine-pitch bumps and a large number of input and output (bump count). In addition, there is also provided a flip-chip-mounted semiconductor device sealed with the sealing epoxy resin molding material of the present invention, having fine-pitch bumps and having a large number of input and output (bump count).

The second aspect of the present invention is to provide a sealing device capable of reducing production problems caused by substrate warping after sealing a flip-chip mounted semiconductor device, and problems such as package warping that prevents mounting on a circuit board. Epoxy resin molding material. In addition, there is also provided a flip-chip sealed with the epoxy resin molding material for sealing of the present invention, which can reduce production problems caused by substrate warpage and package warping that makes it difficult to mount to a circuit board. A chip-mounted semiconductor device.

Contents of the invention

The present invention involves the following matters.

1. An epoxy resin molding material for sealing, comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and the average particle diameter of the inorganic filler (C) is 12 μm or less Its specific surface area is 3.0 m ² /g or more.

2. An epoxy resin molding material for sealing, containing (A) epoxy resin, (B) curing agent and (C) inorganic filler, and described inorganic filler (C) is that the maximum particle size is 63 μm or or less, and contain 5 wt% or more of inorganic fillers with a particle size of 20 μm or more.

3. An epoxy resin molding material for sealing, comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and the average particle diameter of the inorganic filler (C) is 15 μm or less and a specific surface area of 3.0 to 6.0 m ² /g, used in a semiconductor device having one or more of the configurations (a1) to (d1),

(a1) The bump height of the flip chip is 150 μm or less;

(b1) The bump pitch of the flip chip is 500 μm or less;

(c1) The area of the semiconductor chip is 25 mm ² or more;

(d1) The total thickness of the sealing material is 2 mm or less.

4. An epoxy resin molding material for sealing, containing (A) epoxy resin, (B) curing agent and (C) inorganic filler, and the specific surface area of the inorganic filler (C) is 3.0 to 6.0 m ² /g, further containing (D) coupling agent.

5. An epoxy resin molding material for sealing, containing (A) epoxy resin, (B) curing agent and (C) inorganic filler, and the epoxy resin molding material for sealing satisfies vitrification based on the TMA method At least one of the conditions of a temperature of 150° C. or more, a flexural modulus of 19 GPa or less based on JIS-K6911, and a molding shrinkage rate of 0.2% or less according to JIS-K6911.

Description of drawings

FIG. 1 is a cross-sectional view of a flip-chip BGA (underfill type) sealed with an epoxy resin molding material (sealing material) for sealing.

Fig. 2 is a cross-sectional view of a flip-chip BGA (stamper molding) sealed with an epoxy resin molding material (sealing material) for sealing.

FIG. 3 is a plan view (partial perspective view) when a semiconductor chip 3 is disposed on a circuit board 1 with solder bumps 2 interposed therebetween.

4 is a cross-sectional view (x) and a plan view (y) of a semiconductor device (flip-chip BGA) after integral sealing (MAP molding) by molding.

In the figure, 1 is a circuit board; 2 is a solder bump; 3 is a semiconductor chip; 4 is a sealing material; 5 is an underfill; a is a bump height; b is a bump pitch; c is an area of a semiconductor chip; d is the total thickness of the sealing material; 11 is the circuit board; 12 is the welding bump; 13 is the semiconductor chip; 14 is the sealing material.

Detailed ways

As a result of earnest research by the present inventors to solve the above-mentioned problems, it has been found that a specific semiconductor device sealing epoxy resin molding material containing a specific inorganic filler as an essential component, and using the sealing epoxy resin molding material can be sealed. semiconductor device, to achieve the above objects, so that the present invention has been accomplished.

(epoxy resin)

The (A) epoxy resin used in the present invention may be a material commonly used in epoxy resin molding materials for sealing, and is not particularly limited, for example, phenol novolak type epoxy resin; o-cresol novolak type epoxy resin; Oxygen resins; phenols such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, etc. And/or α-naphthol, β-naphthol, dihydroxynaphthalene and other naphthols and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde and other compounds having aldehyde groups Oxides; diglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted bisphenols; stilbene-type epoxy resins; hydroquinone-type epoxy resins; phthalic acid, dimer acid Glycidyl ester type epoxy resin obtained by reacting polybasic acids such as diaminodiphenylmethane and cyanuric acid with epichlorohydrin; ; Epoxides of polycondensation resins of dicyclopentadiene and phenols; epoxy resins with naphthalene rings; epoxides of aralkyl type phenolic resins such as phenol-aralkyl resins, naphthol-aralkyl resins, etc. ; Trimethylolpropane type epoxy resin; Terpene modified epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing olefin bonds with peracids such as peracetic acid; Alicyclic epoxy resin; Sulfur atom-containing epoxy resin Resins, etc., these may be used alone or in combination of two or more.

Among them, from the viewpoints of filling properties and reflow resistance, biphenyl epoxy resins, bisphenol F epoxy resins, stilbene epoxy resins, and sulfur atom-containing epoxy resins are preferred; , preferably novolak-type epoxy resin; from the viewpoint of low hygroscopicity, preferably dicyclopentadiene-type epoxy resin; from the viewpoint of heat resistance and low warpage, preferably naphthalene-type epoxy resin, triphenyl The methane-type epoxy resin preferably contains at least one of the aforementioned epoxy resins.

Biphenyl type epoxy resin can enumerate the epoxy resin etc. shown in following general formula (IV), bisphenol F type epoxy resin can enumerate the epoxy resin shown in following general formula (V), stilbene type Examples of epoxy resins include epoxy resins represented by the following general formula (VI), and examples of sulfur atom-containing epoxy resins include epoxy resins represented by the following general formula (VII).

(In the formula, R ¹ to R ⁸ are selected from hydrogen atoms and substituted or unsubstituted monovalent hydrocarbon groups with 1 to 10 carbon atoms, all of which may be the same or different. n is an integer of 0 to 3.)

(In the formula, R ¹ to R ⁸ are selected from hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, 6 to 6 carbon atoms ～10 aralkyl groups, all of which can be the same or different. n is an integer of 0～3.)

(In the formula, R ¹ to R ⁸ are selected from hydrogen atoms and substituted or unsubstituted monovalent hydrocarbon groups with 1 to 5 carbon atoms, all of which may be the same or different. n is an integer of 0 to 10.)

(In the formula, R ¹ to R ⁸ are selected from hydrogen atoms, substituted or unsubstituted alkyl groups with 1 to 10 carbon atoms, substituted or unsubstituted alkoxy groups with 1 to 10 carbon atoms, all of which may be the same or different. n is an integer from 0 to 3.)

As the biphenyl type epoxy resin represented by the above-mentioned general formula (IV), for example, 4,4'-bis(2,3-epoxypropoxy)biphenyl or 4,4'-bis(2 , 3-glycidoxy)-3,3',5,5'-tetramethylbiphenyl as the main component of epoxy resin, epichlorohydrin and 4,4'-bisphenol or 4,4'- (3,3',5,5'-tetramethyl)bisphenol reaction epoxy resin etc. Among them, an epoxy resin mainly composed of 4,4'-bis(2,3-glycidoxy)-3,3',5,5'-tetramethylbiphenyl is preferable.

As the bisphenol F-type epoxy resin represented by the above-mentioned general formula (V), commercially available products include R ¹ , R ³ , R ⁶ and R ⁸ as methyl groups, R ² , R ⁴ , R ⁵ and R ⁷ is a hydrogen atom and YSLV-80XY (trade name manufactured by Nippon Steel Chemical Co., Ltd.) whose main component is n=0.

The stilbene-type epoxy resin represented by the above general formula (VI) can be obtained by reacting stilbene-based phenols and epichlorohydrin as raw materials in the presence of an alkaline substance. The stilbene-based phenols used as raw materials include, for example, 3-tert-butyl-4,4'-dihydroxy-3',5,5'-trimethylstilbene, 3-tert-butyl-4,4'- Dihydroxy-3',5',6-trimethylstilbene, 4,4'-dihydroxy-3,3',5,5'-trimethylstilbene, 4,4'-dihydroxy-3', 3-di-tert-butyl-5,5'-dimethylstilbene, 4,4'-dihydroxy-3',3-di-tert-butyl-6,6'-dimethylstilbene, etc., among which 3- tert-butyl-4,4'-dihydroxy-3',5,5'-trimethylstilbene and 4,4'-dihydroxy-3',3,5,5'-tetramethylstilbene. These stilbene 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 (VII), preferred are epoxy resins in which 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. Resin; more preferably R ² , R ³ , R ⁶ and R ⁷ are hydrogen atoms, R ¹ and R ⁸ are tert-butyl, and R ⁴ and R ⁵ are methyl epoxy resins. Such a compound is available as a commercial item such as YSLV-120TE (manufactured by Nippon Steel Chemical Co., Ltd.).

The above-mentioned epoxy resins may be used alone or in combination of two or more, but in order to exert its performance, the mixing amount relative to the total amount of the epoxy resin is preferably 20% by weight or more, more preferably 30% by weight or more, and especially preferably 50% by weight or more.

Examples of the novolak-type epoxy resin include epoxy resins represented by the following general formula (VIII), and the like.

(In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group selected from a hydrogen atom and a carbon number of 1 to 10, and n is an integer of 0 to 10.)

The novolak type epoxy resin shown in above-mentioned general formula (VIII) can obtain easily by reacting epichlorohydrin in novolac type phenolic resin, wherein, R in general formula (VIII) is preferably methyl, ethyl , propyl, butyl, isopropyl, isobutyl and other alkyl groups with 1 to 10 carbon atoms; methoxy, ethoxy, propoxy, butoxy and other alkoxy groups with 1 to 10 carbon atoms group, more preferably a hydrogen atom or a methyl group. n is preferably an integer of 0-3. Among the novolak-type epoxy resins represented by the above general formula (VIII), o-cresol novolak-type epoxy resins are preferred.

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

Examples of the dicyclopentadiene-type epoxy resin include epoxy resins represented by the following general formula (IX), and the like.

(In the formula, ^R1 and ^R2 are respectively selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is an integer of 0 to 6.)

^R in above-mentioned formula (IX) can enumerate as hydrogen atom; Methyl, ethyl, propyl, butyl, isopropyl, tert-butyl etc. alkyl; Vinyl, allyl, butenyl etc. Alkenyl; substituted or unsubstituted monovalent hydrocarbon groups with 1 to 5 carbon atoms such as haloalkyl, amino-substituted alkyl, and mercapto-substituted alkyl, among which alkyl groups such as methyl and ethyl groups and hydrogen atoms are preferred, and methyl and ethyl groups are more preferred. groups and hydrogen atoms. ^R can be enumerated as hydrogen atom; Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group; Alkenyl group such as vinyl group, allyl group, butenyl group; Haloalkyl group, A substituted or unsubstituted monovalent hydrocarbon group having 1 to 5 carbon atoms such as an amino-substituted alkyl group and a mercapto-substituted alkyl group, among which a hydrogen atom is preferred.

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

Naphthalene-type epoxy resins include epoxy resins represented by the following general formula (X), and triphenylmethane-type epoxy resins include epoxy resins represented by the following general formula (X1).

(In the formula, R ¹ to R ³ are respectively selected from hydrogen atoms, substituted or unsubstituted monovalent hydrocarbon groups with 1 to 12 carbon atoms, all of which may be the same or different. p is 1 or 0, and 1 and m are each An integer of 0 to 11, and (1+m) is an integer of 1 to 11, and (1+p) is an integer of 1 to 12. i is an integer of 0 to 3, j is an integer of 0 to 2, and k is 0 Integer of ~4.)

Naphthalene-type epoxy resins represented by the above-mentioned general formula (X) include, for example, random copolymers containing one structural unit and m structural units in disorder, alternating copolymers containing alternately, and copolymers containing regularly , The block copolymers contained in the form of blocks can be used alone or in combination of two or more.

(In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group selected from a hydrogen atom and a carbon number of 1 to 10, and n is an integer of 1 to 10.)

These epoxy resins may be used alone or in combination, but in order to exert its performance, the mixing amount is preferably 20% by weight or more, more preferably 30% by weight or more, and especially preferably 50% by weight relative to the total amount of the epoxy resin. %or above.

The above-mentioned biphenyl type epoxy resin, stilbene type epoxy resin, sulfur atom-containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and triphenylmethane type epoxy resin Resins can be used alone or in combination of two or more, but the mixing amount is preferably 50% by weight or more, more preferably 60% by weight or more, and especially preferably 80% by weight or more.

The melt viscosity at 150° C. of the (A) epoxy resin used in the present invention is preferably 2 poise or less, more preferably 1 poise or less, and especially preferably 0.5 poise or less from the viewpoint of filling properties. Here, the melt viscosity refers to a viscosity measured with an ICI cone and plate viscometer.

(Hardener)

The (B) curing agent used in the present invention can be a material commonly used in epoxy resin molding materials for sealing, without particular limitation, for example, condensation or polycondensation of phenol, cresol, resorcinol, Phenols such as catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and/or naphthols such as α-naphthol, β-naphthol, and dihydroxynaphthalene, together with formaldehyde, benzaldehyde, and salicylaldehyde Novolak-type phenolic resins obtained from compounds having aldehyde groups; phenol-aranes obtained by synthesizing phenols and/or naphthols with dimethoxy-p-xylene or bis(methoxymethyl)biphenyl Aralkyl type phenolic resins such as naphthol-aralkyl resins; dicyclopentadiene type phenol novolak type resins obtained by copolymerization of phenols and/or naphthols with cyclopentadiene, naphthol aldehyde Dicyclopentadiene-type phenolic resins such as varnish-type resins; terpene-modified phenolic resins, etc., these may be used alone or in combination of two or more.

Among them, from the viewpoint of flame retardancy, biphenyl type phenolic resin is preferred; from the viewpoint of reflow resistance and curability, aralkyl type phenolic resin is preferred; from the viewpoint of low hygroscopicity, dicyclopentadiene is preferred. Alkene-type phenolic resin; from the viewpoint of heat resistance, low expansion rate and low warpage, triphenylmethane-type phenolic resin is preferred; from the viewpoint of curability, novolak-type phenolic resin is preferred, preferably containing at least one of these Phenolic Resin.

Examples of the biphenyl type phenolic resin include phenolic resins represented by the following general formula (XII), and the like.

R ¹ to R ⁹ in the above formula (XII) may all be the same or different, and are selected from hydrogen atoms, methyl, ethyl, propyl, butyl, isopropyl, isobutyl and other groups with 1 to 1 carbon atoms. Alkyl groups with 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms such as ethoxy, propoxy, and butoxy, aryl groups with 6 to 10 carbon atoms such as phenyl, tolyl, and xylyl groups, and benzyl groups, Aralkyl groups having 6 to 10 carbon atoms such as phenethyl group, among which hydrogen atom and methyl group are preferred. n is an integer of 0-10.

The biphenyl type phenolic resin represented by the above-mentioned general formula (XII) includes, for example, compounds in which all of R ¹ to R ⁹ are hydrogen atoms, etc., and among them, from the viewpoint of melt viscosity, it is preferable to contain 50% by weight or more and n is 1 or A condensate mixture of the above condensate. Such a compound is available as a commercial item such as MEH-7851 (trade name manufactured by Meiwa Kasei Co., Ltd.).

When using a biphenyl type phenolic resin, in order to exert its performance, the compounding amount is preferably 30% by weight or more, more preferably 50% by weight or more, and especially preferably 60% by weight or more, based on the total amount of the curing agent.

The aralkyl type phenolic resin can be enumerated as phenol-aralkyl resin, naphthol-aralkyl resin etc., preferably the phenol-aralkyl resin shown in following general formula (XIII), more preferably general formula (XIII) R in the phenol-aralkyl resin is a hydrogen atom and the average value of n is 0-8. Specific examples include p-xylene type phenol-aralkyl resins, meta-xylene type phenol-aralkyl resins, and the like. When using these aralkyl-type phenolic resins, in order to exhibit their performance, the compounding amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the curing agent.

(In the formula, R is a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 0 to 10.)

Examples of dicyclopentadiene-type phenolic resins include phenolic resins represented by the following general formula (XIV), and the like.

(In the formula, ^R1 and ^R2 are each independently selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, n is an integer of 0 to 10, and m is an integer of 0 to 6. )

When a dicyclopentadiene type phenolic resin is used, in order to exert its performance, the compounding amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the curing agent.

Triphenylmethane type phenolic resins include phenolic resins represented by the following general formula (XV).

(In the formula, R is selected from a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group with 1 to 10 carbon atoms, and n is an integer of 1 to 10.)

When a triphenylmethane type phenolic resin is used, in order to exert its performance, the compounding amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the curing agent.

Examples of novolak-type phenolic resins include phenol novolac resins, cresol novolac resins, and naphthol novolac resins, among which phenol novolak resins are preferred. When a novolac type phenolic resin is used, in order to exert its performance, the compounding amount is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the curing agent.

The above-mentioned biphenyl type phenolic resin, aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, triphenylmethane type phenolic resin and novolac type phenolic resin can be used alone or in combination of two or more. The total compounding amount is preferably 60% by weight or more, more preferably 80% by weight or more, relative to the total amount of the curing agent.

From the viewpoint of fillability, the melt viscosity at 150°C of the curing agent (B) used in the present invention is preferably 2 poise or less, more preferably 1 poise or less. Here, melt viscosity means ICI viscosity.

(A) The equivalent ratio of epoxy resin to (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 (the number of hydroxyl groups in the curing agent/the number of epoxy groups in the epoxy resin) has no It is particularly limited, but it is preferably set in the range of 0.5 to 2, more preferably 0.6 to 1.3 in order to suppress each unreacted component. In order to obtain an epoxy resin molding material for sealing having excellent moldability and reflow resistance, it is more preferable to set it in the range of 0.8 to 1.2.

(inorganic filler)

The (C) inorganic filler used in the present invention is added to the epoxy resin molding material for sealing for the purpose of hygroscopicity, lowering the coefficient of linear expansion, improving thermal conductivity, and increasing strength, such as fused silica, crystalline silica, Alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconia, zircon, forsterite, steatite, spinel Powders such as stone, mullite, titanium dioxide, etc., or made into spherical beads, glass fibers, etc. In addition, examples of inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and the like.

These inorganic fillers may be used alone or in combination of two or more. Among them, fused silica is preferable from the viewpoint of filling property and reduction of the linear expansion coefficient, 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 resistance.

The (C) inorganic filler used in the present invention preferably has an average particle diameter of 15 μm or less and a specific surface area of 3.0 to 6.0 m ² /g, so that it can meet the requirements of underfill for flip-chip mounting with fine-pitch bumps. Filling. The average particle diameter is more preferably 10 μm or less, particularly preferably 8 μm or less. When the thickness exceeds 15 μm, it becomes difficult to inject the epoxy resin molding material into the gap between the chip and the circuit board connected by bumps, and the fillability decreases. In addition, the specific surface area is more preferably 3.5 to 5.5 m ² /g, and particularly preferably 4.0 to 5.0 m ² /g. When it is less than 3.0 m ² /g and exceeds 6.0 m ² /g, voids are likely to be generated in the gaps between chips and circuit boards connected by bumps, and the fillability will be reduced.

The coarse particle component of the (C) inorganic filler may be sieved out with a sieve from the viewpoint of filling properties. In this case, the component (C) with a thickness of 53 μm or more is preferably 0.5% by weight or less, more preferably the component (C) with a thickness of 30 μm or more is 0.5% by weight or less, and it is especially preferable that the component (C) with a thickness of 20 μm or more is 0.5% by weight or less. the following.

From the viewpoint of fillability and reliability, the compounding amount of (C) the inorganic filler is preferably 60 to 95% by weight, more preferably 70 to 90% by weight, and especially preferably 75 to 85% by weight with respect to the sealing epoxy resin molding material. . When it is less than 60% by weight, the reflow resistance tends to be lowered, and when it exceeds 95% by weight, the filling property tends to be lowered.

(coupling agent)

In order to improve the adhesiveness between the resin component and the filler, it is preferable to add a coupling agent to the epoxy resin molding material for sealing of the present invention. A coupling agent can be used together as needed within the range in which the effects of the present invention are obtained. The coupling agent can be a substance commonly used in epoxy resin molding materials for sealing, without particular limitation, for example, silane compounds having primary, secondary or tertiary amino groups, epoxy silane, mercapto silane, alkyl silane, Various silane compounds such as phenyl silane, ureido silane, and vinyl silane, titanium compounds, aluminum chelate compounds, aluminum/zirconium compounds, etc. These may be used alone or in combination of two or more.

The total mixing amount of the coupling agent is preferably 0.037 to 4.75% by weight, more preferably 0.088 to 2.3% by weight, based on the sealing epoxy resin molding material. When it is less than 0.037% by weight, the adhesion to the circuit board tends to be reduced. In addition, when it exceeds 4.75% by weight, volatile components increase, and molding defects related to filling properties such as voids are likely to occur, and the packaging body tends to be reduced. Formability.

(Silane coupling agent with secondary amino group)

The above-mentioned coupling agent is preferably a silane coupling agent (D2) having a secondary amino group, but other coupling agents may be used in combination as necessary within the range in which the effect of the present invention can be achieved.

The (D2) silane coupling agent with a secondary amino group used in the present invention can be a silane compound with a secondary amino group in the molecule, without special limitations, for example, γ-anilinopropyltrimethoxysilane, γ-anilinopropyl trimethoxysilane, γ-anilinopropyl Triethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ- Anilinopropylethyldimethoxysilane, γ-anilinomethyltrimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ -Anilinomethylmethyldiethoxysilane, γ-anilinomethylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N-(p-methoxyphenyl )-γ-aminopropyltrimethoxysilane, N-(p-methoxyphenyl)-γ-aminopropyltriethoxysilane, N-(p-methoxyphenyl)-γ-aminopropyl Methyldimethoxysilane, N-(p-methoxyphenyl)-γ-aminopropylmethyldiethoxysilane, N-(p-methoxyphenyl)-γ-aminopropylethyl Diethoxysilane, N-(p-methoxyphenyl)-γ-aminopropylethyldimethoxysilane, γ-(N-methyl)aminopropyltrimethoxysilane, γ-(N -Ethyl)aminopropyltrimethoxysilane, γ-(N-butyl)aminopropyltrimethoxysilane, γ-(N-benzyl)aminopropyltrimethoxysilane, γ-(N-methyl Base) aminopropyltriethoxysilane, γ-(N-ethyl)aminopropyltriethoxysilane, γ-(N-butyl)aminopropyltriethoxysilane, γ-(N- Benzyl)aminopropyltriethoxysilane, γ-(N-methyl)aminopropylmethyldimethoxysilane, γ-(N-ethyl)aminopropylmethyldimethoxysilane, γ-(N-butyl)aminopropylmethyldimethoxysilane, γ-(N-benzyl)aminopropylmethyldimethoxysilane, N-(β-aminoethyl)-γ- Aminopropyltrimethoxysilane, γ-(β-aminoethyl)aminopropyltrimethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane wait.

Among them, aminosilane coupling agents represented by the following general formula (I) are preferable from the viewpoint of filling properties.

(In the formula, ^R1 is selected from a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 2 carbon atoms, and ^R2 is an alkyl group selected from 1 to 6 carbon atoms and a phenyl group , R ³ is methyl or ethyl, n is an integer of 1 to 6, and m is an integer of 1 to 3.)

The aminosilane coupling agent represented by the above-mentioned general formula (I) can be exemplified as γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldimethoxysilane γ-anilinopropylmethyldiethoxysilane, γ-anilinopropylethyldiethoxysilane, γ-anilinopropylethyldimethoxysilane, γ-anilinomethyl Trimethoxysilane, γ-anilinomethyltriethoxysilane, γ-anilinomethylmethyldimethoxysilane, γ-anilinomethylmethyldiethoxysilane, γ-anilino Methylethyldiethoxysilane, γ-anilinomethylethyldimethoxysilane, N-(p-methoxyphenyl)-γ-aminopropyltrimethoxysilane, N-(p-methyl Oxyphenyl)-γ-aminopropyltriethoxysilane, N-(p-methoxyphenyl)-γ-aminopropylmethyldimethoxysilane, N-(p-methoxyphenyl )-γ-aminopropylmethyldiethoxysilane, N-(p-methoxyphenyl)-γ-aminopropylethyldiethoxysilane, N-(p-methoxyphenyl)- γ-Aminopropylethyldimethoxysilane, etc. Especially preferred is gamma-anilinopropyltrimethoxysilane.

(D2) The amount of the silane coupling agent having a secondary amino group is preferably 0.037 to 4.75% by weight, more preferably 0.088 to 2.3% by weight, based on the epoxy resin molding material for sealing. When the content is less than 0.037% by weight, the fluidity is lowered, and molding defects related to filling properties such as voids are likely to occur, and the adhesiveness to the circuit board tends to be lowered. When it exceeds 4.75% by weight, volatile components will increase, and there will be a tendency to cause molding defects related to filling properties such as voids and lower the moldability of the package.

Other coupling agents that can be used in combination with (D2) silane coupling agents having secondary amino groups may be those used in general sealing epoxy resin molding materials, and are not particularly limited. For example, there are primary amino groups and/or tertiary amino groups. Amino silane compounds, epoxy silane, mercapto silane, alkyl silane, phenyl silane, ureido silane, vinyl silane and other silane compounds, titanium compounds, aluminum chelate compounds, aluminum/zirconium compounds, etc. . Specific examples include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ-Glycidoxypropylmethyldimethoxysilane , Vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxy Silane, γ-aminopropylmethyldiethoxysilane, γ-(N,N-dimethyl)aminopropyltrimethoxysilane, γ-(N,N-diethyl)aminopropyltrimethoxy γ-(N,N-dibutyl)aminopropyltrimethoxysilane, γ-(N-methyl)anilinopropyltrimethoxysilane, γ-(N-ethyl)anilinopropyl Trimethoxysilane, γ-(N,N-dimethyl)aminopropyltriethoxysilane, γ-(N,N-diethyl)aminopropyltriethoxysilane, γ-(N , N-dibutyl)aminopropyltriethoxysilane, γ-(N-methyl)anilinopropyltriethoxysilane, γ-(N-ethyl)anilinopropyltriethoxy Silane, γ-(N,N-dimethyl)aminopropylmethyldimethoxysilane, γ-(N,N-diethyl)aminopropylmethyldimethoxysilane, γ-(N , N-dibutyl)aminopropylmethyldimethoxysilane, γ-(N-methyl)anilinopropylmethyldimethoxysilane, γ-(N-ethyl)anilinopropyl Methyldimethoxysilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxy Dimethoxysilane, Dimethyldimethoxysilane, Methyltriethoxysilane, γ-Chloropropyltrimethoxysilane, Hexamethyldisilane, Vinyltrimethoxysilane, γ-Mercaptopropylmethyl Silane coupling agents such as dimethoxysilane; isopropyl triisostearyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (N-aminoethyl- Aminoethyl) titanate, tetraoctylbis(ditridecylphosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(bistridecyl) Alkyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyltricaprylyl Titanate, Isopropyl Dimethacryl Isostearyl Titanate, Isopropyl Trilaurylbenzenesulfonyl Titanate, Isopropyl Isostearyl Diacryl Titanate, Isopropyl Titanate coupling agents such as tris(dioctyl phosphite) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis(dioctyl phosphite) titanate, etc., These may be used alone or in combination of two or more.

When using such another coupling agent, the compounding amount of (D) the silane coupling agent having a secondary amino group is preferably 30% by weight or more, more preferably 50% by weight or more, based on the total amount of the coupling agent, in order to exert performance.

The total compounding amount of the coupling agent containing the above-mentioned (D2) silane coupling agent having a secondary amino group is preferably 0.037 to 4.75% by weight, more preferably 0.088 to 2.3% by weight, based on the sealing epoxy resin molding material. When it is less than 0.037% by weight, the adhesion to the circuit board tends to be reduced, and when it exceeds 4.75% by weight, the volatile components increase, and it tends to cause molding defects related to filling properties such as voids, and tends to reduce the packaging body. Formability. Moreover, the compounding quantity of the said coupling agent with respect to (C) inorganic filler becomes like this. Preferably it is 0.05 to 5 weight%, More preferably, it is 0.1 to 2.5 weight%. The reason for specifying the mixing amount is the same as above.

(Coupling agent coverage)

When the coupling agent is used in the present invention, the coverage ratio of the coupling agent to the inorganic filler is preferably 0.3-1.0, more preferably 0.4-0.9, and even more preferably 0.5-0.8. When the coverage ratio of the coupling agent is greater than 1.0, air bubbles are increased due to volatile components generated during molding, so voids tend to be easily generated in thin-walled parts. In addition, when the coverage ratio of the coupling agent is less than 0.3, the adhesive force between the resin and the filler decreases, and the strength of the molded product tends to decrease.

The coupling agent coverage X of the epoxy resin molding material is defined as the formula (xxx).

X(%)＝S _c /S _f (xxx)

In the formula, S _c and S _f are respectively the total minimum coverage area of all coupling agents and the total surface area of all fillers of the epoxy resin molding material, which are defined by (yyy) formula and (zzz) formula.

S _c ＝A ₁ ×W ₁ +A ₂ ×W ₂ …+A _n ×M _n (n is the number of coupling agents used)(yyy)

S _f ＝B ₁ ×W ₁ +B ₂ ×W ₂ …+B ₁ ×W ₁ (1 is the number of filling materials used)(zzz)

In the formula, A and M are the minimum coverage area and usage amount of each coupling agent, respectively, and B and W are the specific surface area and usage amount of each filler.

(method of controlling coupler coverage)

If the minimum coverage area and specific surface area of each coupling agent and inorganic filler used in the epoxy resin molding material are known, the target coupling agent coverage can be calculated from the (xxx) formula, (yyy) formula and (zzz) formula rate of coupling agent and filling material usage.

(phosphorus compound)

From the viewpoint of filling properties and flame retardancy, it is preferable that the present invention further contains (E) a phosphorus compound. The (E) phosphorus compound used in the present invention is not particularly limited, for example, red phosphorus with or without coverage; phosphorus and nitrogen compounds such as cyclic phosphazine; -Phosphonates such as 1,1-dicalcium diphosphonate; triphenylphosphine oxide, 2-(diphenylphosphinyl)hydroquinone, 2,2-[(2-(diphenylphosphine oxide) Phosphine compounds such as base)-1,4-phenylene)bis(oxymethylene)]bis-oxirane, tri-n-octylphosphine oxide; ester compounds with phosphorus atoms, cyclic phosphazine, etc. Phosphorus and nitrogen compounds, etc., these may be used alone or in combination of two or more. Among them, phosphoric acid esters and phosphine oxides are preferable from the viewpoint of moisture resistance reliability.

Since red phosphorus acts as a flame retardant, it is not particularly limited as long as the effects of the present invention can be obtained, but red phosphorus covered with a thermosetting resin, red phosphorus covered with an inorganic compound or an organic compound, or the like is preferred.

The thermosetting resin used for the red phosphorus covered with a thermosetting resin is not particularly limited, for example, epoxy resin, phenolic resin, melamine resin, polyurethane resin, cyanate resin, urea-formaldehyde resin, aniline-formaldehyde resin, furan resin , polyamide resin, polyamideimide resin, polyimide resin, etc., these may be used alone or in combination of two or more. In addition, monomers or oligomers of these resins may be used to cover and polymerize at the same time to cover the thermosetting resin obtained by polymerization, or the thermosetting resin may be coated first and then cured. Among them, epoxy resins, phenol resins, and melamine resins are preferable from the viewpoint of compatibility with the matrix resin mixed with the sealing epoxy resin molding material.

The inorganic compound used for the red phosphorus covered with an inorganic compound and an organic compound is not particularly limited, for example, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, titanium hydroxide, zirconium hydroxide, hydrous zirconium oxide, bismuth hydroxide , barium carbonate, calcium carbonate, zinc oxide, titanium oxide, nickel oxide, iron oxide, etc., these can be used alone or in combination of two or more. Among them, zirconium hydroxide, hydrous zirconium oxide, aluminum hydroxide, and zinc oxide are preferable, which are excellent in replenishing effect of phosphate ions.

In addition, the organic compounds used for the red phosphorus covered with inorganic compounds and organic compounds are not particularly limited, for example, low molecular weight compounds used in surface treatment such as coupling agents and chelating agents, thermoplastic resins, thermosetting resins, etc. compounds, etc., these may be used alone or in combination of two or more. Among them, thermosetting resins are preferable from the viewpoint of covering effect, and epoxy resins, phenol resins, and melamine resins are more preferable from the viewpoint of compatibility with the matrix resin mixed with the sealing epoxy resin molding material.

When covering red phosphorus with inorganic compounds and organic compounds, the order of the covering treatment is not particularly limited, and the organic compounds can be covered after covering the inorganic compounds, or the inorganic compounds can be covered after covering the organic compounds, or a mixture of the two can be used for simultaneous covering. In addition, the covering form is not particularly limited, and may be physical adsorption, chemical combination or other forms. In addition, after covering, the inorganic compound and the organic compound may exist separately or may be partially or completely combined.

As long as the effect of the present invention can be obtained, the amount of the inorganic compound and the organic compound is not particularly limited, and the weight ratio (inorganic compound/organic compound) of the inorganic compound to the organic compound is preferably 1/99 to 99/1, more preferably 10/90 to 95/5, especially preferably 30/70 to 90/10, it is preferable to adjust the usage-amounts of monomers and oligomers that are inorganic compounds and organic compounds or their raw materials so as to be this weight ratio.

The production method of red phosphorus covered with thermosetting resin or red phosphorus covered with inorganic compounds and organic compounds is not particularly limited, for example, JP-A-62-21704 and JP-A-52-131695 can be used The known covering method described in et al. In addition, the thickness of the covering film is not particularly limited as long as the effect of the present invention can be obtained, and the covering film may be uniformly or nonuniformly covered on the surface of the red phosphorus.

The particle size of red phosphorus is not particularly limited as long as the effect of the present invention can be obtained, but the average particle size (particle size of 50% by weight based on cumulative particle size distribution) is preferably 1 to 100 μm, more preferably 5 to 50 μm. When the average particle size is less than 1 μm, the concentration of phosphate ions in the molded product tends to increase and the moisture resistance tends to deteriorate. There is a tendency to cause defects such as wire deformation, short circuit, and breakage.

Phosphorous and nitrogen-containing compounds have a flame retardant effect, so as long as the effect of the present invention can be obtained, there is no particular limitation. For example, it can be mentioned that the main chain skeleton contains repeating compounds shown in the following formula (XXV) and/or the following formula (XXVI). A cyclic phosphazine compound of the unit, or a compound containing repeating units represented by the following formula (XXVII) and/or the following formula (XXVIII) with different substitution positions for the phosphorus atom in the phosphazine ring, etc.

In the formulas (XXV) and (XXVII), m is an integer of 1 to 10; R ¹ to R ⁴ are selected from alkyl and aryl groups with 1 to 12 carbon atoms that may have substituents, all of which may be the same or identical. different; A is an alkylene or arylene group with 1 to 4 carbon atoms. In formula (XXVI) and formula (XXVIII), n is an integer of 1 to 10; R ⁵ to R ⁸ are selected from alkyl or aryl groups with 1 to 12 carbon atoms that may have substituents, all of which may be the same or similar different; A is an alkylene or arylene group with 1 to 4 carbon atoms. In addition, m R ¹ , R ² , R ³ , R ⁴ in the formula may all be the same or different, and n R ⁵ , R ⁶ , R ⁷ , R ⁸ may be all the same or different. In the above formula (XXV) to formula (XXVIII), the optionally substituted alkyl or aryl group having 1 to 12 carbon atoms represented by R ¹ to R ⁸ is not particularly limited, and examples thereof include methyl, ethyl Alkyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and other alkyl groups; phenyl, 1-naphthyl, 2-naphthyl and other aryl groups; o-tolyl, m-tolyl , p-tolyl, 2,3-xylyl, 2,4-xylyl, o-cumenyl, m-cumenyl, p-cumenyl, lysyl and other alkyl-substituted aryl groups; benzyl, phenylethyl An aryl group such as a substituent for an alkyl group, etc., and the substituted substituents include, for example, an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an amino group, an epoxy group, a vinyl group, a hydroxyalkyl group, and an alkylamino group.

Among the above, an aryl group is preferable, and a phenyl group or a hydroxyphenyl group is more preferable from the viewpoint of heat resistance and moisture resistance of the epoxy resin molding material. Among them, preferably at least one of R ¹ to R ⁴ is hydroxyphenyl, all of R ¹ to R ⁸ may be hydroxyphenyl, but more preferably one of R ¹ to R ⁴ is hydroxyphenyl. When R ¹ ~ R ⁸ are all hydroxyphenyl groups, it is easy to make the cured epoxy resin brittle. In addition, when R ¹ ~ R ⁸ are all phenyl groups, they cannot enter the cross-linked structure of the epoxy resin, and it is easy to reduce the curing rate of the epoxy resin. The heat resistance of the material.

In the above formula (XXV) to formula (XXVIII), the alkylene or arylene group having 1 to 4 carbon atoms represented by A is not particularly limited, for example, methylene, ethylene, propylene, Isopropylidene, butylene, isobutylene, phenylene, tolylylene, xylylene, naphthylene, etc. Among them, from the viewpoint of heat resistance and moisture resistance of epoxy resin molding materials, Arylene is preferred, and phenylene is more preferred.

Cyclic phospharazine compound can be any polymer in above-mentioned formula (XXV)～formula (XXVIII), the copolymer of above-mentioned formula (XXV) and above-mentioned formula (XXVI), or above-mentioned formula (XXVII) and above-mentioned formula ( XXVIII) copolymer, in addition, the copolymer can be a random copolymer, a block copolymer or an alternating copolymer. The copolymerization molar ratio m/n is not particularly limited, but from the viewpoint of improving the heat resistance and strength of the cured epoxy resin, it is preferably 1/0 to 1/4, and more preferably 1/0 to 1/4. 1.5. Moreover, the degree of polymerization m+n is 1-20, Preferably it is 2-8, More preferably, it is 3-6.

Preferable cyclic phospharazine compounds include polymers of the following formula (XXIX), copolymers of the following formula (XXX), and the like.

(Here, in formula (XXIX), m is an integer of 0 to 9, and R ¹ to R ⁴ are each independently hydrogen or hydroxyl.)

In formula (XXX), m and n are integers of 0 to 9, R ¹ to R ⁴ are each independently selected from hydrogen or a hydroxyl group, and R ⁵ to R ⁸ are each independently selected from hydrogen or a hydroxyl group. In addition, the cyclic phospharazine compound represented by the above-mentioned formula (XXX) can be a substance containing m repeating units (a) and n repeating units (b) shown below in an alternating, block or random form, but It is preferably contained randomly.

Among them, a polymer whose main component is a polymer in which one of R ¹ to R ⁴ in the above formula (XXIX) is a hydroxyl group and m is ³ to ⁶ is preferred; One is a hydroxyl group, R ⁵ to R ⁸ are all hydrogen or one is a hydroxyl group, m/n is 1/2 to 1/3, and m+n is a copolymer of 3 to 6 as the main component. In addition, a commercially available phosphazine compound is, for example, SPE-100 (trade name manufactured by Otsuka Chemical Co., Ltd.).

The phosphoric acid ester may be an ester compound of phosphoric acid and an alcohol compound or a phenol compound, without particular limitation, for example, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylene base phosphate, cresol diphenyl phosphate, xylyl diphenyl phosphate, tris(2,6-dimethylphenyl) phosphate and aromatic condensed phosphate, etc. Among them, aromatic condensed phosphoric acid esters represented by the following general formula (II) are preferable from the viewpoint of hydrolysis resistance.

(In the formula, 8 Rs are alkyl groups having 1 to 4 carbon atoms, all of which may be the same or different. Ar is an aromatic ring).

Examples of the phosphoric acid ester of the above-mentioned formula (II) include phosphoric acid esters represented by the following structural formulas (XVI) to (XX), and the like.

The added amount of the phosphoric acid ester is preferably in the range of 0.2 to 3.0% by weight in terms of phosphorus atomic weight with respect to all the added components except the filler. When it is less than 0.2% by weight, the filling property is lowered, forming defects such as voids are likely to occur, and the flame-retardant effect tends to be lowered. If it exceeds 3.0% by weight, the formability and moisture resistance will be reduced, and the phosphate ester will bleed out during molding to hinder the appearance.

The phosphine oxide is preferably a compound represented by the following general formula (III).

(In the formula, R ¹ , R ² and R ³ are substituted or unsubstituted alkyl groups, aryl groups, aralkyl groups and hydrogen atoms with 1 to 10 carbon atoms, all of which may be the same or different. However, all hydrogen atoms are excluded. case of atoms).

Among the phosphorus compounds represented by the above general formula (I), R ¹ to R ³ are preferably substituted or unsubstituted aryl groups, especially preferably phenyl groups, from the viewpoint of hydrolysis resistance.

The compounding amount of the phosphine oxide relative to the sealing epoxy resin molding material is preferably 0.01 to 0.2% by weight of phosphorus atoms, more preferably 0.02 to 0.1% by weight, and especially preferably 0.03 to 0.08% by weight. If it is less than 0.01% by weight, the flame retardancy will decrease, and if it exceeds 0.2% by weight, the formability and moisture resistance will decrease.

(curing accelerator)

In the present invention, it is preferable to further add (F) a curing accelerator from the viewpoint of curability. The (F) curing accelerator used in the present invention can be a material commonly used in epoxy resin molding materials for sealing, and is not particularly limited. For example, 1,8-diaza-bicyclo(5,4, 0) Undecene-7, 1,5-diaza-bicyclo(4,3,0)nonene, 5,6-dibutylamino-1,8-diaza-bicyclo(5, 4,0) Cyclic amidine compounds such as undecene-7 and maleic anhydride, 1,4-benzoquinone, 2,5-tolylquinone, 1,4-naphthoquinone, 2,3- Dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4- Compounds with intramolecular polarization obtained from quinone compounds such as benzoquinone and phenyl-1,4-benzoquinone, compounds with π bonds such as diazophenylmethane, and phenolic resins; benzyldimethylamine, triethanolamine , dimethylaminoethanol, tris(dimethylaminomethyl)phenol and other tertiary amines and their derivatives; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and other imidazoles and their derivatives; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, diphenylphosphine, phenylphosphine and other organic phosphines and the phosphine Compounds with intramolecular polarization obtained by adding maleic anhydride, the above-mentioned quinone compounds, diazophenylmethane, phenolic resin and other compounds with π bonds; tetraphenylphosphonium tetraphenyl borate, Triphenylphosphine tetraphenyl borate, 2-ethyl-4-methylimidazolium tetraphenyl borate, N-methylmorpholine tetraphenyl borate and other tetraphenyl boron salts and their derivatives etc., these may be used alone or in combination of two or more. Among them, an adduct of an organic phosphine and a quinone compound is preferable from the viewpoint of filling properties and reflow resistance.

The mixing amount of the curing accelerator is not particularly limited as long as it is an amount capable of achieving a curing accelerating effect, but is preferably 0.005 to 2% by weight, more preferably 0.01 to 0.5% by weight, based on the sealing epoxy resin molding material. When it is less than 0.005% by weight, short-term curability tends to deteriorate, and when it exceeds 2% by weight, it is difficult to obtain a good molded article because the curing rate is too fast.

(flame retardant)

In the present invention, various flame retardants can be further added from the viewpoint of flame retardancy. The flame retardant may be a substance commonly used in epoxy resin molding materials for sealing, and is not particularly limited. Examples include diglycidyl ether compounds of tetrabromobisphenol A or brominated phenol novolac epoxy resins epoxy resin. In addition, phosphorus compounds such as antimony oxide, red phosphorus, and the above-mentioned phosphates, nitrogen-containing compounds such as melamine, melamine cyanurate, melamine-modified phenolic resin, and guanamine-modified phenolic resin; phosphorus/nitrogen compounds such as cyclic phosphazine Compounds; metal compounds such as zinc oxide, iron oxide, molybdenum oxide, ferrocene, the above-mentioned aluminum hydroxide, magnesium hydroxide and composite metal hydroxide, etc.

In view of recent environmental problems and high-temperature storage characteristics, non-halogen and non-antimony-based flame retardants are preferable. Among these, phosphoric acid 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 (XXI).

p(M ¹ aOb)·q(M ² cOd)·r(M ³ cOd)·mH ₂ O (XXI)

(In the formula, M ¹ , M ² and M ³ are mutually different metal elements, a, b, c, d, p, q and m are positive numbers, and r is 0 or a positive number).

Among them, the compound in which r is 0 in the compositional formula (XXI), that is, the compound represented by the following compositional formula (XXIa) is more preferable.

m(M ¹ aOb) n(M ² cOd) 1(H ₂ O) (XXIa)

(In the formula, M ¹ and M ² are metal elements different from each other, and a, b, c, d, m, n and 1 are positive numbers).

In the above-mentioned compositional formulas (XXI) and (XXIa), M1 ^{and M2} are metal elements different from each other, and are not particularly limited, but from the viewpoint of flame retardancy, ^M1 and ^M2 are preferably different, and ^M1 It is a metal element selected from the third period, an alkaline earth metal element of group IIA, a metal element belonging to group IVB, group IVB, group VIII, group IB, group IIIA and group IVA, and ^M2 is selected from group IIIB～IIB The transition metal element, more preferably M ¹ is selected from magnesium, calcium, aluminum, tin, titanium, iron, cobalt, nickel, copper and zinc, M ² is selected from iron, cobalt, nickel, copper and zinc. From the standpoint of fluidity, it is preferable that M ¹ is magnesium and M ² is zinc or nickel, and it is more preferable that M ¹ is magnesium and M ² is zinc.

As long as the effect of the present invention can be obtained, the molar ratio of p, q, and r in the above composition formula (XXI) is not particularly limited, but preferably r=0, and the molar ratio P/q of p and q is 99/1～ 50/50. That is, the molar ratio m/n of m and n in the composition formula (XXIa) is preferably 99/1 to 50/50.

In addition, the classification of metal elements is based on the long-period periodic table with typical elements as A subgroup and transition elements as B ferrous (published by Kyoritsu Publishing Co., Ltd. "Chemical Encyclopedia 4" on February 15, 1987 30th printing of miniature edition).

The shape of the composite metal hydroxide is not particularly limited, but it is preferably a polyhedral shape with an appropriate thickness from the viewpoint of fluidity and filling properties. In addition, composite metal hydroxides are more likely to obtain polyhedral crystals than metal hydroxides.

The mixing amount of the composite metal hydroxide is not particularly limited, but is preferably 0.5 to 20% by weight, more preferably 0.7 to 15% by weight, and particularly preferably 1.4 to 12% by weight relative to the sealing epoxy resin molding material. When it is less than 0.5% by weight, the flame retardancy tends to be insufficient, and when it exceeds 20% by weight, the filling property and reflow resistance tend to decrease.

(other ingredients)

In addition, an anion exchanger may be added to the sealing epoxy resin molding material of the present invention from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of semiconductor elements such as ICs. The anion exchanger is not particularly limited, and it can be a known substance, such as hydrotalcites or hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, bismuth, etc. These can be used alone or in combination of two or more . Among them, 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.)

Furthermore, other additives such as higher fatty acid, higher fatty acid metal salt, ester wax, polyolefin wax, release agent such as polyethylene and oxidized polyethylene, and coloring agents such as carbon black may be added to the sealing epoxy resin molding material of the present invention if necessary. Stress relieving agents such as silicone oil or silicone rubber powder, etc.

(heating loss rate)

The heating loss rate of the epoxy resin molding material must be 0.25% by weight or less, preferably 0.22% by weight or less, more preferably 0.20% by weight or less. If the heating weight loss rate exceeds 0.25% by mass, air bubbles will increase due to volatile components generated during molding, so voids are likely to occur in the thin portion.

(Definition of heating loss rate)

The weight W ₀ after adding the resin composition to the weight A heat-resistant container was measured. After leaving this to stand in 200 degreeC atmosphere for 1 hour, the total weight W of a container and a resin composition was measured. The heating loss rate Y at this time was calculated|required from the following formula.

Y＝100×(W ₀ -W)/(W ₀ -A)

(Control method of heating loss rate)

The volatile components produced when measuring the heating weight loss rate are mainly water and alcohols. Therefore, effective methods include reducing the moisture content of the epoxy resin molding material before molding, optimizing the minimum necessary amount of coupling agent, and using a coupling agent that is difficult to generate volatile components.

(Physical properties of epoxy resin molding material after curing)

It is preferable to use an epoxy resin molding material for sealing that satisfies at least one of the following conditions: a glass transition temperature of 150° C. or higher based on the TMA method, a flexural modulus of 19 GPa or lower based on JIS-K6911, a The molding shrinkage is 0.2% or less. More preferably, two or more of the above conditions are met, and it is especially preferred that all three are met. From the viewpoint of warpage, the glass transition temperature is preferably 160°C or higher, more preferably 170°C or higher. Warpage tends to increase below 150°C. From the viewpoint of warpage, the flexural modulus is preferably 18.5 GPa or less, more preferably 18 GPa or less. When it exceeds 19 GPa, warpage tends to increase. In addition, from the viewpoint of warpage, the molding shrinkage is preferably 0.18% or less, more preferably 0.15% or less. When it exceeds 0.2%, warpage tends to increase.

(Preparation and usage method)

The epoxy resin molding material for sealing of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, there are examples of sufficient mixing of a given amount of raw materials with a stirrer, etc. Finally, after mixing or melt-kneading with grinding rolls, extruders, grinders, planetary mixers, etc., cooling, and methods such as defoaming and pulverization as needed. In addition, if necessary, it can be made into tablets with a size and weight that meet the molding conditions.

Among the methods for sealing semiconductor devices using the sealing epoxy resin molding material of the present invention as a sealing material, the most common method is low-pressure transfer molding, and there are other methods such as injection molding and compression molding. Dispensing methods, casting methods, printing methods, etc. may also be used. From the viewpoint of filling properties, a molding method capable of molding under reduced pressure is preferable.

The epoxy resin molding material for sealing of the present invention will be described below with reference to several embodiments.

(first embodiment)

The first embodiment of the epoxy resin molding material for sealing of the present invention includes (A) an epoxy resin, (B) a curing agent, and (C) an average particle diameter of 12 μm or less and a specific surface area of 3.0 M ² /g or more inorganic filler epoxy resin molding material for sealing. At this time, the inorganic filler (C) preferably meets at least one of the following conditions: 50 wt% or more of particles with a particle size of 12 μm or less, 70 wt% or more of particles with a particle size of 24 μm or less, and 32 μm or less 80wt% and 90wt% or more of particles with a particle size of 48 μm or less. In addition, (C) the average particle diameter of the inorganic filler is preferably 10 μm or less. (C) The specific surface area of the inorganic filler is preferably 3.5 to 5.5 m ² /g.

It is preferable to select (A) epoxy resin, (B) curing agent, and (C) inorganic filler from the following viewpoints.

When the (A) epoxy resin is selected, the melt viscosity at 150° C. is preferably 2 poise or less, more preferably 1 poise or less. This selection is particularly effective when the mixing ratio of (C) the inorganic filler is high. Among them, at least one selected from biphenyl type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins, and sulfur atom-containing epoxy resins is preferably used from the viewpoint of filling properties and reliability. . Moreover, it is preferable to use at least 1 sort(s) selected from the naphthalene type epoxy resin and the triphenylmethane type epoxy resin from a viewpoint of reducing the warpage of a flip-chip mounting type package. In order to take into account filling and warping properties, it is preferable to use at least one selected from biphenyl type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins, and sulfur atom-containing epoxy resins together with naphthalene type epoxy resins. At least one selected from epoxy resins and triphenylmethane-type epoxy resins.

The (B) curing agent is preferably selected to have a melt viscosity at 150° C. of 2 poise or less, more preferably 1 poise or less. This selection is particularly effective when the mixing ratio of (C) the inorganic filler is high. And it is effective in the case of selecting at least one selected from novolak type epoxy resins as (A) epoxy resin from the viewpoint of formability, and in the case of selecting dicyclopentadiene type epoxy resin from the viewpoint of low hygroscopicity. In this case, at least one selected from naphthalene-type epoxy resins and triphenylmethane-type epoxy resins is selected from the viewpoint of heat resistance and low warpage.

(C) When selecting an inorganic filler with an average particle diameter of 15 μm or less and a specific surface area of 3.0 to 6.0 m ² /g, it is preferably within the range of an average particle diameter of 15 μm or less, considering that it is suitable for the flip-chip mounting of the present invention. It is enough to select the size that can be implanted according to the bump height and pitch of the type semiconductor device, but if the material is selected to be smaller than the required size, the fluidity and filling performance will be reduced. In order to avoid this situation, it is preferable to select a substance with a specific surface area in the range of 3.0 to 6.0 m ² /g. In order to make the average particle size and specific surface area fit within the above range, it is effective to adjust by combining two or more commercially available inorganic fillers.

In addition, coarse particle components in the (C) inorganic filler may be screened out with a sieve if necessary. The component (C) of 53 μm or more is preferably 0.5% by weight or less, the component (C) of 30 μm or more is more preferably 0.5% by weight or less, and the component (C) of 20 μm or more is especially preferably 0.5% by weight or less.

(C) When selecting an inorganic filler having an average particle diameter of 12 μm or less and a specific surface area of 3.0 m ² /g or more, it is preferably within the range of an average particle diameter of 12 μm or less, which is considered to be suitable for the flip-chip mounting type semiconductor of the present invention. It is enough to choose the size that can be injected according to the bump height and bump pitch of the device, but if the material is selected to be smaller than the required size, the fluidity will be reduced, so it should be avoided. In addition, it is preferable to select a material having a specific surface area of 3.0 m ² /g or more and a material as small as possible in the average particle diameter that can be injected. In order to make both the average particle diameter and the specific surface area fall within the above-mentioned ranges, it is effective to combine two or more commercially available inorganic fillers. In addition, coarse particle components in the (C) inorganic filler may be screened out if necessary. The component (C) of 53 μm or more is preferably 0.5% by weight or less, the component (C) of 30 μm or more is more preferably 0.5% by weight or less, and the component (C) of 20 μm or more is especially preferably 0.5% by weight or less.

In addition to the above components, any of (D2) a silane coupling agent having a secondary amino group, (E) a phosphorus compound, and (F) a curing accelerator may be added as needed. The epoxy resin molding material for flip-chip mounting type underfill sealing can be obtained by adjusting the combination and mixing amount of each component. The epoxy resin molding material for flip-chip mounting type underfill sealing can be obtained by adjusting the combination and mixing amount of each component.

(second embodiment)

A second embodiment of the epoxy resin molding material for sealing of the present invention includes (A) an epoxy resin, (B) a curing agent, and (C) a maximum particle size of 63 μm or less and a particle size of 20 μm or The above epoxy resin molding material for sealing with 5 wt % or more of inorganic filler. In this case, (C) the average particle diameter of the inorganic filler is preferably 10 μm or less. In addition, (C) the specific surface area of the inorganic filler is preferably 3.5 to 5.5 m ² /g. In addition, (A) epoxy resin, (B) hardening|curing agent, and (C) inorganic filler can be selected from the viewpoint similar to 1st Embodiment.

In addition to the above components, any of (D2) a silane coupling agent having a secondary amino group, (E) a phosphorus compound, and (F) a curing accelerator may be added as needed. The epoxy resin molding material for flip-chip mounting type underfill sealing can be obtained by adjusting the combination and mixing amount of each component.

When manufacturing next-generation flip-chip semiconductor devices with fine-pitch solder bumps, etc., when conventional solid-type sealing epoxy resins are used, the underfill cannot be filled due to the generation of slightly large voids with a diameter of about 0.1 mm. . However, by using the sealing epoxy resin molding material of the present invention according to the first and second embodiments as the sealing material, the above problems can be solved.

(third embodiment)

Regarding the third embodiment of the epoxy resin molding material for sealing of the present invention, the essential components contained are (A) epoxy resin, (B) curing agent, and (C) an average particle diameter of 15 μm or less and less than An epoxy resin molding material for sealing with an inorganic filler having a surface area of 3.0 to 6.0 m ² /g. The (A) epoxy resin, (B) curing agent, and (C) inorganic filler can be selected from the same viewpoint as in the first embodiment.

In addition to the above components, any of (D2) a silane coupling agent having a secondary amino group, (E) a phosphorus compound, and (F) a curing accelerator may be added as needed. The epoxy resin molding material for flip-chip mounting type underfill sealing can be obtained by adjusting the combination and mixing amount of each component. Especially for semiconductor devices with one or more of the following (a1) to (d1):

(a1) The bump height of the flip chip is 150 μm or less;

(b1) The bump pitch of the flip chip is 500 μm or less;

(c1) The area of the semiconductor chip is 25 mm ² or more;

(d 1) The total thickness of the sealing material is 2 mm or less.

(fourth embodiment)

A fourth embodiment of the epoxy resin molding material for sealing of the present invention includes a ring for sealing containing (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) a coupling agent. The oxygen resin molding material, wherein (C) the specific surface area of the inorganic filler is 3.0 to 6.0 m ² /g. The (A) epoxy resin, (B) curing agent, and (C) inorganic filler can be selected from the same viewpoint as in the first embodiment.

(D) The filler coverage of the coupling agent is preferably 0.3 to 1.0. In addition, the heating loss rate after heating at 200° C./1 hr is preferably 0.25% by weight or less. Other additives other than the above-mentioned components may also be added as needed. The epoxy resin molding material for flip-chip mounting type underfill sealing can be obtained by adjusting the combination and mixing amount of each component.

(fifth embodiment)

Regarding the fifth embodiment of the epoxy resin molding material for sealing of the present invention, among the epoxy resin molding materials for sealing containing at least (A) epoxy resin, (B) curing agent, and (C) inorganic filler, , an epoxy resin molding material for sealing that meets at least one of the following conditions: a glass transition temperature of 150°C or higher based on the TMA method; a flexural modulus of 19 GPa or lower based on JIS-K6911; a molding based on JIS-K6911 The shrinkage rate is 0.2% or less. The (A) epoxy resin, (B) curing agent, and (C) inorganic filler can be selected from the same viewpoint as in the first embodiment.

In this case, it can be used for semiconductor devices having one or more of the following (c1), (d1) and (g1):

(c1) The area of the semiconductor chip is 25 mm ² or more;

(d1) The total thickness of the sealing material is 2 mm or less;

(g1) The sealing material forming area of the one-shot forming method is 3000 mm ² or more.

In addition, it can be used in semiconductor devices having one or more of the following (c2), (d2) and (g2):

(c2) The area of the semiconductor chip is 50 mm ² or more;

(d2) The total thickness of the sealing material is 1.5 mm or less;

(g2) The sealing material forming area of the one-time forming method is 5000 mm ² or more.

The warp of the semiconductor device obtained in the fifth embodiment is 5.0 mm or less, and preferably the warp of the semiconductor device is 2.0 mm or less.

When manufacturing next-generation flip-chip semiconductor devices with fine-pitch solder bumps, etc., the bottom cannot be fully filled due to the generation of slightly large voids with a diameter of about 0.1 μm when using conventional solid-type sealing epoxy resin sealing. filling part. However, by using the sealing epoxy resin of the present invention typified by the above-mentioned first to fifth embodiments as a sealing material, the above-mentioned problems can be solved. That is, the epoxy resin molding material for encapsulation of the present invention is suitable for the manufacture of a semiconductor device having a given structure described in the semiconductor device section below.

In addition, according to the fifth embodiment, it is possible to reduce the warping of the substrate and the warping of the package after sealing while maintaining a suitable filling property as an underfill for flip-chip mounting.

(Embodiment 1 of semiconductor device)

Embodiments of the semiconductor device of the present invention will be described below with reference to FIGS. 1 to 4 . However, the semiconductor device of the present invention is not limited thereto.

FIG. 1 is a cross-sectional view of an underfilled flip-chip BGA, and FIG. 2 is a cross-sectional view of a press-molded flip-chip BGA. 3 is a plan view (partial perspective view) when a semiconductor chip 3 is disposed on a flip-chip BGA circuit board 1 via solder bumps 2 .

The semiconductor device 10 of the flip-chip type BGA of the underfill type shown in FIG. 1 is obtained as follows: As shown in FIG. 2. The semiconductor chip 3 is connected and fixed on the circuit board 1 at the bump height a; the underfill portion 5 formed between the circuit board 1 and the semiconductor chip 3 is sealed with an epoxy resin molding material (sealing material) 4 for sealing. The flip-chip BGA semiconductor device 20 shown in FIG. 2 is fabricated in the same manner as above except that the underfill portion 5 is sealed during the sealing process and the entire semiconductor chip 3 is covered.

Here, in the embodiment of manufacturing the semiconductor device of the present invention, it is preferable to set the bump height a, the bump pitch b, the area c of the semiconductor chip, and the total thickness d of the sealing material of the semiconductor device as follows.

The height a of the solder bump 2 is preferably 150 μm or less, more preferably 100 μm or less, and particularly preferably 80 μm or less. The pitch b of the solder bumps 2 , that is, the center-to-center spacing of the solder bumps is preferably 500 μm or less, more preferably 400 μm or less, and particularly preferably 300 μm or less.

The number of welding bumps 2 is preferably 100 or more, more preferably 150 or more, and especially preferably 200 or more.

The area of the semiconductor chip 3 is preferably 25 mm ² or more, more preferably 50 mm ² or more, and especially preferably 80 mm ² or more.

The total thickness d of the sealing material 4 is preferably 2 mm or less, more preferably 1.5 mm or less, particularly preferably 1.0 mm or less.

In addition, the total thickness of the underfill type is the same value as the bump height a.

(Embodiment 2 of semiconductor device)

Fig. 4 is a flip-chip type BGA sealed with an epoxy resin molding material (sealing material) 4 after connecting and fixing a semiconductor chip 3 with solder bumps 2 on a circuit board 1, where (x) in Fig. 4 is a cross section Figure (compression molding), (y) is a top view (partial perspective view).

In the semiconductor device of the present invention shown in FIG. 4, the area c of the semiconductor chip 3 is preferably 25 mm ² or more, more preferably 50 mm ² or more, and particularly preferably 70 mm ² or more.

The total thickness d of the sealing material 4 is preferably 2 mm or less, more preferably 1.5 mm or less, particularly preferably 1.0 mm or less.

The sealing material forming area g of the one-time forming method is preferably 3000 mm ² or more, more preferably 5000 mm ² or more.

(Other embodiment of semiconductor device)

Other embodiments of the semiconductor device of the present invention include mounting semiconductor chips, transistors, diodes, thyristors and other active elements, capacitors, etc. Flip-chip mounted semiconductor devices, etc., which are sealed with epoxy resin molding material for sealing after passive components such as resistors and coils.

Here, as the sealing epoxy resin molding material constituting the semiconductor device, the sealing epoxy resin molding material according to the embodiment of the present invention can be used. For example, use an inorganic filler containing (A) epoxy resin, (B) curing agent and (C) at least meeting any one of the following (1) and (2):

(1) The average particle size is 12 μm or less, and the specific surface area is 3.0 m ² /g or more;

(2) The maximum particle size is 63 μm or less, and the content of inorganic fillers with a particle size of 20 μm or more is 5 wt% or more;

Also, an epoxy resin molding material for sealing containing (D2) a silane coupling agent having a secondary amino group and (E) a curing accelerator as needed.

From the point of view of improving the fillability, (C) the inorganic filler is preferably an inorganic filler that meets the condition (1), and from the point of view of improving the flashing property, it is preferable to use an inorganic filler that meets the condition (2), but From these two viewpoints, fillers satisfying conditions (1) and (2) are more preferable.

The mounting substrate is not particularly limited, and examples include interposer substrates such as organic substrates, organic thin films, ceramic substrates, and glass substrates, glass substrates for liquid crystals, substrates for MCM (multi-chip modules), hybrid IC substrates, etc.

As an embodiment of the semiconductor device of the present invention, it is preferable to have one or more of the following configurations each specified as a given value: (a) bump height of flip chip, (b) bump pitch of flip chip, (c) The area of the semiconductor chip, (d) the total thickness of the sealing material, (e) the number of bumps of the flip chip, and (f) the thickness of the vent hole during molding. Specifically, it is preferred to have one or more of the following (a1) to (f1):

(a1) The bump height for flip-chip mounting is 150 μm or less;

(b1) The bump pitch of the flip chip is 500 μm or less;

(c1) The area of the semiconductor chip is 25 mm ² or more;

(d1) The total thickness of the sealing material is 2 mm or less;

(e1) The number of bumps of the flip chip is 100 or more;

(f1) The vent thickness at the time of molding is 40 μm or less.

More preferably, a semiconductor device having one or more of the following (a2) to (f2):

(a2) The bump height for flip-chip mounting is 100 μm or less;

(b2) The bump pitch of the flip chip is 400 μm or less;

(c2) The area of the semiconductor chip is 50 mm ² or more;

(d2) The total thickness of the sealing material is 1.5 mm or less;

(e2) The number of bumps of the flip chip is 150 or more;

(f2) The vent thickness at the time of molding is 30 μm or less.

Especially preferred are semiconductor devices having one or more of the following (a3) to (f3):

(a3) The bump height for flip-chip mounting is 150 μm or less;

(b3) The bump pitch of the flip chip is 300 μm or less;

(c3) The area of the semiconductor chip is 80 mm ² or more;

(d2) The total thickness of the sealing material is 1.0 mm or less;

(e3) The number of bumps of the flip chip is 200 or more;

(f3) The vent thickness at the time of molding is 20 μm or less.

Hereinafter, a semiconductor device will be described with reference to preferred embodiments, and among them, it is preferable to include a semiconductor device having the configurations (a) to (f) in the following combinations.

From the viewpoint of packing properties, it is preferable to have a semiconductor device including at least one of the configuration (a) and the configuration (b). More specifically, it is preferable to include a semiconductor device including the configurations (a1) and (b1), a semiconductor device including the configurations (a1) and (d1), a semiconductor device including the configurations (a1) and (c1), and a semiconductor device including the configuration (b) The semiconductor device of (d) includes the semiconductor devices constituting (b1) and (c1). More preferably, a semiconductor device having the structures (a2) and (b2), a semiconductor device having the structures (a2) and (d2), a semiconductor device having the structures (a2) and (c2), and a semiconductor device having the structures (b2) and (d2) A semiconductor device including configurations (b2) and (c2). More preferably, a semiconductor device having the structures (a3) and (b3), a semiconductor device having the structures (a3) and (d3), a semiconductor device having the structures (a3) and (c3), and a semiconductor device having the structures (b3) and (d3) A semiconductor device, a semiconductor device including configurations (b3) and (c3).

As such a semiconductor device, for example, a semiconductor chip is connected to wiring formed on a circuit board or glass with a flip-chip adhesive, and then sealed with the epoxy resin molding material for sealing of the present invention. Semiconductor devices such as COB (Chip On Board) and COG (Chip On Glass) are mounted on bare chips; semiconductor chips, transistors, diodes, thyristors and other active components and/or capacitors, resistors, A hybrid IC obtained by connecting passive components such as coils to wiring formed on a circuit board or glass, and then sealing it with the sealing epoxy resin molding material of the present invention; mounting a semiconductor chip on a MCM (Multi-Chip Module) On the interposer substrate of the terminal for motherboard connection, after connecting the semiconductor chip and the wiring formed on the interposer substrate with bumps, the side on which the semiconductor chip is mounted is sealed with the sealing epoxy resin molding material of the present invention. BGA (Ball Grid Array Package), CSP (Chip Scale Package), MCP (Multi-Chip Package), etc. In addition, the semiconductor device may be a stacked (laminated) type package in which two or more elements are stacked on a mounting substrate, or a one-time molding in which two or more elements are sealed together with an epoxy resin molding material for sealing. type package.

(Embodiment 2 of semiconductor device)

The sealing epoxy resin molding material used is preferably the sealing epoxy resin molding material of the present invention. That is, among epoxy resin molding materials for sealing containing at least (A) epoxy resin, (B) curing agent, and (C) inorganic filler, it is preferable that the epoxy resin molding material for sealing used satisfies at least one of the following conditions: One condition: The epoxy resin molding material for sealing has a glass transition temperature of 150°C or higher based on the TMA method, a flexural modulus of 19 GPa or lower based on JIS-K6911, and a mold shrinkage ratio of 0.2% or lower based on JIS-K6911. More preferably, two or more conditions are met, and it is especially preferred that all three conditions are met. From the viewpoint of warpage, the glass transition temperature is preferably 160°C or higher, more preferably 170°C or higher. When the temperature is lower than 150°C, the degree of warpage tends to increase. From the viewpoint of warpage, the flexural modulus is preferably 18.5 GPa or less, more preferably 18 GPa or less. When it exceeds 19 GPa, the degree of warpage tends to increase. In addition, from the viewpoint of warpage, the molding shrinkage is preferably 0.18% or less, more preferably 0.15% or less. When it exceeds 0.2%, the degree of warpage tends to increase.

The degree of warpage of a semiconductor device sealed using the above-mentioned epoxy resin molding compound for sealing is preferably 5.0 mm or less, more preferably 2.0 mm or less, and particularly preferably 1.5 mm or less. When the thickness exceeds 5.0 mm, for the semiconductor device of the one-shot molding method, the work at the time of dicing the semiconductor device into individual pieces and mounting the circuit board will be impaired.

The mounting substrate is not particularly limited, and examples include interposer substrates such as organic substrates, organic thin films, ceramic substrates, and glass substrates, glass substrates for liquid crystals, substrates for MCM (multi-chip modules), hybrid IC substrates, etc.

As the semiconductor device of the present invention, it is preferable to have one or more of the following configurations each defined as a given value: (a) bump height of flip chip, (b) bump pitch of flip chip, (c) semiconductor chip area, (d) the total thickness of the sealing material, (e) the number of bumps of the flip chip, and (g) the forming area of the sealing material in one-shot molding.

Specifically, it is preferable to have one or more configurations of the following (a1) to (g1).

Here, the "total thickness of the sealing material" in the present invention refers to the bump height for the underfill type.

(a1) The bump height of the flip chip is 150 μm or less;

(b1) The bump pitch of the flip chip is 500 μm or less;

(c1) The area of the semiconductor chip is 25 mm ² or more;

(d1) The total thickness of the sealing material is 2 mm or less;

(e1) The number of bumps of the flip chip is 100 or more;

(g1) The sealing material forming area of the one-shot forming method is 3000 mm ² or more.

It is more preferable to have one or more of the following (a2)-(g2) structures.

(a2) The bump height of the flip chip is 100 μm or less;

(b2) The bump pitch of the flip chip is 400 μm or less;

(c2) The area of the semiconductor chip is 50 mm ² or more;

(d2) The total thickness of the sealing material is 1.5 mm or less;

(e2) The number of bumps of the flip chip is 150 or more;

(g2) The sealing material forming area of the one-time forming method is 5000 mm ² or more.

In particular, it is preferable to have one or more of the following (a3) to (g3) configurations.

(a3) The bump height of the flip chip is 80 μm or less;

(b3) The bump pitch of the flip chip is 300 μm or less;

(c3) The area of the semiconductor chip is 80 mm ² or more;

(d3) The total thickness of the sealing material is 1.0 mm or less;

(e3) The number of bumps of the flip chip is 200 or more;

(g3) The sealing material forming area of the one-shot forming method is 7000 mm ² or more.

Hereinafter, a semiconductor device will be described with reference to preferred embodiments, but a semiconductor device including the following configurations (a) to (g) in the following combinations is particularly preferable.

From the viewpoint of packing properties, a semiconductor device including at least one of the configuration (a) and the configuration (b) is preferable. More specifically, it is preferable to include a semiconductor device including the configurations (a1) and (b1), a semiconductor device including the configurations (a1) and (d1), a semiconductor device including the configurations (a1) and (c1), and a semiconductor device including the configuration (b) and the semiconductor device of (d), and the semiconductor device including the configurations (b1) and (c1). More preferably, a semiconductor device having the structures (a2) and (b2), a semiconductor device having the structures (a2) and (d2), a semiconductor device having the structures (a2) and (c2), and a semiconductor device having the structures (b2) and (d2) A semiconductor device including configurations (b2) and (c2). Especially preferably, a semiconductor device having the structures (a3) and (c3), a semiconductor device having the structures (a3) and (d3), a semiconductor device having the structures (a3) and (c3), and a semiconductor device having the structures (b3) and (d3) A semiconductor device, a semiconductor device including configurations (b3) and (c3).

In addition, from the viewpoint of warpage, a semiconductor device including at least one of the configuration (c), the configuration (d) and the configuration (g) is preferable. More specifically, it is preferable to include a semiconductor device including the configurations (c1) and (g1), a semiconductor device including the configurations (c1) and (d1), and a semiconductor device including the configurations (d1) and (g1). More preferably, it is a semiconductor device provided with configurations (c2) and (g2), a semiconductor device provided with configurations (c2) and (d2), and a semiconductor device provided with configurations (d2) and (g2). In particular, a semiconductor device including the structures (c3) and (g3), a semiconductor device including the structures of the structures (c3) and (d3), and a semiconductor device including the structures (d3) and (g3) are preferable.

Example

Examples of the present invention are shown below, but the scope of the present invention is not limited to these Examples. In addition, unless otherwise specified, the evaluation of each sealing epoxy resin molding material and a semiconductor device was performed based on the evaluation method mentioned later.

Example A

(Examples A1 to A7, Comparative Examples A1 to A6)

After premixing (dry mixing) each material with the mixing composition shown in Table 1 to Table 3, kneading for 10 minutes with a twin-shaft roll mill with a roll surface temperature of about 80°C, and then cooling and pulverizing to obtain Examples A1 to A7 and comparative Each sealing epoxy resin molding material A1-A13 of Examples A1-A6. Here, the compositions in the table are parts by weight.

(A) epoxy resin

The biphenyl type epoxy resin used is a product named Epicoat YH-4000H (epoxy equivalent 196, melting point 106° C.) manufactured by Japan Epikisilesin Co., Ltd., and the brominated epoxy resin is a product manufactured by Sumitomo Chemical Co., Ltd. Named as ESB-400 (epoxy equivalent 400, bromine content 49% epibis type (Epibis type) epoxy resin, 2,2'-bis(4-hydroxyl-3,5-dibromophenyl) propane is obtained from the table Diglycidyl etherification modification of chlorohydrins).

(B) curing agent

The (B) curing agent used is the phenol-benzaldehyde-xylylenedimethoxide polycondensate represented by the following structural formula (XXII) with a hydroxyl equivalent of 156 and a softening point of 73° C. 05), and the phenol-hydroxybenzaldehyde resin represented by the following structural formula (XXIII) with a hydroxyl equivalent of 100 and a softening point of 83° C. (Meiwa Chemicals’ product name MEH-7500-3S).

(In the formula, n is a positive number from 0 to 8.)

(In the formula, n is a positive number from 0 to 8.)

A total of 13 types of molding materials obtained were molded using a transfer molding machine under the conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, and then evaluated by spiral flow and gel time tests.

[Production of semiconductor device A1 (flip-chip BGA)]

Next, semiconductor devices of Examples A1 to A7 and Comparative Examples A1 to A6 were fabricated using epoxy resin molding materials A1 to A13 for sealing. In addition, the method of sealing with an epoxy resin molding material for sealing is to use a transfer molding machine to mold at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and then post-cure at 180°C for 5 hours.

Examples A1 to A7 (Table): After forming a fine wiring pattern on an insulating base material (glass cloth-epoxy resin laminate, manufactured by Hitachi Chemical, trade name E-679), an insulating protective resist ( Manufactured by Taiyo Inky, trade name PSR4000AUS5) Coated on the surface except the gold-plated terminal on the semiconductor chip mounting side and the external connection terminal on the reverse side, and then at 120°C, the obtained semiconductor with an outer shape of 22 mm in length x 14 mm in width x 0.3 mm in thickness The substrate for device mounting was dried for 2 hours, and then 9 mm in length x 8 mm in width x 0.4 mm in thickness (area 72 mm ² ), bump diameter 145 μm, bump pitch 200 μm, A semiconductor element with 160 bumps was reflow-processed and mounted. The bump height after mounting was 100 μm. Next, using epoxy resin molding materials 1 to 7 for sealing, vacuum transfer molding was performed on the semiconductor element mounting surface with dimensions of 22 mm in length x 14 mm in width x 0.7 mm in thickness under the above conditions to obtain flip-chip BGA devices of Examples 1 to 7. .

Comparative Examples A1 to A6 (Table): Except for using sealing epoxy resin molding materials A8 to A13, the same procedure as in Examples A1 to A7 was performed to produce semiconductor devices in Comparative Examples A1 to A6.

[Production of semiconductor device A2 (flip-chip BGA)]

Next, semiconductor devices of Examples A1 to A7 and Comparative Examples A1 to A6 were produced using epoxy resin molding materials A1 to A13 for sealing. In addition, the method of sealing with an epoxy resin molding material for sealing is to use a transfer molding machine to mold at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and then post-cure at 180°C for 5 hours.

Examples A1 to A7 (Table): After forming a fine wiring pattern on an insulating base material (glass cloth-epoxy resin laminate, manufactured by Hitachi Chemical, trade name E-679), an insulating protective resist ( Manufactured by Taiyo Inky, trade name PSR4000AUS5) Coated on the surface other than the gold-plated terminal on the semiconductor element mounting side and the external connection terminal on the reverse side, and then at 120°C, the obtained semiconductor with an outer shape of 22 mm in length x 14 mm in width x 0.3 mm in thickness The substrate for device mounting was dried for 2 hours, and then subjected to the IR reflow process at 260°C for 10 seconds on the condition of 6 mm in length x 5 mm in width x 0.4 mm in thickness (area 30 mm ² ), bump diameter 300 μm, and bump pitch 490 μm. A semiconductor element with 120 bumps was reflow-processed and mounted. The bump height after mounting was 260 μm. Next, using epoxy resin molding materials 1 to 7 for sealing, the semiconductor element mounting surface was vacuum transfer molded with dimensions of 22 mm in length x 14 mm in width x 1.2 mm in thickness under the above conditions to obtain the flip-chip BGA device of the embodiment.

Comparative Examples A1 to A6 (Table): Except for using sealing epoxy resin molding materials A8 to A13, the same procedure as in Examples A1 to A7 was carried out to produce semiconductor devices in Comparative Examples A1 to A6.

[Production of semiconductor device A3 (flip-chip BGA)]

Next, semiconductor devices of Examples A1 to A7 and Comparative Examples A1 to A6 were produced using epoxy resin molding materials A1 to A13 for sealing. In addition, the method of sealing with an epoxy resin molding material for sealing is to use a transfer molding machine to mold at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and then post-cure at 180°C for 5 hours.

Examples A1 to A7 (Table): After forming a fine wiring pattern on an insulating base material (glass cloth-epoxy resin laminate, manufactured by Hitachi Chemical, trade name E-679), an insulating protective resist ( Manufactured by Taiyo Inky, trade name PSR4000AUS5) Coated on the surface other than the gold-plated terminal on the semiconductor element mounting side and the external connection terminal on the reverse side, and then at 120°C, the obtained semiconductor with an outer shape of 22 mm in length x 14 mm in width x 0.3 mm in thickness The element mounting substrate was dried for 2 hours, and then subjected to the IR reflow process at 260°C and 10 seconds for 5 mm in length x 4 mm in width x 0.4 mm in thickness (area 20 mm ² ), bump diameter 390 μm, bump pitch 700 μm, A semiconductor element having 40 bumps is reflow-processed and mounted. The bump height after mounting was 350 μm. Next, using epoxy resin molding materials 1 to 7 for sealing, vacuum transfer molding was performed on the semiconductor element mounting surface with dimensions of 22 mm in length x 14 mm in width x 2.5 mm in thickness under the above conditions to obtain flip-chip BGA devices of Examples 1 to 7. .

Comparative Examples A1-A6 (table): Except having used sealing epoxy resin molding materials 8-13, it carried out similarly to Examples A1-A7, and produced the semiconductor device of Comparative Examples A1-A6.

The obtained semiconductor devices of Examples A1 to A7 and Comparative Examples A1 to A6 were evaluated by the following tests. The results are shown in Table 2-Table 3.

Table 1 project Filler A Filler B Filler C Filler D Filler E Filler F Filler G Particle size distribution (cumulative weight%) ~1gm 11 11 27 27 10 10 11 ~2μm 20 20 38 42 20 twenty one 25 ~4μm 30 30 45 54 29 31 41 ~6μm 37 36 50 63 34 37 52 ~12μm 50 53 73 86 45 48 82 ~24μm 71 75 87 96 61 68 100 ~32μm 81 83 93 100 72 80 100 ~48μm 95 96 98 100 86 94 100 ~64μm 100 100 100 100 92 97 100 ~96μm 100 100 100 100 98 100 100 The average particle size μm 12 11 6 3 18 15 6 specific surface area m ² /g 3.5 3.3 4.0 3.5 3.5 3.8 2.7 Maximum particle size μm 63 53 53 30 105 75 30 20μm or more filling material amount wt% 33 30 15 5 43 37 4

Table 2 project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Resin No. 1 2 3 4 5 6 7 epoxy resin YX-4000H 85 85 85 85 85 85 85 ^* 1 15 15 15 15 15 15 15 Hardener Structural formula (XXII) 75 75 75 75 - - - Structural formula (XXIII) - - - - 50 50 50 curing accelerator ^* 2 3.5 3.5 3.5 3.5 2.5 2.5 2.5 Coupler ^* 3 5 5 5 5 5 5 5 Antimony trioxide Sb ₂ O ₃ 5 5 5 5 5 5 5 Release agent carnauba wax 2 2 2 2 2 2 2 Colorant carbon black 3 3 3 3 3 3 3 filler A 1850 - - - - - - B - 1850 - - 1320 - - C - - 1850 - - 1320 - D. - - - 1400 - - 1179 E. - - - - - - - f - - - - - - - G - - - - - - - spiral flow cm 105 115 95 100 160 145 130 gel time sec 38 43 42 45 50 50 52 overflow - good good good good good good good void generation Semiconductor device 1 0/20 0/20 0/20 0/20 0/20 0/20 0/20 Semiconductor device 2 0/20 0/20 0/20 0/20 0/20 0/20 0/20 Semiconductor device 3 0/20 0/20 0/20 0/20 0/20 0/20 0/20

^* 1: 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane ether-modified epichlorohydrin

^* 2: Adduct of triphenylphosphine and benzoquinone

^* 3: γ-Glycidoxypropyltrimethoxysilane

table 3 project Comparative Example A1 Comparative example A2 Comparative Example A3 Comparative Example A4 Comparative Example A5 Comparative Example A6 Resin No. 8 9 10 11 12 13 epoxy resin YX-4000H 85 85 85 85 85 85 ^* 1 15 15 15 15 15 15 Hardener Structural formula (XXII) 75 75 75 - - - Structural formula (XXIII) - - - 50 50 50 curing accelerator ^* 2 3.5 3.5 3.5 2.5 2.5 2.5 Coupler ^* 3 5 5 5 5 5 5 Antimony dioxide Sb ₂ O ₃ 5 5 5 5 5 5 Release agent carnauba wax 2 2 2 2 2 2 Colorant carbon black 3 3 3 3 3 3 filler A - - - - - - B - - - - - - C - - - - - - D. - - - - - - E. 1850 - - 1320 - - f - 1850 - - 1320 - G - - 1400 - - 1179 spiral flow cm 95 100 75 150 160 105 gel time sec 37 38 42 49 50 50 overflow - good good NG good good NG void generation Semiconductor device 1 20/20 10/20 15/20 20/20 8/20 11/20 Semiconductor device 2 15/20 0/20 0/20 13/20 0/20 0/20 Semiconductor device 3 0/20 0/20 0/20 0/20 0/20 0/20

^* 1: Ether modification of 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane with epichlorohydrin

^* 2: Adduct of triphenylphosphine and benzoquinone

^* 3: γ-Glycidoxypropyltrimethoxysilane

[Evaluation method]

(1) Spiral flow (fluidity index)

The flow distance was obtained after molding with a mold for measuring spiral flow according to EMMI-1-66.

(2) Gel time

Using the Curelasto meter vulcanization testing machine manufactured by JSR, measure the time (s) from the torque curve to the rise under the conditions of 3 g of the sample and a temperature of 180 °C.

(3) Amount of void generation

Use an ultrasonic probe imaging device (HYE-HOCUS type manufactured by Hitachi Construction Machinery Co., Ltd.) to see through the semiconductor device to observe whether there are voids with a diameter of 0.1mm or more, and then evaluate by the number of semiconductor devices with voids/the number of test semiconductor devices.

(4) Spill

After molding with a die provided with a gap 10 μm thicker than the pot, the length of the flash flowing out of the gap was obtained with a vernier caliper. In addition, it is set that the flash length in the gap is less than 10 μm as good, and 10 μm or more as NG.

The sealing epoxy resin molding material for flip-chip mounting according to the present invention has high filling properties required as an underfill and has few molding defects such as voids, so it has great industrial value.

Example B

[Production of epoxy resin molding materials for sealing]

The following components were added in parts by weight shown in Table 4 and Table 5, and then kneaded by a roll mill at a kneading temperature of 80°C and a kneading time of 10 minutes to obtain sealing epoxy resin molding materials B1 to B19.

(epoxy resin)

The epoxy resin used is a biphenyl type epoxy resin with an epoxy equivalent of 196 and a melting point of 106° C. (trade name Epicoat YX-4000H manufactured by Japan Epoch Resin Co., Ltd.); an epoxy equivalent of 186 and a melting point of 75° C. Phenol F-type epoxy resin (trade name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd.); stilbene-type epoxy resin with an epoxy equivalent of 210 and a melting point of 120° C. (trade name ESLV-210 manufactured by Sumitomo Chemical Industries, Ltd.); Sulfur atom-containing epoxy resin with oxygen equivalent of 245 and melting point of 110°C (trade name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd.); triphenol with epoxy equivalent of 170, softening point of 60°C, and melt contact viscosity of 2.4 poise at 150°C Methane type epoxy resin 1 (trade name Epicoat E1032H produced by Japan Epoch Resin Co., Ltd.); epoxy equivalent 170, softening point 70 DEG C, 150 DEG C of melting particle size 3.1 poise trisphenol methane type epoxy resin 2 (JIAPANE EPOKISHI RESIN CO., LTD. Resin Co., Ltd. (trade name: Epicoat E1032H); epoxy equivalent 195, softening point 65° C. o-cresol novolac epoxy resin (Sumitomo Chemical Industries, Ltd., trade name: ESCN-190).

(Hardener)

The curing agent used is a phenol-aralkyl resin with a softening point of 70°C and a hydroxyl equivalent of 175 (trade name Milex XL-225 manufactured by Mitsui Chemicals Co., Ltd.); a biphenyl type phenolic resin with a softening point of 80°C and a hydroxyl equivalent of 199 (Meiwa Kasei Co., Ltd. trade name MEH-7851); softening point 83° C., hydroxyl equivalent 103, 150° C. trisphenolmethane type epoxy resin 1.3 poise melt viscosity (Meiwa Kasei trade name MEH-7500-3S) 101 DEG C of softening point, the melt viscosity of 101,150 DEG C of hydroxyl equivalents 3.0 poise trisphenol methane type epoxy resin 2 (Minghe chemical into the trade name MEH-7500-SS); 80 DEG C of softening points, the phenol novolac of hydroxyl equivalent 106 Varnish resin (trade name H-1 manufactured by Meiwa Kasei Co., Ltd.).

(curing accelerator)

The curing accelerator used is an adduct (curing accelerator) of triphenylphosphine and p-benzoquinone, and the coupling agent is a silane coupling agent containing a secondary amino group (γ-anilinopropyltrimethoxysilane (anilinosilane )), γ-glycidoxypropyltrimethoxysilane (epoxysilane).

(flame retardant)

The flame retardant used is aromatic condensed phosphoric acid ester (product name PX-200 manufactured by Dahachi Chemical); triphenylphosphine oxide; composite metal hydroxide Ekomag Z-10 manufactured by Tateho Chemical; antimony trioxide Bisphenol A type brominated epoxy resin having an epoxy equivalent of 375, a softening point of 80° C., and a bromine content of 48% by weight (trade name ESB-400T manufactured by Sumitomo Chemical Industries, Ltd.).

(inorganic filler)

The inorganic fillers used are spherical fused silica 1 with an average particle size of 6.7 μm and a specific surface area of 3.0 m ² /g; spherical fused silica 2 with an average particle size of 8.8 μm and a specific surface area of 4.6 m ² /g; an average particle size of 12.5 Spherical fused silica 3 with μm and a specific surface area of 3.2m ² /g; spherical fused silica 4 with an average particle size of 6.0 μm and a specific surface area of 2.7m ² /g; spherical fused silica with an average particle size of 17 μm and a specific surface area of 3.8m ² /g 5. Spherical fused silica 6 with an average particle diameter of 0.8 μm and a specific surface area of 6.3 m ² /g.

(other additives)

Other additives used were carnauba wax (manufactured by Clariant Co., Ltd.) and carbon black (trade name MA-100, manufactured by Mitsubishi Chemical Corporation).

Table 4 Mixing composition of epoxy resin molding materials for sealing 1 mixed ingredients Example sealing epoxy resin molding material B 1 2 3 4 5 6 7 8 9 10 Biphenyl type epoxy resin - - - - - - - - - 85 Bisphenol F type epoxy resin 10 10 10 10 10 10 10 10 10 - Stilbene epoxy resin - - - - - - - - - - Sulfur atom containing epoxy resin - - - - - - - - - - Trisphenol methane type epoxy resin 1 75 75 75 75 75 75 - 75 75 - Trisphenol methane type epoxy resin 2 - - - - - - 75 - - - o-cresol novolac epoxy resin - - - - - - - - - - brominated epoxy resin 15 15 15 15 15 15 15 15 15 15 Phenol-Aralkyl Resins - - - - - - - - - - Biphenyl type phenolic resin - - - - - - - - - - Trisphenol methane type phenolic resin 1 55 55 55 55 55 55 55 - 55 49 Trisphenol methane type phenolic resin 2 - - - - - - - 55 - - Phenol Novolac Resin - - - - - - - - - - curing accelerator 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 3.0 Aromatic condensed phosphate - - - - - - - - - - triphenylphosphine oxide - - - - - - - - - - Composite metal hydroxide - - - - - - - - - - Antimony trioxide 15 15 15 15 15 15 15 15 15 15 Anilinosilane 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 - 4.5 epoxy silane - - - - - - - - 4.5 - Spherical Fused Silica 1 868 - - - - - - - - - Spherical Fused Silica 2 - 868 - - - - 868 868 868 933 Spherical Fused Silica 3 - - 868 - - - - - - - Spherical Fused Silica 4 - - - 868 - - - - - - Spherical Fused Silica 5 - - - - 868 - - - - - Spherical Fused Silica 6 - - - - - 868 - - - - carnauba wax 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 carbon black 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Inorganic filler dosage (weight%) 83 83 83 83 83 83 83 83 83 84

Table 5 Mixing composition of epoxy resin molding materials for sealing 2 mixed ingredients Example sealing epoxy resin molding material B 11 12 13 14 15 16 17 18 19 Biphenyl type epoxy resin - - - 85 - - - - - Bisphenol F type epoxy resin 85 - - - - 100 10 10 10 Stilbene epoxy resin - 85 - - - - - - - Sulfur atom containing epoxy resin - - 85 - - - - - - Trisphenol methane type epoxy resin 1 - - - - - - 90 90 90 Trisphenol methane type epoxy resin 2 - - - - - - - - - o-cresol novolac epoxy resin - - - - 85 - - - - brominated epoxy resin 15 15 15 15 15 - - - - Phenol-Aralkyl Resins - - - 83 - - - - - Biphenyl type phenolic resin - - - - - 107 - - - Trisphenol methane type phenolic resin 1 51 46 40 - - - 60 60 60 Trisphenol methane type phenolic resin 2 - - - - - - - - - Phenol Novolac Resin - - - - 50 - - - - curing accelerator 3.5 3.5 3.5 3.5 2.0 3.5 3.0 3.0 3.0 Aromatic condensed phosphate - - - - - - 35 - - triphenylphosphine oxide - - - - - - - 35 - Composite metal hydroxide - - - - - - - - 150 Antimony trioxide 15 15 15 15 15 15 15 15 15 Anilinosilane 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 epoxy silane - - - - - - - - - Spherical Fused Silica 1 - - - - - - - - - Spherical Fused Silica 2 951 922 890 1121 613 1756 1076 1076 757 Spherical Fused Silica 3 - - - - - - - - - Spherical Fused Silica 4 - - - - - - - - - Spherical Fused Silica 5 - - - - - - - - - Spherical Fused Silica 6 - - - - - - - - - carnauba wax 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 carbon black 3.5 3.5 3.5 3.5 3.5 3.5 3.0 3.0 3.0 Inorganic filler dosage (weight%) 84 84 84 84 78 88 83 83 83

The characteristics of the obtained sealing epoxy resin molding materials B1 to B19 were evaluated by the test items (spiral flow, disk flow, hot hardness, flame retardancy) shown in Table 3 and Table 4. The results are shown in Table 6 and Table 7.

Table 6 Characteristics of epoxy resin molding materials for sealing 1 characteristic Example sealing epoxy resin molding material B 1 2 3 4 5 6 7 8 9 10 Spiral flow(cm) 171 175 174 100 175 68 113 107 166 232 Moving plate flow(mm) 121 130 127 76 127 56 88 81 102 125 Hardness when hot (Shore D) 77 77 78 77 78 76 82 83 76 82 UL-94 test V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0

Table 7 Characteristics of epoxy resin molding materials for sealing 2 characteristic Example sealing epoxy resin molding material B 11 12 13 14 15 16 17 18 19 Spiral flow(cm) 237 229 225 206 145 118 180 178 117 Disc flow(mm) 127 115 113 110 100 95 133 132 92 Hardness when hot (Shore D) 80 83 79 73 83 75 70 71 78 UL-94 test V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0

[Production of semiconductor device B1 (flip-chip BGA)]

Next, semiconductor devices of Examples B1 to B16 and Comparative Examples B1 to B3 were produced using epoxy resin molding materials B1 to B19 for sealing. In addition, the method of sealing with an epoxy resin molding material for sealing is to post-cure at 165°C for 5 hours after molding at a mold temperature of 165°C, a molding pressure of 9.8MPa, a vacuum of 530Pa, and a curing time of 90 seconds.

Embodiments B1-B16 (Table 8, Table 9): After forming a fine wiring pattern on an insulating base material (glass cloth-epoxy resin laminated board, manufactured by Hitachi Chemical, trade name E-679), the insulation protection A resist (manufactured by Sun Inky, trade name PSR4000AUS5) is applied on the surface other than the gold-plated terminal on the semiconductor element mounting side and the external connection terminal on the reverse side, and the resulting shape is 40 mm in length x 40 mm in width x thickness at 120°C The 1.3mm substrate for semiconductor device mounting was dried for 2 hours, and then 9mm in length x 8mm in width x 0.4mm in thickness (area 72mm ² ), bump diameter 145μm, bump Semiconductor elements with a pitch of 200 μm were reflow-processed and mounted. The bump height after mounting was 100 μm. Next, using epoxy resin molding materials B1-B3 and B7-B19 for sealing, the semiconductor element mounting surface was vacuum transfer-molded with the dimensions of 12 mm in length x 12 mm in width x 0.7 mm in thickness under the above-mentioned conditions to obtain the inverted molds of Examples B1-B16. Install the chip BGA device.

Comparative Examples B1 to B3 (Table 12): Except for using sealing epoxy resin molding materials 4 to 6, the same procedure was performed as in Examples B1 to B16 to produce semiconductor devices in Comparative Examples B1 to B3.

[Production of semiconductor device B2 (flip-chip BGA)]

Next, semiconductor devices of Examples B17 to B32 and Comparative Examples B4 to B6 were produced using epoxy resin molding materials B1 to B19 for sealing. In addition, the method of sealing with an epoxy resin molding material for sealing is to use a transfer molding machine to mold at a mold temperature of 165°C, a molding pressure of 9.8MPa, a vacuum of 530Pa, and a curing time of 90 seconds, and then post-cure at 180°C for 5 hours. .

Examples 17-32 (Table 10, Table 11): After forming a fine wiring pattern on an insulating base material (glass cloth-epoxy resin laminated board, manufactured by Hitachi Chemical, trade name E-679), the insulating protection A resist (manufactured by Sun Inky, trade name PSR4000AUS5) is applied on the surface other than the gold-plated terminal on the semiconductor element mounting side and the external connection terminal on the reverse side, and the resulting shape is 40 mm in length x 40 mm in width x thickness at 120°C The 1.3mm substrate for semiconductor device mounting was dried for 2 hours, and then processed by IR reflow process at 260°C for 10 seconds on the condition of 6mm in length x 5mm in width x 0.4mm in thickness (area 30mm ² ), bump diameter 175μm, bump Semiconductor elements with a pitch of 400 μm were reflow-processed and mounted. The bump height after mounting was 120 μm. Next, using epoxy resin molding materials B1-B3 and B7-B19 for sealing, the semiconductor element mounting surface is vacuum transfer-molded with the dimensions of 12 mm in length x 12 mm in width x 1.2 mm in thickness under the above-mentioned conditions to obtain flip-chips of Examples B17-B32. Chip BGA device.

Comparative Examples B4 to B6 (Table 13): Except for using sealing epoxy resin molding materials 4 to 6, the same procedure as in Examples B17 to B32 was carried out to produce semiconductor devices in Comparative Examples B4 to B6.

[Production of semiconductor device B3 (flip-chip BGA)]

Semiconductor devices of Comparative Examples B7 to B25 were fabricated using epoxy resin molding materials B1 to B19 for sealing. In addition, the method of sealing with epoxy resin molding material is to use a transfer molding machine to mold at a mold temperature of 165°C, a molding pressure of 9.8MPa, a vacuum of 530Pa, and a curing time of 90 seconds. After molding, it is post-cured at 180°C for 5 hours. .

Comparative Examples 7 to 25 (Table 14, Table 15): After forming a fine wiring pattern on an insulating base material (glass cloth-semiconductor device laminate, manufactured by Hitachi Chemical, trade name E-679), the insulating protection resist An etchant (manufactured by Sun Inky, trade name PSR4000AUS5) was applied to the surface other than the gold-plated terminal on the semiconductor element mounting side and the external connection terminal on the reverse side, and the resulting shape was 40 mm in length x 40 mm in width x 1.3 in thickness at 120°C. The semiconductor element mounting substrate of mm was dried for 2 hours, and then the bumps with a diameter of 250 μm and a bump diameter of 250 μm were processed according to the IR reflow process under the ^conditions of 260 ° C and 10 seconds. Semiconductor elements with a pitch of 700 μm were reflow-processed and mounted. The bump height after mounting was 180 μm. Next, using epoxy resin molding materials 1-19 for sealing, the semiconductor element mounting surface was vacuum transfer-molded with the dimensions of 12 mm in length x 12 mm in width x 2.5 mm in thickness under the above-mentioned conditions to obtain flip-chip BGA devices of Comparative Examples B7-B25.

The void formation test of the obtained semiconductor devices of Examples B1 to B32 and Comparative Examples B1 to B25 was conducted for evaluation, and the evaluation results are shown in Tables 8 to 15.

Table 8 Evaluation Results of Semiconductor Devices 1 (Semiconductor Device B1) characteristic Example B 1 2 3 4 5 6 7 8 9 Sealing epoxy resin molding material B 1 2 3 7 8 9 10 11 12 void formation 2/20 0/20 2/20 3/20 4/20 3/20 0/20 0/20 1/20

Table 9 Evaluation Results 2 of Semiconductor Devices (Semiconductor Device B1) characteristic Example B 10 11 12 13 14 15 16 Sealing epoxy resin molding material B 13 14 15 16 17 18 19 void formation 0/20 0/20 2/20 2/20 0/20 0/20 3/20

Table 10 Evaluation results of semiconductor devices 3 (semiconductor device B2) characteristic Example B 17 18 19 20 twenty one twenty two twenty three twenty four 25 Sealing epoxy resin molding material B 1 2 3 7 8 9 10 11 12 void formation 1/20 0/20 1/20 3/20 3/20 2/20 0/20 0/20 0/20

Table 11 Evaluation result 4 of semiconductor device (semiconductor device B2) characteristic Example B 26 27 28 29 30 31 32 Sealing epoxy resin molding material B 13 14 15 16 17 18 19 void formation 0/20 0/20 1/20 1/20 0/20 0/20 2/20

Table 12 Evaluation Results 5 of Semiconductor Devices (Semiconductor Device B1) characteristic Comparative Example B 1 2 3 Sealing epoxy resin molding material B 4 5 6 void formation 11/20 not filled 18/20

Table 13 Evaluation result 6 of semiconductor device (semiconductor device B2) characteristic Comparative Example B 4 5 6 Sealing epoxy resin molding material B 4 5 6 void formation 8/20 not filled 10/20

Table 14 Evaluation Results 7 of Semiconductor Devices (Semiconductor Device B3) characteristic Comparative Example B 7 8 9 10 11 12 13 14 15 16 Sealing epoxy resin molding material B 1 2 3 4 5 6 7 8 9 10 void formation 0/20 0/20 0/20 2/20 3/20 2/20 0/20 0/20 0/20 0/20

Table 15 Evaluation Results 8 of Semiconductor Devices (Semiconductor Device B3) characteristic Comparative Example B 17 18 19 20 twenty one twenty two twenty three twenty four 25 Sealing epoxy resin molding material B 11 12 13 14 15 16 17 18 19 void formation 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20

[Evaluation reliability]

Embodiment B33～B48 (Table 16, Table 17), comparative example B26～B28 (Table 17):

Next, various reliability (reflow resistance, moisture resistance, high-temperature storage characteristics) were evaluated using the sealing epoxy resin molding materials B1 to B19. The evaluation results are shown in Table 16 and Table 17. In addition, the semiconductor device 2 produced under the same conditions as above was used for evaluation.

Table 16 Reliability 1 (semiconductor device B2) characteristic Example B 33 34 35 36 37 38 39 40 41 42 Sealing epoxy resin molding material B 1 2 3 7 8 9 10 11 12 13 Reflow resistance 72h96h168h336h 0/50/51/53/5 0/50/52/53/5 0/50/51/54/5 0/51/53/55/5 0/51/55/55/5 0/50/50/53/5 0/50/50/52/5 0/50/50/52/5 0/50/50/52/5 0/50/50/50/5 Moisture resistance 100h300h500h1000h 0/100/100/100/10 0/100/100/100/10 0/100/100/100/10 0/100/100/100/10 0/100/100/100/10 0/100/100/100/10 0/100/100/100/10 0/100/100/100/10 0/100/100/100/10 0/100/100/100/10 High temperature storage characteristics 100h300h500h1000h 0/100/102/1010/10 0/100/102/1010/10 0/100/103/1010/10 0/100/101/107/10 0/100/102/107/10 0/100/108/1010/10 0/100/105/1010/10 0/100/106/1010/10 0/100/103/108/10 0/100/105/1010/10

Table 17 Reliability 2 (semiconductor device B2) characteristic Example B Comparative Example B 43 44 45 46 47 48 26 27 28 Sealing epoxy resin molding material B 14 15 16 17 18 19 4 5 6 Reflow resistance 72h96h168h336h 0/50/50/50/5 3/55/55/55/5 0/50/50/50/5 0/50/50/51/5 0/50/50/52/5 0/50/53/55/5 0/52/54/55/5 5/55/55/55/5 0/54/55/55/5 Moisture resistance 100h300h500h1000h 0/100/100/100/10 0/100/100/100/10 0/100/100/100/10 0/100/102/105/10 0/100/100/102/10 0/100/100/100/10 3/105/108/1010/10 10/1010/1010/1010/10 5/108/1010/1010/10 High temperature storage characteristics 100h300h500h1000h 0/102/108/1010/10 0/50/53/55/5 0/100/100/100/10 0/100/100/102/10 0/100/100/100/10 0/100/100/100/10 0/100/103/109/10 0/100/102/1010/10 0/100/102/1010/10

Semiconductor devices of Comparative Examples B1 to B6 sealed with (C) inorganic fillers for sealing with an average particle diameter of 15 μm or less and a specific surface area of 3.0 to 6.0 m ² /g (C) epoxy resin molding materials B4 to B6, There will be a large number of voids and unfilled conditions, and the filling performance is poor. In addition, the semiconductor devices of Comparative Examples B26 to B28 had reduced reflow resistance and moisture resistance.

In contrast, the semiconductor devices of Examples B1-B32 sealed with the sealing epoxy resin molding materials B1-B3, B7-B19 containing (A)-(C) components had less voids and excellent filling properties. In addition, the semiconductor devices of Examples B33 to B48 had excellent reflow resistance and moisture resistance.

For the semiconductor devices of Comparative Examples B7 to B25 that do not have one or more of the present invention configurations (a) to (b), the amount of void generation is also small, and the filling property is excellent. The epoxy resin molding material B1 for sealing There is no advantage difference between ~B3, B7~B19 and sealing epoxy resin molding materials B4~B6.

In addition, Examples B45 to B48 sealed with the sealing epoxy resin molding material B16 without flame retardant and the sealing epoxy resin molding material B17~B19 containing non-halogen flame retardant have excellent high-temperature storage characteristics .

Since the epoxy resin molding material for sealing flip-chip mounting of Example A has high filling properties required as an underfill, there are few molding defects such as voids, and it is also excellent in reliability such as reflow resistance and moisture resistance, Therefore, its industrial value is great.

[Evaluation method]

(1) spiral flow

Using a mold for spiral flow measurement based on EMMI-1-66, the epoxy resin molding material for sealing is molded with a transfer molding machine at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and the flow distance is obtained. (cm).

(2) Circular plate flow

Using a flat mold for flow measurement of a circular plate with an upper mold of 200mm (W) x 200mm (D) x 25mm (H) and a lower mold of 200mm (W) x 200mm (D) x 15mm (H), heat it to 180 Place 5g of an accurately weighed sample (epoxy resin molding material for sealing) at the center of the lower die, close the upper die heated to 180°C after 5 seconds, and compress under the conditions of a load of 78N and a curing time of 90 seconds For forming, measure the major diameter (mm) and minor diameter (mm) of the molded product with a vernier caliper, and set the average value (mm) as the disc flow.

(3) Hardness when hot

Immediately after molding the epoxy resin molding material for sealing into a circular plate with a diameter of 50 mm x a thickness of 3 mm under the above conditions, it was measured with a Shore D-type hardness meter.

(4) Flame retardancy

Using a mold for forming a test piece with a thickness of 1/16 inch, the epoxy resin molding material for sealing was molded under the above conditions, and post-cured at 180° C. for 5 hours, and the flame retardancy was evaluated by the UL-94 test method.

(5) Amount of void generation

Use an ultrasonic probe imaging device (HYE-HOCUS type manufactured by Hitachi Construction Machinery Co., Ltd.) to see through the semiconductor devices to observe whether there are voids with a diameter of 0.1mm or more, and then evaluate by the number of semiconductor devices with voids / the number of test conductor devices.

(6) Reflow resistance

After humidifying various semiconductor devices 3 at 85°C and 85% RH, reflow treatment was performed at 260°C and 10 seconds at regular intervals, and the presence or absence of cracks was observed. ) to evaluate the number of cracked packages.

(7) Moisture resistance After pretreatment of various semiconductor devices 3, humidification is performed, and disconnection defects caused by corrosion of aluminum wiring are checked at regular intervals, and the number of defective packages relative to the number of test packages (10) is measured. to evaluate.

Here, the pretreatment method is to perform vapor phase reflow treatment at 215° C. for 90 seconds after humidifying the flat package under the conditions of 85° C., 85% RH, and 72 hours. Thereafter, it was humidified under conditions of 0.2 MPa and 121°C.

(8) High temperature storage characteristics

Various semiconductor devices 3 were stored in a high-temperature bath at 200°C, taken out at regular intervals for a conduction test, and the high-temperature storage characteristics were evaluated by the number of poor conduction packages relative to the number of test packages (10).

Example C

[Production of epoxy resin molding materials for sealing]

After mixing the following components in parts by weight shown in Table 18, carry out roller mill kneading under the conditions of kneading temperature 80 and kneading time 10 minutes to obtain the sealing epoxy of Examples C1-C4 and Comparative Examples C1-C4 Resin molding material.

(epoxy resin)

Epoxy resin A: epoxy equivalent 196, biphenyl type epoxy resin (trade name Epicoat YX-4000H manufactured by Japan Epoch Resin Co., Ltd.) with a melting point of 106° C.

Epoxy resin B: Epoxy equivalent 176, biphenyl type epoxy resin with a melting point of 125° C. (trade name Epicoat YL-6121H manufactured by Japan Epoch Resin Co., Ltd.)

Epoxy resin C: a trisphenolmethane type epoxy resin having a softening point of 60° C. and a melt viscosity of 2.4 poise at 150° C. (trade name Epicoat E1032H manufactured by Japan Epoch Resin Co., Ltd.)

Epoxy resin D: bisphenol F type epoxy resin with an epoxy equivalent of 186 and a melting point of 75° C. (trade name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd.)

(Hardener)

Phenolic resin A: a trisphenolmethane type phenolic resin with a hydroxyl equivalent of 103 and a melt viscosity of 1.3 poise at 150° C. (Meiwa Chemicals, trade name MEH-7500-3S)

Phenolic resin B: a softening point of 80° C. and a phenol novolak resin with a hydroxyl equivalent of 106 (trade name H-1 manufactured by Meiwa Chemicals Co., Ltd.)

(curing accelerator)

Curing accelerator A: adduct of triphenylphosphine and p-benzoquinone

Curing accelerator B: adduct of tris(4-methylphenyl)phosphine and p-benzoquinone

(release agent)

Release agent A: Polyethylene wax (manufactured by Clariant Co., Ltd.)

Release agent B: montanic acid ester (manufactured by Clariant Co., Ltd.)

(flame retardant)

Flame retardant: epoxy equivalent 375, softening point 80°C, bisphenol A type brominated epoxy resin with a bromine content of 48% by weight (trade name ESB-400T manufactured by Sumitomo Chemical Industries, Ltd.) flame retardant aid: antimony trioxide

(Colorant)

Carbon black: carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Corporation)

(other additives)

Additive A: polyether modified silicone oil (manufactured by Dow Corning Toray Silicone Co., Ltd.)

Additive B: Epoxy modified silicone oil (manufactured by Dow Corning Toray Silicone Co., Ltd.)

Additive C: hydrotalcite

Additive D: bismuth hydroxide

(coupling agent)

Coupling agent A: γ-anilinopropyl trimethoxysilane (anilino silane)

Coupling agent B: Methyltrimethoxysilane

Coupling agent C: γ-mercaptopropyltrimethoxysilane

Coupling agent D: γ-glycidoxypropyl trimethoxysilane (epoxy silane)

(inorganic filler)

Fused silica: all spherical fused silica

Table 18 Example C 1 2 3 4 5 6 7 8 Epoxy resin A 6.06 5.96 5.06 Epoxy resin B 6.84 6.97 6.26 Epoxy resin C 5.41 6.74 epoxy resin 2.25 0.90 Phenolic Resin 3.60 4.42 4.51 4.87 3.54 3.54 4.95 4.07 curing accelerator 0.32 0.24 0.25 0.18 0.32 0.16 0.16 0.18 Release agent 0.32 0.14 0.33 0.15 0.32 0.06 0.15 0.12 flame retardant 1.07 1.2 1.23 1.35 1.05 0.56 1.35 1.10 Flame Retardant Ribs 1.07 1.2 1.23 1.35 1.05 0.34 1.35 1.10 carbon black 0.36 0.24 0.25 0.27 0.35 0.15 0.27 0.22 additive 1.72 1.93 1.97 1.71 1.68 0.06 2.16 1.76 Coupler A ^* 1 0.31 0.35 0.17 0.19 0.47 0.39 0.32 Coupler B ^* 2 0.21 0.24 0.12 0.14 0.32 0.25 0.27 0.22 Coupler C ^* 3 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Coupler D ^* 4 0.37 Fused Silica A ^* 5 76.46 76.48 80.46 Fused Silica B ^* 6 66.52 66.50 65.35 Fused Silica C ^* 7 56.92 Fused Silica D ^* 8 76.00 Fused Silica E ^* 9 8.49 8.47 8.93 8.47 Fused Silica F ^* 10 16.65 16.65 16.31 24.37 Average particle size (μm) 13.5 8.46 8.46 8.46 13.5 13.5 4.3 15.3 Specific surface area (m ² /g) 3.43 4.62 4.62 4.62 3.43 3.43 3.04 3.40 Coupler coverage (%) 0.77 0.65 0.34 0.375 1.13 0.86 1.14 0.79 Heating weight loss rate (mass%) 0.185 0.223 0.142 0.142 0.279 0.254 0.216 0.191 Void area(mm ² ) 0.103 0.124 0.115 0.110 0.181 0.146 0.149 0.175

The omitted words in the formula have the following meanings.

^* 1: The minimum coverage area is 307.0m ² /g;

^* 2: The minimum coverage area is 575.6m ² /g;

^* 3: The minimum coverage area is 399.4m ² /g;

^* 4: The minimum coverage area is 315.2m ² /g;

^* 5: Average particle size 11.7μm, specific surface area 3.2m ² /g;

^* 6: Average particle size 10.8μm, specific surface area 4.2m ² /g;

^* 7: Average particle size 9.3μm, specific surface area 1.6m ² /g;

^* 8: Average particle size 13.5μm, specific surface area 3.2m ² /g;

^* 9: Average particle size 0.6μm, specific surface area 5.5m ² /g;

^* 10: average particle diameter 0.5 μm, specific surface area 6.3 m ² /g.

(1) Void area evaluation method

Fix a semiconductor element with a length of 9.1 mm x width 8.2 mm x a thickness of 0.4 mm (area 74.6 mm ² ), a bump diameter of 200 μm, a bump depth of 135 μm, and a bump pitch of 490 μm in the center of the mold cavity, and then the mold temperature is 165 ° C, Under the molding conditions of molding pressure 4.4MPa, vacuum degree 0.1MPa, cavity filling time 7.5 seconds, and curing time 90 seconds, the epoxy resin molding material for sealing is used for vacuum transfer molding to obtain a molding with a length of 14mm x width 22mm x thickness 0.7mm Taste.

The voids appearing in the bumps of the obtained molded product were photographed at a magnification X, and the actual void area SB was calculated from the void area SP on the photograph and the photograph magnification according to the formula (xx).

SB＝SP/X (xx)

The sealing epoxy resin molding material for flip-chip mounting according to the present invention has high fillability required as an underfill, has few molding defects such as voids, and is also excellent in reliability such as reflow resistance and moisture resistance. The industrial value is great.

Example D

The present invention will be described below with examples, but the scope of the present invention is not limited to these examples. In addition, unless otherwise specified, the evaluation of each sealing epoxy resin molding material and a semiconductor device was performed based on the evaluation method demonstrated later.

[Production of epoxy resin molding materials for sealing]

After adding the following components in parts by weight shown in Table 19 and Table 20, kneading and kneading under the condition of the mixed powder supply rate of 200Kg/h, the epoxy resin molding materials D1-13 for sealing were obtained.

(epoxy resin)

The epoxy resin used is a biphenyl type epoxy resin with an epoxy equivalent of 196 and a melting point of 106° C. (trade name Epicoat YX-4000H manufactured by Japan Epoch Resin Co., Ltd.); an epoxy equivalent of 186 and a melting point of 75° C. Phenol F-type epoxy resin (trade name YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd.); sulfur atom-containing epoxy resin with an epoxy equivalent of 245 and a melting point of 110°C (trade name YSLV-120TE manufactured by Nippon Steel Chemical Co., Ltd.) O-cresol novolak type epoxy resin (trade name ESCN-190 manufactured by Sumitomo Chemical Industry Co., Ltd.) of epoxy equivalent 195, softening point 65 DEG C and melt viscosity 3.1 of epoxy equivalent 170, softening point 70 DEG C, 150 DEG C Porous trisphenol methane type epoxy resin (polyfunctional epoxy resin) (trade name Epicoat E1032H manufactured by Japan Epikisilesin Co., Ltd.)

(Hardener)

The curing agent used is a phenol-aralkyl resin with a softening point of 70° C. and a hydroxyl equivalent of 175 (trade name Mirex XL-225 manufactured by Mitsui Chemicals Co., Ltd.), and a phenol novolak resin with a softening point of 80° C. and a hydroxyl equivalent of 106 ( Meiwa Kasei Co., Ltd. trade name H-1); softening point 83° C., polyfunctional phenolic resin with a hydroxyl equivalent of 103 (Meiwa Kasei Co., Ltd. trade name MEH-7500-3S).

(curing accelerator)

The curing accelerator used is an adduct of triphenylphosphine and p-benzoquinone (curing accelerator).

(coupling agent)

The coupling agent used is, γ-glycidoxypropyl trimethoxysilane (epoxy silane), secondary amino-containing silane coupling agent (γ-anilinopropyl trimethoxysilane (anilinosilane)) .

(flame retardant)

The flame retardant used was antimony trioxide and a bisphenol A brominated epoxy resin having a softening point of 80° C. and a bromine content of 4.8% by weight (trade name ESB-400T manufactured by Sumitomo Chemical Industries, Ltd.).

(Silicone)

The silicone resin used is methylphenyl silicone resin and silicone rubber.

(inorganic filler)

The inorganic filler used was spherical fused silica with an average particle diameter of 28 μm, an average particle diameter of 20 μm, an average particle diameter of 8 μm, and an average particle diameter of 0.5 μm.

(other additives)

Other additives used are higher fatty acid waxes and carbon black.

Table 19 project Epoxy molding material D 1 2 3 4 5 6 7 o-cresol novolac epoxy resin 7.4 6.7 4.6 Biphenyl type epoxy resin 6.9 7 1.4 Sulfur atom containing epoxy resin Multifunctional epoxy resin 4 5.5 Bisphenol F type epoxy resin 3.6 2.3 Bisphenol A Brominated Epoxy Resin 1.3 1.4 1.2 1.2 1.3 1.2 0.7 Phenol Novolac Resin 1.8 Phenol Aralkyl Resin 6.2 5.7 2.2 Multifunctional phenolic resin 4.8 4.9 4.5 4.6 Adducts of triphenylphosphine and p-benzoquinone 0.2 0.2 0.2 0.2 0.2 0.2 0.1 epoxy silane 0.4 0.4 Anilinosilane 0.4 0.2 0.4 0.2 0.3 Advanced Fatty Acid Wax 0.1 0.1 0.1 0.1 0.1 0.1 0.1 carbon black 0.3 0.3 0.2 0.2 0.2 0.2 0.1 Antimony trioxide 1.3 1.4 1.2 1.2 0.5 0.5 0.4 Silicone Rubber Methylphenyl silicone resin 1.3 1.4 1.2 1.2 Spherical fused silica with an average particle size of 28 μm Spherical fused silica with an average particle size of 20 μm 75.3 76.5 Spherical fused silica with an average particle size of 8 μm 66.1 65.9 67.3 67.3 79.4 Spherical fused silica with an average particle size of 0.5 μm 16.6 16.4 16.8 16.8 8.4 8.5 8.9 total 100 100 100 100 100 100 100

Table 20 project Epoxy molding material D 8 9 10 11 12 13 o-cresol novolac epoxy resin Biphenyl type epoxy resin 6.7 5.1 6.3 5.2 Sulfur atom containing epoxy resin 5.1 Multifunctional epoxy resin 7.6 Bisphenol F type epoxy resin Bisphenol A Brominated Epoxy Resin 1.2 0.6 0.9 1.3 1.1 0.9 Phenol Novolac Resin Phenol Aralkyl Resin 6.6 4.9 2.9 Multifunctional phenolic resin 4.9 1.9 1.5 Adducts of triphenylphosphine and p-benzoquinone 0.3 0.2 0.2 0.1 0.2 0.2 epoxy silane 0.4 Anilinosilane 0.3 0.3 0.4 0.3 0.3 Advanced Fatty Acid Wax 0.1 0.1 0.1 0.1 0.1 0.1 carbon black 0.1 0.1 0.2 0.3 0.2 0.2 Antimony trioxide 0.5 0.3 0.4 1.3 1.1 0.9 Silicone Rubber 3.3 2.7 Methylphenyl silicone resin 1.3 Spherical fused silica with an average particle size of 28 μm 50.5 61.9 67.5 Spherical fused silica with an average particle size of 20 μm 74.4 77.0 79.3 Spherical fused silica with an average particle size of 8 μm 25.2 17.7 17.9 Spherical fused silica with an average particle size of 0.5 μm 8.4 8.9 4.5 8.3 8.5 8.7 total 100 100.1 100 100 100 100

The properties of the obtained sealing epoxy resin molding materials D1 to D13 were evaluated by the test items shown in the table (spiral flow, disc flow, hardness when hot, flexural modulus, mold shrinkage, glass transition temperature). The results are shown in Table 21 and Table 22.

Table 21 project unit Epoxy molding material D 1 2 3 4 5 6 7 spiral flow inch 90 73 92 93 53 52 45 disc flow mm 125 107 117 114 79 92 88 Shore D hardness when hot - 77 85 86 80 82 81 89 Flexural modulus GPa 17.8 18.3 18.5 18.5 21.6 22.3 23.8 Forming shrinkage % 0.189 0.122 0.13 0.142 0.344 0.339 0.165 glass transition temperature ℃ 163 184 165 161 140 142 146

Table 22 project unit Epoxy molding material D 8 9 10 11 12 13 spiral flow inch 58 54 47 77 75 57 disc flow mm 90 100 93 117 95 86 Shore D hardness when hot - 84 81 80 84 75 82 Flexural modulus GPa 20.8 23.4 25.6 17.1 19.7 22.2 Forming shrinkage % 0.362 0.169 0.164 0.177 0.181 0.145 glass transition temperature ℃ 118 138 132 185 163 159

[Production of semiconductor device D1 (flip-chip BGA)]

Next, semiconductor devices of Examples D1 to D10 and Comparative Examples D1 to D3 were produced using epoxy resin molding materials D1 to D13 for sealing. In addition, the method of sealing with an epoxy resin molding material for sealing is to use a transfer molding machine to mold at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and then post-cure at 180°C for 5 hours.

Examples D1-D10 (Tables 23 and 24): After forming a fine wiring pattern on an insulating base material (glass cloth-epoxy resin laminate, Hitachi Chemical’s trade name E-679), the insulating protection resist (Taiyang Inky product name PSR4000AUS5) was applied to the surface except the gold-plated terminal on the semiconductor element mounting side and the external connection terminal on the reverse side, and the resulting shape was 40 mm in length x 80 mm in width x 0.6 mm in thickness at 120°C. The substrate for semiconductor device mounting was dried for 2 hours, and then 9 mm in length x 8 mm in width x 0.4 mm in thickness (area 72 mm ² ), bump diameter 145 μm, and bump pitch 200 μm were processed by the IR reflow process at 260°C for 10 seconds. , Semiconductor elements with 160 bumps are reflow processed and mounted. The bump height after mounting was 110 μm. Next, using epoxy resin molding materials D1-D4, D7, and D9-D13 for sealing, the semiconductor element mounting surface was vacuum transfer-molded with the dimensions of 30 mm in length x 70 mm in width x 0.8 mm in thickness under the above-mentioned conditions to obtain Examples D1-D10 of flip-chip BGA devices.

Comparative Examples D1 to D3 (Table 25): Using sealing epoxy resin molding materials D5, D6, and D8, the same procedure as in Examples D1 to D10 was performed to produce semiconductor devices D in Comparative Examples 1 to 3.

Table 23 project Example D 1 2 3 4 5 Epoxy molding material D 1 2 3 4 7 Outline of Substrate for Mounting Semiconductor Elements Vertical 40mm x horizontal 80mm x thick 0.6mm Shape of semiconductor element Vertical 9mm x horizontal 8mm x thick 0.4mm Semiconductor element bump diameter 145μm Semiconductor element bump pitch 200μm Semiconductor element bump count 160 Semiconductor element sealing shape Vertical 30mm x horizontal 70mm x thick 0.8mm

Table 24 project Example D 6 7 8 9 10 Epoxy molding material D 9 10 11 12 13 Outline of Substrate for Mounting Semiconductor Elements Vertical 40mm x horizontal 80mm x thick 0.6mm Shape of semiconductor element Vertical 9mm x horizontal 8mm x thick 0.4mm Semiconductor element bump diameter 145μm Semiconductor element bump pitch 200μm Semiconductor element bump count 160 Semiconductor element sealing shape Vertical 30mm x horizontal 70mm x thick 0.8mm

Table 25 project comparative example D 1 2 3 Epoxy molding material D 5 6 8 Outline of Substrate for Mounting Semiconductor Elements Vertical 40mm x horizontal 80mm x thick 0.6mm Shape of semiconductor element Vertical 9mm x horizontal 8mm x thick 0.4mm Semiconductor element bump diameter 145μm Semiconductor element bump pitch 200μm Semiconductor element bump count 160 Semiconductor element sealing shape Vertical 30mm x horizontal 70mm x thick 0.8mm

[Production of semiconductor device D2 (flip-chip BGA)]

Semiconductor devices of Examples D11 to D20 and Comparative Examples D4 to D6 were fabricated using epoxy resin molding materials D1 to D13 for sealing. In addition, the method of sealing with an epoxy resin molding material for sealing is to use a transfer molding machine to mold at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and then post-cure at 180°C for 5 hours.

Embodiment D11～D20 (Table 26, Table 27): After forming fine wiring patterns on the insulating base material (glass cloth-epoxy resin laminated board, Hitachi Chemical Manufacturing, trade name E-679), the insulation protection A resist (manufactured by Taiyo Inky, trade name PSR4000AUS5) was applied on the surface other than the gold-plated terminal on the semiconductor element mounting side and the external connection terminal on the reverse side, and the resulting shape was 50 mm in length x 100 mm in width x thickness at 120°C. The 0.6mm semiconductor element mounting substrate was dried for 2 hours, and then processed by the IR reflow process at 260°C and 10 seconds on the condition of 9mm in length x 8mm in width x 0.4mm in thickness (area 72mm ² ), bump diameter 145μm, bump A semiconductor element with a block pitch of 200 μm and a bump count of 160 was mounted by reflow processing. The bump height after mounting was 110 μm. Next, using epoxy resin molding materials D1-D4, D7, and D9-D13 for sealing, the semiconductor element mounting surface is vacuum transfer-molded with the dimensions of 40 mm in length x 90 mm in width x 0.8 mm in thickness using the above-mentioned conditions to obtain examples D11-D20. Flip-chip BGA device.

Comparative Examples D4-D6 (Table 28): Using sealing epoxy resin molding materials D5, D6, and D8, the same procedure as in Examples D11-D20 was performed to produce semiconductor devices in Comparative Examples D4-D6.

Table 26 project Example D 11 12 13 14 15 Epoxy molding material D 1 2 3 4 7 Outline of Substrate for Mounting Semiconductor Elements Vertical 50mm x horizontal 100mm x thick 0.6mm Shape of semiconductor element Vertical 9mm x horizontal 8mm x thick 0.4mm Semiconductor element bump diameter 145μm Semiconductor element bump pitch 200μm Semiconductor element bump count 160 Semiconductor element sealing shape Vertical 40mm x horizontal 90mm x thick 0.8mm

Table 27 project Example D 16 17 18 19 20 Epoxy molding material D 9 10 11 12 13 Outline of Substrate for Mounting Semiconductor Elements Vertical 50mm x horizontal 100mm x thick 0.6mm Shape of semiconductor element Vertical 9mm x horizontal 8mm x thick 0.4mm Semiconductor element bump diameter 145μm Semiconductor element bump pitch 200μm Semiconductor element bump count 160 Semiconductor element sealing shape Vertical 40mm x horizontal 90mm x thick 0.8mm

Table 28 project comparative example D 4 5 6 Epoxy molding material D 5 6 8 Outline of Substrate for Mounting Semiconductor Elements Vertical 50mm x horizontal 100mm x thick 0.6mm Shape of semiconductor element Vertical 9mm x horizontal 8mm x thick 0.4mm Semiconductor element bump diameter 145μm Semiconductor element bump pitch 200μm Semiconductor element bump count 160 Semiconductor element sealing shape Vertical 40mm x horizontal 90mm x thick 0.8mm

[Production of semiconductor device 3 (flip-chip BGA)]

Semiconductor devices of Examples D21 to D30 and Comparative Examples D7 to D9 were produced using epoxy resin molding materials D1 to D13 for sealing. In addition, the method of sealing with an epoxy resin molding material for sealing is to use a transfer molding machine to mold at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and then post-cure at 180°C for 5 hours.

Examples D21-D30 (Tables 29 and 30): After forming a fine wiring pattern on an insulating base material (glass cloth-epoxy resin laminate, manufactured by Hitachi Chemical, trade name E-679), the insulating protection resist An etchant (manufactured by Sun Inky, trade name PSR4000AUS5) was applied to the surface other than the gold-plated terminal on the semiconductor element mounting side and the external connection terminal on the reverse side, and the resulting shape was 60 mm in length x 120 mm in width x 0.6 in thickness at 120°C. The semiconductor element mounting substrate of mm was dried for 2 hours, and then processed by IR reflow process under the conditions of 260°C and 10 seconds for 9 mm in length x 8 mm in width x 0.4 mm in thickness (area 72 mm ² ), bump diameter 145 μm, bump A semiconductor element with a pitch of 200 μm and a number of bumps of 160 was mounted by reflow processing. The bump height after mounting was 110 μm. Next, using epoxy resin molding materials 1-4, 7, and 9-13 for sealing, the semiconductor element mounting surface is vacuum transfer-molded with the dimensions of 50 mm in length x 110 mm in width x 0.8 mm in thickness using the above-mentioned conditions to obtain examples D21-D30. Flip-chip BGA device.

Comparative Examples D7-D9 (Table 31): Using sealing epoxy resin molding materials D5, D6, and D8, the same procedure as in Examples D21-D30 was performed to produce semiconductor devices in Comparative Examples D7-D9.

Table 29 project Example D twenty one twenty two twenty three twenty four 25 Epoxy molding material D 1 2 3 4 7 Outline of Substrate for Mounting Semiconductor Elements Vertical 60mm x horizontal 120mm x thick 0.6mm Shape of semiconductor element Vertical 9mm x horizontal 8mm x thick 0.4mm Semiconductor element bump diameter 145μm Semiconductor element bump pitch 200μm Semiconductor element bump count 160 Semiconductor element sealing shape Vertical 50mm x horizontal 110mm x thick 0.8mm

Table 30 project Example D 26 27 28 29 30 Epoxy molding material D 9 10 11 12 13 Outline of Substrate for Mounting Semiconductor Elements Vertical 60mm x horizontal 120mm x thick 0.6mm Shape of semiconductor element Vertical 9mm x horizontal 8mm x thick 0.4mm Semiconductor element bump diameter 145μm Semiconductor element bump pitch 2001μm Semiconductor element bump count 160 Semiconductor element sealing shape Vertical 50mm x horizontal 110mm x thick 0.8mm

Table 31 project comparative example D 7 8 9 Epoxy molding material D 5 6 8 Outline of Substrate for Mounting Semiconductor Elements Vertical 60mm x horizontal 120mm x thick 0.6mm Shape of semiconductor element Vertical 9mm x horizontal 8mm x thick 0.4mm Semiconductor element bump diameter 145μm Semiconductor element bump pitch 200μm Semiconductor element bump count 160 Semiconductor element sealing shape Vertical 50mm x horizontal 110mm x thick 0.8mm

The obtained semiconductor devices of Examples D1 to D30 and Comparative Examples D1 to D9 were evaluated by the substrate warpage test to compare the glass transition temperature, flexural modulus, mold shrinkage, and fillability during semiconductor element molding. The evaluation results are shown in Tables 32-35.

Table 32 project unit Example D 1 2 3 4 5 6 7 8 9 10 Epoxy molding material D - 1 2 3 4 7 9 10 11 12 13 glass transition temperature ℃ 163 184 165 161 146 138 132 185 163 159 Flexural modulus GPa 17.8 18.3 18.5 18.5 23.8 23.4 25.6 17.1 19.7 22.2 Forming shrinkage % 0.189 0.122 0.130 0.142 0.165 0.169 0.164 0.177 0.181 0.145 Substrate Warpage mm 0.9 1.1 1.1 1.0 4.5 3.8 4.2 1.1 2.4 1.8 Forming fill rate area% 100 100 100 100 66 100 71 100 100 75

Table 33 project unit Example D 11 12 13 14 15 16 17 18 19 20 Epoxy molding material D - 1 2 3 4 7 9 10 11 12 13 glass transition temperature ℃ 163 184 165 161 146 138 132 185 163 159 Flexural modulus GPa 17.8 18.3 18.5 18.5 23.8 23.4 25.6 17.1 19.7 22.2 Forming shrinkage % 0.189 0.122 0.130 0.142 0.165 0.169 0.164 0.177 0.181 0.145 Substrate Warpage mm 1.5 1.6 1.4 1.5 4.9 4.0 4.8 1.7 2.8 2.2 Forming fill rate area% 100 100 100 100 54 90 71 98 94 71

Table 34 project unit Example D twenty one twenty two twenty three twenty four 25 26 27 28 29 30 Epoxy molding material D - 1 2 3 4 7 9 10 11 12 13 glass transition temperature ℃ 163 184 165 161 146 138 132 185 163 159 Flexural modulus GPa 17.8 18.3 18.5 18.5 23.8 23.4 25.6 17.1 19.7 22.2 Forming shrinkage % 0.189 0.122 0.130 0.142 0.165 0.169 0.164 0.177 0.181 0.145 Substrate Warpage mm 1.8 2.0 1.9 1.9 5.0 4.3 5.0 2.0 3.1 2.5 Forming fill rate area% 100 100 100 100 66 77 52 88 84 58

Table 35 project unit comparative example D 1 2 3 4 5 6 7 8 9 Epoxy molding material D - 5 6 8 5 6 8 5 6 8 glass transition temperature ℃ 140 142 118 140 142 118 140 142 118 Flexural modulus GPa 21.6 22.3 20.8 21.6 22.3 20.8 21.6 22.3 20.8 Forming shrinkage % 0.344 0.339 0.362 0.344 0.339 0.362 0.344 0.339 0.362 Substrate Warpage mm 10.5 12.8 8.8 13.6 15.1 10.2 15.5 18.0 12.7 Shape fill rate area% 62 84 95 52 77 84 41 63 71

Those that do not meet any of the conditions that the glass transition temperature based on the TMA method (differential expansion method) is 150°C or higher, the flexural modulus based on JIS K6911 is 19GPa or lower, and the molding shrinkage based on JIS K6911 is 0.2% or lower In Comparative Examples 1 to 9, in which materials 5, 6, and 8 were sealed by epoxy resin molding, the warpage of the substrate was large, and the filling property during molding was not good.

Relatively speaking, Examples 1 to 30 sealed with epoxy resin molding materials 1 to 4, 7 and 9 to 10 that meet at least one of the above conditions have less warpage of the substrate and good filling properties during molding. . In addition, the embodiment sealed with epoxy resin molding materials 1-4 and 11 meeting all the conditions has a particularly good substrate warpage of less than or equal to 2.0 mm, and the filling property during molding is also particularly good without voids.

[Evaluation method]

(1) spiral flow

Using a mold for measuring spiral flow based on EMMI-1-66, an epoxy resin molding material for sealing was molded with a transfer molding machine under the conditions of mold temperature 180°C, molding pressure 6.9MPa, and curing time 90 seconds, and the flow distance ( inch).

(2) Circular plate flow

Using a flat mold for flow measurement of a circular plate with an upper mold of 200mm (w) x 200mm (D) x 25mm (H) and a lower mold of 200mm (w) x 200mm (D) x 15mm (H), accurately weigh the 5g of the sample (epoxy resin molding material for sealing) was placed in the center of the lower mold heated to 180°C. After 5 seconds, the upper mold heated to 180°C was closed, and compression molding was carried out under the conditions of a load of 78N and a curing time of 90 seconds. , Measure the long diameter (mm) and short diameter (mm) of the molded product with a vernier caliper, and use the average value (mm) as a disc flow.

(3) Hardness when hot

The sealing epoxy resin molding material was molded into a circular plate with a diameter of 50mm x a thickness of 3mm under the conditions of a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and was immediately measured with a Shore D-type hardness tester.

(4) Flexural modulus

Using a mold for forming a bending test piece based on JIS K6911, use a transfer molding machine to mold at a mold temperature of 180°C, a molding pressure of 6.9GPa, and a curing time of 90 seconds, then post-cure at 180°C for 5 hours, and then conform to JIS K6911. The flexural modulus of elasticity was determined by the flexural test method.

(5) Forming shrinkage

Using a mold for measuring the molding shrinkage rate according to JIS K6911, use a transfer molding machine to mold at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds. After curing at 180°C for 5 hours, it is recorded in accordance with JIS K6911. The forming shrinkage rate test method is used to determine the forming shrinkage rate.

(6) Glass transition temperature

Using a mold that can produce a test piece of 20mm×4mm×4mm, use a transfer molding machine to mold at a mold temperature of 180°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds, and then post-cure at 180°C for 5 hours. TMA apparatus (TSC 1000) manufactured by Mac Systems, measured the glass transition temperature and thermal expansion coefficient according to the TMA method (differential expansion method).

(7) Substrate warpage

Place the resin-molded flip-chip BGA substrate on a horizontal and smooth surface, fix one end of the substrate in the length direction with a 50g weight, and use a ruler to read the size of the other end floating from the smooth surface to 1/10mm.

(8) Filling rate during molding

The semiconductor device was observed transparently with an ultrasonic probe imaging device (HYE-HOCUS type manufactured by Hitachi Construction Machinery Co., Ltd.), and the filling area ratio (area %) to the sealing area was calculated and evaluated.

Industrial Utilization Possibility

The sealing epoxy resin molding material for flip-chip mounting according to the present invention has high filling properties required as an underfill and has few molding defects such as voids, so it has great industrial value. In addition, the sealing epoxy resin molding material for flip-chip mounting according to the present invention has low warpage required as an underfill and exhibits good flow characteristics, so it has great industrial value.

As described above, those skilled in the art can make many changes and modifications to the preferred embodiments of the present invention without departing from the spirit and scope of the present invention.

Claims (35)

1. epoxy resin molding material for encapsulation contains (A) Resins, epoxy, (B) solidifying agent and (C) inorganic filler, it is characterized by, and the median size of described inorganic filler (C) is that 12 μ m or following and specific surface area are 3.0m ²/ g or more than.

2. epoxy resin molding material for encapsulation, contain (A) Resins, epoxy, (B) solidifying agent and (C) inorganic filler, it is characterized by, described inorganic filler (C) is, maximum particle diameter is at 63 μ m or following, and contains 5wt% or above particle diameter at 20 μ m or above inorganic filler.

3. epoxy resin molding material for encapsulation contains (A) Resins, epoxy, (B) solidifying agent and (C) inorganic filler, it is characterized by, and the median size of described (C) inorganic filler is that 15 μ m or following and specific surface area are 3.0～6.0m ²/ g is used for possessing (a1)～(d1) constitute one or more semiconductor device,

(a1) bump height of flip-chip is 150 μ m or following;

(b1) bump pitch of flip-chip is 500 μ m or following;

(c1) area of semi-conductor chip is 25mm ²Or more than;

(d1) total thickness of sealing material is 2mm or following.

4. epoxy resin molding material for encapsulation, contain (A) Resins, epoxy, (B) solidifying agent and (C) inorganic filler, it is characterized by, described epoxy resin molding material for encapsulation meets at least one condition in the following condition: based on the second-order transition temperature of TMA method be 150 ℃ or more than; Crooked elastic rate based on JIS-K6911 is 19GPa or following; Based on the shaping shrinkage rate of JIS-K6911 be 0.2% or below.

5. according to each the described epoxy resin molding material for encapsulation in the claim 1～4, it is characterized by, (A) Resins, epoxy 150 ℃ melt viscosity be 2 pools or below.

6. according to each the described epoxy resin molding material for encapsulation in the claim 1～4, it is characterized by, (A) Resins, epoxy contains in biphenyl type epoxy resin, bisphenol f type epoxy resin, stilbene type Resins, epoxy, sulfur atom-containing Resins, epoxy, phenolic resin varnish type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene type Resins, epoxy and the tritane type Resins, epoxy at least a kind.

7. according to each the described epoxy resin molding material for encapsulation in the claim 1～4, it is characterized by, (B) solidifying agent 150 ℃ melt viscosity be 2 pools or below.

8. according to each the described epoxy resin molding material for encapsulation in the claim 1～4, it is characterized by, (B) solidifying agent contains at least a in biphenyl type resol, aralkyl-type phenol resin, dicyclopentadiene-type resol, tritane type resol and the phenolic varnish type resol.

9. according to each the described epoxy resin molding material for encapsulation in the claim 1～4, it is characterized by, further contain (F) curing catalyst.

10. epoxy resin molding material for encapsulation according to claim 1 is characterized by, and described inorganic filler (C) meets at least one condition in the following condition: particle diameter 12 μ m or following for 50wt% or more than; Particle diameter 24 μ m or following be 70wt% or more than; Particle diameter 32 μ m or following be 80wt% or more than; Particle diameter 48 μ m or following be 90wt% or more than.

11. each the described epoxy resin molding material for encapsulation according in the claim 1～3 is characterized by, (C) median size of inorganic filler is 10 μ m or following.

12. each the described epoxy resin molding material for encapsulation according in the claim 1～3 is characterized by, (C) specific surface area of inorganic filler is 3.5～5.5m ²/ g.

13. each the described epoxy resin molding material for encapsulation according in the claim 1～4 is characterized by, and further contains (D) coupler.

14. epoxy resin molding material for encapsulation according to claim 13 is characterized by, (D) coupler has the silane coupling agent of secondary amino group for (D2).

15. epoxy resin molding material for encapsulation according to claim 14 is characterized by, the silane coupling agent that (D2) has secondary amino group contains the compound shown in the following general formula (I),

In the formula, R ¹Be selected from the alkyl of hydrogen atom, carbonatoms 1～6, the alkoxyl group of carbonatoms 1～2; R ²Be selected from the alkyl and the phenyl of carbonatoms 1～6; R ³Expression methyl or ethyl; N represents 1～6 integer; M represents 1～3 integer.

16. each the described epoxy resin molding material for encapsulation according in the claim 1～4 is characterized by, and further contains (E) phosphorus compound.

17. epoxy resin molding material for encapsulation according to claim 16 is characterized by, (E) phosphorus compound contains phosphoric acid ester.

18. epoxy resin molding material for encapsulation according to claim 17 is characterized by, phosphoric acid ester contains the compound shown in the following general formula (II),

In the formula, 8 R represent the alkyl of carbonatoms 1～4, can be all identical or different; Ar represents aromatic ring.

19. epoxy resin molding material for encapsulation according to claim 16 is characterized by, (E) phosphorus compound contains phosphine oxide.

20. epoxy resin molding material for encapsulation according to claim 19 is characterized by, phosphine oxide contains the compound shown in the following general formula (III),

In the formula, R ¹, R ²And R ³The replacement of expression carbonatoms 1～10 or alkyl, aryl, aralkyl and the hydrogen atom of non-replacement can be all identical or different, all are the situation of hydrogen atom but get rid of.

21. each the described epoxy resin molding material for encapsulation according in the claim 1～3 is characterized by, and is used for possessing (a1)～(f1) constitute one or more semiconductor device,

(a1) bump height of flip-chip is 150 μ m or following;

(b1) bump pitch of flip-chip is 500 μ m or following;

(c1) area of semi-conductor chip is 25mm ²Or more than;

(d1) total thickness of sealing material is 2mm or following;

(e1) number of lugs of flip-chip be 100 or more than;

Ventage thickness when (f1) being shaped is 40 μ m or following.

22. each the described epoxy resin molding material for encapsulation according in the claim 1～3 is characterized by, and is used for possessing (a2)～(f2) constitute one or more semiconductor device,

(a2) bump height of flip-chip is 100 μ m or following;

(b2) bump pitch of flip-chip is 400 μ m or following;

(c2) area of semi-conductor chip is 50mm ²Or more than;

(d2) total thickness of sealing material is 1.5mm or following;

(e2) number of lugs of flip-chip be 150 or more than;

Ventage thickness when (f2) being shaped is 30 μ m or following.

23. epoxy resin molding material for encapsulation according to claim 13 is characterized by, (D) the filler fraction of coverage of coupler is 0.3～1.0.

24. epoxy resin molding material for encapsulation according to claim 13 is characterized by, the weight loss on heating rate after the 200 ℃/1hr heating is 0.25 weight % or following.

25. epoxy resin molding material for encapsulation according to claim 23 is characterized by, the weight loss on heating rate after the 200 ℃/1hr heating is 0.25 weight % or following.

26. epoxy resin molding material for encapsulation according to claim 4 is characterized by, and is used for possessing following (c1), (d1) and one or more the semiconductor device that (g1) constitutes,

(c1) area of semi-conductor chip is 25mm ²Or more than;

(d1) total thickness of sealing material is 2mm or following;

(g1) the sealing material shaping area of once-forming mode is 3000mm ²Or more than.

27. epoxy resin molding material for encapsulation according to claim 4 is characterized by, and is used for possessing following (c2), (d2) and one or more the semiconductor device that (g2) constitutes,

(c2) area of semi-conductor chip is 50mm ²Or more than;

(d2) total thickness of sealing material is 1.5mm or following;

(g2) the sealing material shaping area of once-forming mode is 5000mm ²Or more than.

28. epoxy resin molding material for encapsulation according to claim 4 is characterized by, the warpage of semiconductor device is 5.0mm or following.

29. epoxy resin molding material for encapsulation according to claim 4 is characterized by, the warpage of semiconductor device is 2.0mm or following.

30. epoxy resin molding material according to claim 4, wherein, (C) the inorganic filler containing ratio is 70～90wt% with respect to epoxy resin molding material.

31. a semiconductor device is characterized by, to contain (A) Resins, epoxy, (B) solidifying agent and (C) the epoxy resin molding material for encapsulation sealing of inorganic filler.

32. semiconductor device according to claim 29 is characterized by, and possesses in following (a1)～(f1) formation one or more,

(a1) bump height of flip-chip is 150 μ m or following;

(b1) bump pitch of flip-chip is 500 μ m or following;

(c1) area of semi-conductor chip is 25mm ²Or more than;

(d1) total thickness of sealing material is 2mm or following;

(e1) number of lugs of flip-chip be 100 or more than;

Ventage thickness when (f1) being shaped is 40 μ m or following.

33. semiconductor device according to claim 29 is characterized by, and possesses in following (a2)～(f2) formation one or more,

(a2) bump height of flip-chip is 100 μ m or following;

(b2) bump pitch of flip-chip is 400 μ m or following;

(c2) area of semi-conductor chip is 50mm ²Or more than;

(d2) total thickness of sealing material is 1.5mm or following;

(e2) number of lugs of flip-chip be 150 or more than;

Ventage thickness when (f2) being shaped is 30 μ m or following.

34. semiconductor device according to claim 29 is characterized by, and possesses following (c1), (d1) and (g1) one or more in constituting,

(c1) area of semi-conductor chip is 25mm ²Or more than;

(d1) total thickness of sealing material is 2mm or following;

(g1) the sealing material shaping area of once-forming mode is 3000mm ²Or more than.

35. semiconductor device according to claim 29 is characterized by, and possesses following (c2), (d2) and (g2) one or more in constituting,

(c2) area of semi-conductor chip is 50mm ²Or more than;

(d2) total thickness of sealing material is 1.5mm or following;

(g2) the sealing material shaping area of once-forming mode is 5000mm ²Or more than.

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