WO2005108483A1

WO2005108483A1 - Electronic component device

Info

Publication number: WO2005108483A1
Application number: PCT/JP2005/008520
Authority: WO
Inventors: Kazumasa Igarashi; Ichiro Hazeyama; Masahiro Kubo
Original assignee: Nitto Denko Corporation; Nec Corporation
Priority date: 2004-05-11
Filing date: 2005-05-10
Publication date: 2005-11-17
Also published as: JP2005350646A

Abstract

A high-reliability electronic component device resin-sealed with a low-viscosity sealing epoxy resin composition, which electronic component device even when having a defect in electrical connection after once underfilling, permits removal of any residual at about room temperature to thereby excel in repair easiness and when in connected and mounted structure, ensures high reliability. There is provided an electronic component device having semiconductor element (flip chip) (1) mounted on wiring circuit substrate (2) in such a fashion that electrode part for connection (solder bump) (3) provided on the semiconductor element (flip chip) (1) is opposed to electrode part for connection (solder pad) (5) provided on the wiring circuit substrate (2). Any gap between the wiring circuit substrate (2) and the semiconductor element (flip chip) (1) is resin-sealed with sealing resin layer (4) consisting of a liquid epoxy resin composition comprising not only the undermentioned constituents (A)-(C) but also the undermentioned constituent (D): (A) liquid epoxy resin, (B) aromatic diamine curing agent, (C) inorganic filler, and (D) organic filler.

Description

Specification

Electronic component equipment

Technical field

[0001] The present invention relates to a connection electrode section for a semiconductor package such as a BGA (ball-grid 'array) or CSP (chip-scale' package or chip-size 'package) or a semiconductor component such as a semiconductor element. In the board mounting connection method, which electrically connects the semiconductor component and the opposing electrodes of the circuit board via bumps), the gap between the semiconductor package and the circuit board is filled with a liquid epoxy resin composition and sealed with a resin. The present invention relates to an electronic component device having good repairability.

Background art

In recent years, semiconductor packages such as BGAs and CSPs have been mounted on printed wiring boards with high density. Conventionally, in mounting a semiconductor package having such an array type bump electrode on a substrate, the connection pitch between the bumps is widened and the connection metal bump is large, so that underfill or the like is required to disperse stress and mechanical reinforcement.とも Sufficient reliability was maintained without resin sealing. However, in recent years, since the bump electrodes have a narrow pitch and a small force, reinforcement with a resin such as underfill has come to be performed.

[0003] On the other hand, a direct chip attachment method using a bare chip such as a semiconductor element flip chip has attracted attention. In this flip-chip connection method, a so-called “C4 technology” is known, in which a high-melting-point solder bump is formed on the chip side and metal-to-metal bonding with the solder on the ceramic circuit board side is performed.

However, when a resin-based substrate such as a printed circuit board made of glass epoxy resin is used in place of the ceramic circuit substrate, the difference is caused by a difference in thermal expansion coefficient between the chip and the resin-based substrate. There are problems such as the destruction of the solder bump joints, resulting in insufficient connection reliability. As a countermeasure for such a problem, a technology for improving reliability by dispersing thermal stress by sealing a gap between the semiconductor element and the resin-based substrate using, for example, a liquid resin composition, V It is common to do so-called underfill.

[0005] While pressing, the liquid resin composition used for the underfill is generally Since a one-pack type thermosetting resin composition containing a siloxane resin as a main component is used, it does not melt, has high adhesive strength, does not decompose, and is insoluble in solvents after being heated and cured. However, there is a problem that repair cannot be easily performed. Therefore, once underfill is performed, for example, there is a problem that an electronic component device having a defective electrical connection is scrapped and must be discarded. This means that in recent years, recyclability has been required for global environmental protection, and it is necessary to avoid generating waste as much as possible, and it is possible to repair even underfill. Is required.

[0006] As such a repairable liquid epoxy resin composition, an epoxy resin is used as a main component, a capsule-type curing agent coated with a thermoplastic resin is used as a curing agent, and a resin is imparted with a resin. An electronic component bonding adhesive using an acrylic resin as an agent has been disclosed (see Patent Document 1).

[0007] Further, an adhesive composition comprising a thermosetting resin, a thermoplastic resin such as polymethyl methacrylate, an inorganic filler, and a coupling agent has been proposed! Puru (see Patent Document 2).

[0008] A repairable thermosetting resin composition containing an epoxy resin, a curing agent, and a plasticizer has been disclosed (see Patent Document 3). However, the effect on physical properties such as the glass transition point of the cured product, which is important for the reliability of the connected mounting structure, is described.

Patent Document 1: JP-A-7-102225

Patent Document 2: JP 2001-81439A

Patent Document 3: JP-A-10-204259

Disclosure of the invention

Problems to be solved by the invention

[0009] However, it is difficult to say that the adhesive for bonding electronic components described in Patent Document 1 has thixotropic properties and thus is suitable for fluidity as an underfill. It is desirable for the fill to have flow characteristics that do not exhibit shear rate dependence. In addition, the adhesive described in Patent Document 2 obtained by uniformly stirring and mixing generally has a high viscosity in accordance with the molecular weight of the thermoplastic resin. After mixing the prepared inorganic filler, the viscosity increased, and it was difficult to say that the low viscosity required for the underfill could be achieved. In addition, the thermoplastic resin is used for electronic parts. The aim is to lower the glass transition point and softening point of the cured product in order to improve the ease of removal by heating, and the viewpoint of maintaining the glass transition point to ensure connection reliability has been mentioned. Absent. Furthermore, the thermosetting resin composition described in Patent Document 3 does not describe the effect on the physical properties such as the glass transition point of the cured product which is important for the reliability of the connected mounting structure. It is insufficient as an adhesive material for underfill.

[0010] Generally, as a means for improving the repairability of a thermosetting resin composition such as an epoxy resin, a thermoplastic resin such as polymethyl methacrylate is used as described in the above-mentioned technology. Although the resin is mixed, there is a difficulty in that a step of removing the cured product residue remaining on the circuit board with a solvent after heating the silicon chip and removing the chip needs to be performed at a high temperature. It has been difficult to say that the above-mentioned conventional technique is sufficient because it is desired that the work of repairing the cured body can be performed at around room temperature.

[0011] The present invention has been made in view of such circumstances, and it is possible to remove a residue near room temperature even in an electronic component device having an electrical connection failure once underfilled. A highly reliable electronic component that is easily sealed with a low-viscosity epoxy resin composition for encapsulation that has excellent repairability and that has a connected mounting structure and high reliability. Its purpose is to provide a device.

Means for solving the problem

[0012] In order to achieve the above object, the electronic component device of the present invention provides the electronic component device, wherein the connection electrode portion provided on the semiconductor component and the connection electrode portion provided on the circuit board face each other. An electronic component device in which a semiconductor component is mounted on a substrate and a gap between the circuit board and the semiconductor component is sealed by a sealing resin layer, wherein the sealing resin layer has the following (A) to When it is formed by a liquid epoxy resin composition containing the following component (D) together with the component (C), the composition takes the following structure.

(A) Liquid epoxy resin.

(B) Aromatic diamine curing agents.

(C) an inorganic filler.

(D) Organic additives.

[0013] The present inventors have achieved a circuit board and a semiconductor component (semiconductor device) in order to achieve the above object. And semiconductor devices, etc.), the epoxy resin composition which is an underfill material for sealing the voids with the resin. First, the present inventors have found that a cured product of a specific epoxy resin composition is solvated with a specific solvent and subsequently swells, and as a result, a decrease in the film strength of the cured product as a sealing resin and It has been found that the adhesive strength is reduced, the cured body can be mechanically peeled, and the semiconductor element (flip chip) can be repaired (Japanese Patent Application Laid-Open No. 2003-119454). In other words, the specific fluorinated aromatic diamines as the curing agent decrease the solubility parameter [Solubility Parameter (SP)] value of the cured product due to the trifluoromethyl substituent or the fluorine substituent, so that the specific solvent is used. The effect of solvation and subsequent swelling is easy to occur, and repairability is exhibited.

Further, in the present invention, it has been found that the combined use of an organic additive can further improve the repairability. That is, the present inventors have repeatedly studied an epoxy resin composition which is an underfill material for resin sealing a gap between a circuit board and a semiconductor component in order to achieve the above object. As a result, when an organic additive [component (D)] is blended together with the above components (A) to (C), the cured product of the epoxy resin composition is solvated with a specific solvent, and swelling occurs continuously. As a result, the coating strength of the cured resin, which is the sealing resin, and the adhesive strength are reduced, and the cured product can be mechanically peeled off, and the resin residue remaining on the circuit board can be easily removed at room temperature or the like. The present inventors have found that repair of semiconductor components such as the above becomes easier, and arrived at the present invention.

That is, the present invention includes the following aspects.

[0016] 1. A semiconductor component is mounted on the circuit board in a state where the connection electrode section provided on the semiconductor component and the connection electrode section provided on the circuit board face each other. Wherein the sealing resin layer contains the following components (A) to (C) together with the following components (D). An electronic component device formed by a epoxy resin composition.

(A) Liquid epoxy resin.

(B) Aromatic diamine curing agents.

(C) an inorganic filler. (D) Organic additives.

[0017] 2. The electronic component device according to the above item 1, wherein the aromatic diamine curing agent as the component (B) is at least one of an aromatic diamine represented by the following general formula (1) and a derivative thereof. Place.

[0018] [Formula 1]

[In the formula (1), X is hydrogen and / or C „H _E „ ₊₁ (n is 1 to 10

Is a positive number). m is a positive number from 1 to 4. R ^{1 to} R ⁴ are hydrogen

Or monovalent ^ IS, which is the same or different,

Good. ]

3. The electronic component device according to the above item 1, wherein the aromatic diamine curing agent as the component (B) is at least one of a fluorinated aromatic diamine represented by the following general formula (2) and a derivative thereof.

[Formula 2]

[In the formula (2), Y is fluorine and Z or C, F ^, (η is from 1 to 10

It is a positive number. ). m is a positive number from 1 to 4. R * ⁵ ~R ^e is hydrogen

Or a monovalent organic group, which may be the same or different 1 /

No. ]

[0020] 4. The aromatic diamine curing agent as the component (B) is a monoepoxy compound having one epoxy group in one molecule, and 2,2′-ditrifluoromethyl—4, 4. The electronic component device according to the above item 1, which is a reaction product with 4'-diaminobiphenyl.

[0021] 5. Monoepoxy conjugate containing one epoxy group in one molecule of n-butyl glycidyl ether, aryl glycidyl ether, 2-ethylhexyl glycidyl ether Tere, styrene oxide, phenyldaricidyl ether, cresyl glycidyl ether, lauryl glycidyl ether, p-sec-butylphenol glycidyl ether, phenol glycidyl ether, glycidyl ether of carbinol, glycidyl methacrylate 5. The electronic component device according to the above item 4, wherein the device is at least one selected from the group consisting of butylcyclohexene monoepoxide and α-pinene oxide.

[0022] 6. The above-mentioned compound containing a prepolymer obtained by reacting at least one of the aromatic diamine represented by the general formula (1) and a derivative thereof with a liquid epoxy resin as the component (II). Electronic component device according to the above.

7. The above-mentioned resin containing a prepolymer obtained by reacting at least one of the fluorine-containing aromatic diamine represented by the above general formula (2) and a derivative thereof with a liquid epoxy resin as the component (Α). Electronic component device according to 3.

8. The electronic component device according to any one of the above items 1 to 7, wherein the inorganic filler as the component (C) is a spherical silica powder having an average particle diameter of 10 m or less.

9. The inorganic filler as the component (C) is a spherical silica powder having an average particle diameter of 10 m or less, the surface of which is coated with an organic silane compound represented by the following general formula (3). 8. The electronic component device according to any one of 1 to 7 above.

[0026]

(α '-O-^-S i-"f 3 ^l ) _b ■■■ (3)

Wherein _(3), α 'is than monovalent than hydrogen, J3 ¹ is at least

1 amino group, epoxy group, vinyl group, styryl group, methacryloxy

And monovalent organic groups including ureido groups. A and b are a + b = 4

And each is a positive number between 1 and 3. ]

10. The electronic component device according to the above item 9, wherein the organosilane compound represented by the general formula (3) is an organosilane compound represented by the following general formula (4). [0028]

{a ¹ -Oh ^ — S i—— y-NI I ₂ … (4)

[In the formula (4), α ¹ is a monovalent organic group other than hydrogen, and 7 is a divalent organic group.

It is. ]

[0029] 11. A spherical silica having an average particle diameter of 10 m or less, wherein the surface of the inorganic filler as the component (C) is coated with an organic titanium conjugate represented by the following general formula (5): The electronic component device according to any one of the above items 1 to 7, which is a powder.

[0030] [Formula 5]

(α ¹ -0)-^ —T i− (β ^ι ) _b- (5)

[In equation (5), ^1- element is monovalent 1S, and β ΐ is at least

1 amino group, epoxy group, butyl group, styryl group, methacryloxy

Group, ureido group is t ¾S with ^ tf "" "valence, and a and b are a + b = 4

And each is a positive number between 1 and 3. ]

12. The organic additive as the component (D) is at least one of spherical thermoplastic resin particles having an average particle diameter of 10 m or less and spherical crosslinked resin particles having an average particle diameter of 10 μm or less. (1) The electronic component device according to any one of (1) to (1).

13. The electronic component device according to the above item 12, wherein at least one of the spherical thermoplastic resin particles and the spherical crosslinked resin particles is a spherical polymethylmetharylate particle.

14. The weight-average molecular weight of the spherical polymethyl methacrylate particles is from 100,000 to 5,000.

14. The electronic component device according to the above item 13, wherein the number is in the range of 000,000,000.

15. The electronic component device according to the above item 13, wherein the spherical polymethyl methacrylate particles are spherical crosslinked polymethyl methacrylate particles having a glass transition temperature of 100 ° C. or higher.

16. The electronic component device according to any one of the above 1 to 15, wherein the semiconductor component is a semiconductor element.

[0036] 17. The electronic component device according to any one of the above 1 to 15, wherein the semiconductor component is a semiconductor device.

The invention's effect

As described above, the present invention provides an organic additive [component (D)] together with the components (A) to (C). This is an electronic component device in which the gap between the circuit board and the semiconductor component is sealed by a sealing resin layer containing a liquid epoxy resin composition. Therefore, the liquid epoxy resin composition easily solvates with a specific organic solvent at room temperature and swells even after being cured with low viscosity and without generation of voids due to filling. As a result, the strength of the cured product is significantly reduced, and the cured product can be easily separated from the adherend (such as an electrode). Therefore, an electronic component device obtained by resin encapsulation using this liquid epoxy resin composition has excellent connection reliability, and even if a connection failure occurs due to positional displacement between electrodes, etc. An electronic component device with excellent repairability can be obtained without discarding the electronic component device itself.

[0038] Then, as the aromatic diamine curing agent [component (B)], at least one of an aromatic diamine and a derivative thereof represented by the following general formula (1) or a general formula (2) The use of at least one of the fluorine-containing aromatic diamines and derivatives thereof represented by the following formula (1) is preferred because the effect of rapid swelling and ease of repair can be exhibited.

As the aromatic diamine curing agent [component (B)], a monoepoxy compound containing one epoxy group in one molecule and 2,2′-ditrifluoromethyl-4,4 Use of the reaction product with '-diaminobiphenyl enhances solvation and swelling, and enables good repair.

As the aromatic diamine curing agent [component (B)], at least one of an aromatic diamine represented by the following general formula (1) and a derivative thereof, or a compound represented by the general formula (2): The use of at least one of the fluorinated aromatic diamines and derivatives thereof and the reaction of the liquid epoxy resin (component (A)) with a prepolymer yields a further improvement in the curing speed. Can be achieved. Moreover, since the liquid epoxy resin composition can be formed in advance from the liquefaction to the viscous paste-like state, complicated steps are not required in the measurement at the time of mixing and the subsequent dispersion step, and the liquid epoxy resin composition can be easily obtained. be able to.

[0041] Furthermore, when the above-mentioned inorganic filler [component (C)] is used, spherical silica powder having a specific average particle diameter, the surface of which is coated with a specific organosilane compound or a specific organic titanium compound, is used. The effect is that the viscosity of the composition can be reduced or the thixotropy can be reduced. [0042] When at least one of the spherical thermoplastic resin particles having a specific average particle diameter and the spherical crosslinked resin particles having a specific average particle diameter is used as the organic additive [(D) component], This has the effect that the narrow gap between the component and the resin-based circuit board can be sufficiently injected and filled.

Brief Description of Drawings

FIG. 1 is a cross-sectional view schematically showing one example of an electronic component device of the present invention.

FIG. 2 is a cross-sectional view schematically showing another example of the electronic component device of the present invention.

Explanation of symbols

[0044] 1 Semiconductor element (flip chip)

2, 12 Wiring circuit board

3 Connecting electrodes for semiconductor devices (solder bumps)

4, 14 Sealing resin layer

5, 15 Connection electrode part of printed circuit board (solder pad)

11 Semiconductor device (semiconductor package)

13 Electrodes for connecting semiconductor devices (solder bumps)

BEST MODE FOR CARRYING OUT THE INVENTION

[0045] The electronic component device of the present invention provides a semiconductor component, a connection electrode portion provided on the semiconductor component, a circuit board, a connection electrode portion provided on the circuit board, and a gap between the circuit board and the semiconductor component. Including resin to be sealed, the semiconductor component is mounted on the circuit board such that the connection electrode provided on the semiconductor component and the connection electrode provided on the circuit board face each other. Further, the sealing resin is a cured product of a liquid epoxy resin composition containing the following components (A), (B), (C) and (D).

(A) Liquid epoxy resin.

(B) Aromatic diamine curing agents.

(C) an inorganic filler.

(D) Organic additives.

As an example of the configuration of the electronic component device of the present invention, a case where the semiconductor component is a semiconductor element (flip chip) will be described. That is, as shown in FIG. With the connection electrode portion (solder bump) 3 provided on 1 and the connection electrode portion (solder pad) 5 provided on the printed circuit board 2 facing each other, the semiconductor is placed on the printed circuit board 2. Element (flip chip) 1 is mounted. Then, a gap between the wiring circuit board 2 and the semiconductor element (flip chip) 1 is resin-sealed by a sealing resin layer 4 formed using a liquid epoxy resin composition.

In the above electronic component device, the connection electrode portion 3 provided on the semiconductor element 1 is formed in a bump shape, but is not particularly limited to this, and is provided on the printed circuit board 2. The connection electrode portion 5 may be provided in a bump shape.

Next, as another example of the configuration of the electronic component device of the present invention, a case where the semiconductor component is a semiconductor device (semiconductor package) will be described. That is, as shown in FIG. 2, the connection electrode portion (solder bump) 13 provided on the semiconductor device (semiconductor package) 11 and the connection electrode portion (solder pad) 15 provided on the wiring circuit board 12 face each other. In this state, the semiconductor package 11 is mounted on the wiring circuit board 12. Then, a gap between the printed circuit board 12 and the semiconductor package 11 is resin-sealed by a sealing resin layer 14 formed using a liquid epoxy resin composition.

The shape of the semiconductor package 11 is not particularly limited as long as it is provided with a connection electrode portion (solder bump) 13 and can be mounted on the wiring circuit board 12. Ball 'grids' arrays and CSPs (chip' scale 'packages or chip size' packages) are useful.

In the above electronic component device, the connection electrode portion 13 provided on the semiconductor package 11 is formed in a bump shape. However, the connection electrode portion 13 provided on the wiring circuit board 12 is not particularly limited to this. The electrode section 15 may be provided in a bump shape.

[0051] The liquid epoxy resin composition, which is a material for forming the sealing resin layer 4 and the sealing resin layer 14, is prepared by curing the liquid epoxy resin (A component) and the aromatic diamines even when the V difference is large. It is obtained by blending an organic additive (D component) together with an agent (B component) and an inorganic filler (C component). In the liquid epoxy resin composition used in the present invention, the liquid refers to a liquid that exhibits fluidity at 25 ° C. In other words, the viscosity at 25 ° C is in the range of 0.1 OlmPa's to: LOOOO Pa's. The viscosity is measured using, for example, an EMD type rotational viscometer. Can be done.

The liquid epoxy resin (A component) is not particularly limited as long as it is a liquid epoxy resin containing two or more epoxy groups in one molecule. For example, bisphenol A type, Various liquid epoxy resins such as bisphenol F type, hydrogenated bisphenol A type, bisphenol AF type and phenol novolak type, and derivatives thereof, polyhydric alcohol and epichlorohydrinka Induced liquid epoxy resins and derivatives thereof Glycidylamine type, hydantoin type, aminophenol type, arin type, toluidine type, etc. various glycidyl type liquid epoxy resins and derivatives thereof First edition, 3rd printing, issued on April 20, 1996, pages 211 to 225) and these liquid epoxy resins Liquid mixture of various glycidyl type solid-type epoxy 榭脂 the like. These may be used alone or in combination of two or more.

The aromatic diamine curing agent (component B) has a function of curing the liquid epoxy resin (component A), and it is preferable to use at least one of aromatic diamine and a derivative thereof. It is more preferable to use at least one of a fluorine-containing aromatic diamine and a derivative thereof from the viewpoint of solvation with a specific solvent and subsequent swelling.

The aromatic diamine in at least one of the above aromatic diamines and derivatives thereof includes p-phenylenediamine, m-phenylenediamine, 2,5 toluenediamine, 2,4 toluenediamine, and 4,6 dimethyl m-diamine. Aromatic mononuclear diamines such as phenylenediamine and 2,4 diaminomesitylene, 4, 4 'diamino diphenyl ether, 3, 3'- diamino diphenyl ether, 3, 4' diamino diphenyl ether, 4, 4 'diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, 4, 4 'diaminodiphenylsulfone, 3, 3'-diaminodiphenylsulfone, 4, 4 '-diaminodiphenylsulfide, 3, 3'-diaminodiphenyl -Risulfide, 4, 4'-Diaminobenzophenone, 3,3'-Aromatic dinuclear diamine such as diaminobenzophenone, 1,4-bis 4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) aromatic trinuclear Jiamin such as benzene, 4, 4 ' —Di- (4-aminophenoxy) diphenylsulfone, 4, 4 ′ —Di- (3-aminophenoxy) diphenylsulfone, 4, 4 ′ —Di- (4-aminophenoxy) diphenylpropane, 4, 4′-Di Aromatic tetranuclear diamines such as mono (3-aminophenoxy) diphenylpropane, 4,4'-di (4-aminophenoxy) diphenyl ether, and 4,4'-di (3-aminophenoxy) diphenyl ether These may be used alone or in combination of two or more.

[0055] In particular, the use of at least one of an aromatic diamine represented by the following general formula (1) and a derivative thereof as the aromatic diamine curing agent (component B) is advantageous in pot life at room temperature. Is also preferably used.

[0056] [Formula 1]

[In the formula (1), X is hydrogen and / or C _n H _2n (η is 1 to 10

Is a positive number). m is a positive number from 1 to 4. R ¹ ~! T is hydrogen

Or a monovalent organic group, even if they are the same or different

Good. ]

In the above formula (1), R ^{1 to} R ⁴ are hydrogen or a monovalent organic group. Examples of the monovalent organic group include a saturated alkyl group represented by Cn H2n + 1 (n is a positive number of 1 to 10), an aryl group, -CH2CH (OH) CH2—OCnH2n 3 alkoxy substitution represented by +1 — 2 hydroxypropyl group, CH2 CH (OH) CH2 — O — 3 aryl substitution represented by R ⁹ (R ⁹ is an aryl group) — 2 hydroxypropyl group, etc. can give . Then, the Ri～R ⁴ may be different be the same as each other.

[0058] The fluorinated aromatic diamine in at least one of the above fluorinated aromatic diamines and derivatives thereof is not particularly limited as long as it is a fluorinated aromatic diamine having a primary amino group. For example, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,2 bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3 amino-4-methylphenyl) ) Hexafluoropropane, 2, 2 bis (3 amino —4 hydroxyphenyl) hexafluoropropane, 2,2-bis [4- (4 aminophenoxy) phenyl] hexafluoropropane, 2,2 bis (3 amino-4,5 dimethylphenyl) ) Hexafluoropropane, 2,2 bis (4-hydroxy-13-aminophenol) hexafluoropropane, 4,4'bis [2- (4 carboxyphenyl) hexafluoroisopropyl] diphenyl ether And 4,4'-bis [2- (4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether and the like, which may be used alone or in combination of two or more.

[0059] In particular, as the aromatic diamine curing agent (component B), at least one of a fluorine-containing aromatic diamine represented by the following general formula (2) and a derivative thereof can be used at room temperature. It is preferably used because the pot life becomes longer.

[0060] [Formula 2]

[In the formula (2), Y is fluorine and / or C „F (niil to l0

It is a positive number. ). m is a positive number from 1 to 4. R ⁵ is hydrogen

Or monovalent; which may be the same or different

[0061] In the above formula (2), R ^{5 to} R ° are hydrogen or a monovalent organic group. Examples of the monovalent organic group include a saturated alkyl group represented by Cn H2n + 1 (n is a positive number of 1 to 10), an aryl group, -CH2CH (OH) CH2—OCnH2n 3-alkoxy-substituted 1-hydroxypropyl group represented by +1; 3-aryl-substituted 2-hydroxypropyl group represented by CH2 CH (OH) CH2—O—R ¹⁰ (R ¹⁰ is aryl group) And so on. And, R ^{5 to} R ⁸ may be the same or different from each other.

[0062] In particular, in the present invention, 2,2'-ditrifluoromethyl-4,4'-diaminobihue having the smallest active hydrogen equivalent is used as the aromatic diamine curing agent (component B). Or the use of p-phenylenediamine or m-phenylenediamine, which also has the lowest active hydrogen equivalent, can reduce the amount of compounding, It is preferable from the viewpoint that the viscosity of the epoxy resin composition can be reduced.

Further, as the aromatic diamine curing agent (component B), the above-mentioned fluorinated aromatic diamine, particularly 2,2′-ditrifluoromethyl-1,4,4′-diaminobiphenyl, in one molecule The use of a reaction product with a monoepoxy compound containing one epoxy group is preferred from the viewpoint that the solvation and swelling properties are improved and good repair is possible. In the reaction of the above-mentioned fluorinated aromatic diamine with a monoepoxy compound having one epoxy group in one molecule, generally, a predetermined amount of each component is charged into a reaction vessel without a catalyst, and the reaction is carried out by nitriding. The reaction is carried out by heating to about 60 to 120 ° C under a stream of air until the epoxy groups are consumed. And, in this way, for example, N, N, Ν ′, Ν′—4-substituted fluorine-containing aromatic diamine compound is obtained.

The monoepoxy conjugate is not particularly limited as long as it is an epoxy compound containing one epoxy group in one molecule. For example, η-butyldaricidyl ether, aryl glycidyl ether , 2-ethylhexyl glycidyl ether, styrene oxide, phenol glycidyl ether, cresyl glycidyl ether, lauryl glycidyl ether, ρ-sec-butyl phenyl glycidyl ether, norphenyl glycidyl ether, glycidyl ether of carbinol Glycidyl methacrylate, vinylcyclohexene monoepoxide, _a- binene oxide and the like. These may be used alone or in combination of two or more.

[0065] In the present invention, the mixing ratio of the liquid epoxy resin (Component A) and the aromatic diamine curing agent (Component B) is one epoxy group of the liquid epoxy resin (Component A). On the other hand, the number of active hydrogens in the aromatic diamine curing agent (component B) is preferably set in the range of 0.4 to 1.6. More preferably, it is in the range of 0.6 to 1.2. That is, when the number of active hydrogens per epoxy group exceeds 1.6, the viscosity of the liquid epoxy resin composition tends to increase, and when it is less than 0.4, the liquid epoxy resin composition tends to increase. This is because the glass transition temperature of the cured product tends to decrease.

On the other hand, in the present invention, when the above-mentioned liquid epoxy resin (component A), particularly, a polyfunctional aliphatic liquid epoxy resin is used, the aromatic diamine represented by the above general formula (1) and its aromatic diamine At least one derivative or a fluorinated aromatic represented by the above general formula (2) Preliminary reaction of at least one of diamine and its derivatives with a polyfunctional aliphatic liquid epoxy resin to form a prepolymer resulted in evaporation and volatilization of low-boiling compounds contained in the polyfunctional aliphatic liquid epoxy resin and the like. The possibility of generation of voids can be reduced.

The prepolymer is, for example, at least one of the aromatic diamine represented by the general formula (1) and a derivative thereof or the fluorine-containing aromatic diamine represented by the general formula (2) and a derivative thereof And a polyfunctional aliphatic liquid epoxy compound having two or more epoxy groups in one molecule. Generally, a predetermined amount of each component is charged into a reaction vessel without a catalyst, and heated to about 60 to 120 ° C under a nitrogen stream to react until a predetermined molecular weight is reached, thereby producing a pre-polymer. . The prepolymer preferably has a molecular weight of about 400 to 5,000 in terms of polystyrene equivalent weight average molecular weight.Preferably, such a prepolymer is used to form a volatile low-boiling low molecular weight compound. It is possible to prevent voids in the underfill sealing resin layer due to evaporation and volatilization of the resin.

[0068] Specific examples of the polyfunctional aliphatic liquid epoxy resin include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl diphosphorus, and triglycidyl diglycidyl ether. Examples include aliphatic diols and triols such as methylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, and glycerin triglycidyl ether, and polyfunctional glycidyl ethers of aliphatic polyfunctional alcohols.

[0069] In the present invention, various known curing accelerators can be used to shorten the curing time. Specific examples include an acidic catalyst such as salicylic acid, and a Lewis acid such as copper acetyl acetate and zinc acetyl acetate. These may be used alone or in combination of two or more.

[0070] The amount of the curing accelerator is not particularly limited, but may be a desired curing amount for the mixture of the liquid epoxy resin (A component) and the aromatic diamine curing agent (B component). It is preferable to appropriately set the ratio so that the speed can be obtained. For example, the cure speed As an index, it is possible to easily determine the usage amount while measuring the time of geli dwelling with a hot plate. As an example, it is preferable to set the content in the range of 0.01 to 3% by weight in the whole liquid epoxy resin composition.

[0071] As the inorganic filler (component C) used together with the liquid epoxy resin (component A) and the aromatic diamine curing agent (component B), silica powder such as synthetic silica and fused silica is used.

, Alumina, silicon nitride, aluminum nitride, boron nitride, magnesia, calcium silicate, magnesium hydroxide, aluminum hydroxide, titanium oxide and the like. Among the above-mentioned inorganic fillers, it is particularly preferable to use spherical silica powder because the effect of reducing the viscosity of the liquid epoxy resin composition is large. It is preferable to use the inorganic filler having a maximum particle diameter of 24 m or less. Further, those having an average particle diameter of 10 m or less are preferably used together with the above-mentioned maximum particle diameter.

5 / zm is preferably used. Further, it is preferable to use one having a specific surface area of 1 to 4 m ² / g by the BET method. The maximum particle size and the average particle size can be measured using, for example, a laser diffraction / scattering type particle size distribution analyzer.

[0072] Further, the inorganic filler (component C) preferably has an average particle diameter of 10 µm or less, the surface of which is coated with an organosilane conjugate represented by the following general formula (3). Spherical silica particles are used, and the above-mentioned surface-coated spherical silica particles having an average particle diameter of 1 to 5 m are particularly preferable.

[0073]

(a ¹ -O)-^ — S i ~ β ^ι ) _b ■■■ (3)

[In equation (3), ¾ «a is a monovalent other than 素 k element, and β ¹ is at least

1 II Amino group, epoxy group, vinyl group, styryl group, methacryloxy

Group and a peridot group are monovalent S. A, b is a + b = 4

Where each is a positive number between 1 and 3. )

[0074] Among the spherical silica particles having an average particle diameter of 10 m or less whose surface is coated with the organosilane compound represented by the general formula (3), the aminosilane cup represented by the following general formula (4) is included. Spherical silica particles having an average particle diameter of 10 μm or less whose surface is coated with a ring agent are used, and spherical silica particles having an average particle diameter of 1 to 5 / ζπι are particularly preferred. in this way, By coating the surface of the spherical silica particles with the above aminosilane coupling agent, the dispersibility is improved and the viscosity is reduced due to the interaction such as wettability with the liquid epoxy resin (component A) and the like.

[0075] [Formula 4]

(a ⁵ -OH? — S i — y -NH ₂ -"(4)

[In the formula (4), α ′ is a monovalent group other than hydrogen, and is a divalent group.

It is. ]

Examples of the organosilane conjugate represented by the above general formula (3) include, for example, Ν-2 (aminoethyl) -3-aminopropyl-methyldimethoxysilane, Ν-2 (aminoethyl) -13-aminopro Pill-triethoxysilane, -2- (aminoethyl) -3-aminopropyl-trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like. These may be used alone or in combination of two or more.

On the other hand, as the above-mentioned inorganic filler (component C), spherical silica particles having an average particle diameter of 10 μm or less and whose surface is coated with an organic titanium compound represented by the following general formula (5) are preferably used. Particularly preferred are spherical silica particles having an average particle diameter of 1 to 5 m coated on the surface.

[0078] [Formula 5]

(α ¹ — O —T i ~ (β ¹ ) _b ■ ·· (5)

[In the formula (5), α ¹ is a monovalent group other than hydrogen, and β is at least

1 Healthy amino group, epoxy group, vinyl group, styryl group, methacryloxy

Group, ureido group ^ ", and a and b are a + b = 4

And each is a positive number between 1 and 3. ]

Examples of the organotitanium conjugate represented by the general formula (5) include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, and isopropyl tris (dioctyl pyrophosphate) titanate. , Isopropyl tri (N-aminoethyl monoaminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, Bis (dioctyl pyrophosphate) oxyacetate titanate, Bis (dioctyl pyrophosphate) ethylene titanate and the like can be mentioned. These may be used alone or in combination of two or more.

[0080] Such spherical silica particles whose surface is coated with the organosilane compound or the organotitanium conjugate are produced, for example, as follows. That is, using the above-mentioned organosilane compound or organotitanium compound, and using a conventionally known technique such as a treatment for an inorganic filler such as a vapor spray method or a wet method, spherical silica particles whose surface is coated with the compound are used. It is made. The surface can also be obtained by dissolving in an aqueous alcohol solution or solvent and subjecting it to a surface treatment.

[0081] The amount of the inorganic filler (component C) is preferably set in the range of 10 to 80% by weight of the entire liquid epoxy resin composition, and particularly preferably 30 to 70% by weight. . In other words, if the amount is less than 10% by weight, the effect of reducing the linear expansion coefficient of the liquid epoxy resin composition cured product may be small, and if it exceeds 80% by weight, the liquid epoxy resin composition may not be effective. This is because the viscosity of the product tends to increase.

[0082] The organic additive (D component) used together with the liquid epoxy resin (A component), the aromatic diamine curing agent (B component) and the inorganic filler (C component) includes the liquid epoxy resin (A Component) is a component which is melted by hardening or heat treatment so as to be incompatible with each other to form a domain structure. For example, spherical thermoplastic resin particles, spherical crosslinked resin particles and the like are used. These may be used alone or in combination of two or more.

[0083] Examples of the above-mentioned spherical thermoplastic resin particles include particles having a strong force such as polyacrylic resin, polyethersulfone resin, ethylene-butyl acetate copolymer, polyamide resin, and butadiene-styrene copolymer. These may be used alone or in combination of two or more. As the spherical thermoplastic resin particles, those having an average particle diameter of 10 m or less are preferably used, and those having an average particle diameter of 1 to 5 / ζπι are particularly preferably used. The average particle diameter can be measured using, for example, a laser diffraction / scattering type particle size distribution analyzer as described above.

[0084] Among the above-mentioned spherical thermoplastic resin particles, spherical polymethyl methacrylate particles are particularly preferably used, and more preferably spherical polymethyl methacrylate particles having a weight average molecular weight of 100,000 or more are used. Among them, the weight average molecular weight is 100,000 to 5,000, 0 00 spherical polymethyl methacrylate particles are particularly preferably used. The upper limit of the weight average molecular weight is usually 10,000,000.

[0085] The spherical polymethyl methacrylate particles also include epoxy group-containing polymethyl methacrylate particles, carboxy group-containing polymethyl methacrylate particles, polymethyl methacrylate-poly acrylate copolymer particles, and the like. It is the purpose.

[0086] As the above-mentioned spherical cross-linked resin particles, particularly, spherical cross-linked polymethylmetharylate particles are preferably used. More preferably, spherical cross-linked polymethyl methacrylate particles having a glass transition temperature of 100 ° C. or higher are used. By using the spherical crosslinked polymethyl methacrylate particles having a glass transition temperature of 100 ° C. or higher as described above, the filling temperature can be set high, and the sealing time can be reduced with a low viscosity. The effect is that it can be done. The above glass transition temperature is a value measured by a thermomechanical analysis (TMA) device.

[0087] The amount of the organic additive (component D) is not particularly limited as long as the effects of the present invention can be obtained, but is set in the range of 2 to 20% by weight of the entire liquid epoxy resin composition. Particularly preferred is 3 to 15% by weight. That is, if the amount of the organic additive is less than 2% by weight, the effect of improving the repairability of the cured liquid epoxy resin composition may not be obtained.力 This is the force that tends to increase the viscosity of the resin composition.

[0088] Further, in addition to the above-mentioned components, a reactive diluent can be appropriately compounded for the purpose of lowering the viscosity and the like. However, as described in the description of the prepolymer, this reactive diluent is volatile. Since it may contain a low boiling point compound, it must be used at the prescribed curing temperature of the liquid epoxy resin composition which is an underfill resin. It is preferable to use the volatile low-boiling compound after removing it in advance. Further, when the reactive diluent itself is volatile, voids are easily generated in the sealing resin layer at a predetermined curing temperature of the liquid epoxy resin thread and the underfill resin, As such, the use of such reactive diluents is limited.

[0089] Examples of the reactive diluent include n-butyldaricidyl ether, arylglycidylether, 2-ethylhexylglycidylether, styrene oxide, and phen- Luglycidyl ether, cresyl glycidyl ether, lauryl glycidyl ether, p sec butylphenol glycidyl ether, norphenyl glycidyl ether, glycidyl ether of rubinol, glycidyl methacrylate, bulcyclohexene monoepoxide, pinene oxide, tertiary Glycidyl ethers of carboxylic acids, diglycidyl ethers, glycidyl ethers of (poly) ethylene glycol, glycidyl ethers of (poly) propylene glycol, bisphenol A with propylene oxide, bisphenol A epoxy resin and polymerized fatty acids With polyglycidyl ether of polymerized fatty acid, diglycidyl ether of butanediol, vinylcyclohexenedioxide, neopentyl glycol digly Jill ether, Jigurishijirua diphosphate, trimethylene opening ~~ Norepurono down diglycidyl Shishi Norre d ~ ~ Tenore, I Rimechiro ~~ Norepurono down Bok Rigurishijinoree ~~ Tenore, glycerin diglycidyl ether, glycerin triglycidyl ether, and the like. These may be used alone or in combination of two or more.

[0090] In the present invention, in addition to the above components, the liquid epoxy resin composition may further contain a flame retardant such as antimony trioxide, antimony pentaoxide, or brominated epoxy resin. Flame-retardant aids, low-stress agents such as silicones, coloring agents, and the like can be appropriately compounded without departing from the spirit of the present invention.

[0091] Such a liquid epoxy resin composition can be produced, for example, as follows. That is, each component such as the liquid epoxy resin (A component), the aromatic diamine curing agent (B component), the inorganic filler (C component), the organic additive (D component) and, if necessary, the curing accelerator. The desired one-part solvent-free liquid epoxy resin is obtained by mixing and dispersing under a high shearing force such as a three-roll or homomixer, and optionally defoaming under reduced pressure. A composition can be manufactured.

[0092] Alternatively, a liquid epoxy resin (A component), particularly a polyfunctional aliphatic liquid epoxy resin, and at least one of the aromatic diamine represented by the general formula (1) and a derivative thereof, or When using a prepolymer with at least one of the fluorine-containing aromatic diamine represented by the general formula (2) and its derivative, these components are preliminarily reacted as described above. Next, after blending a predetermined amount of this prepolymer and other components, the desired one-part solvent-free liquid epoxy resin composition can be produced in the same manner as described above. [0093] A semiconductor component (eg, a semiconductor element such as a flip chip, a semiconductor package) using the liquid epoxy resin composition obtained in this way and an electronic component device by resin sealing of a wiring circuit board include, for example, It is manufactured as follows. That is, a semiconductor component having a connection electrode portion (solder bump) in advance and a wiring circuit board having a connection electrode portion (solder pad) facing the solder bump are connected by solder metal. Next, by utilizing a capillary phenomenon in a gap between the semiconductor component and the printed circuit board, a liquid epoxy resin composition of one component and no solvent is filled and thermally cured to form a sealing resin layer. Seal with grease.

Thus, for example, when the semiconductor component is a semiconductor element (flip chip), as shown in FIG. 1, the connection electrode portion (solder bump) 3 provided on the semiconductor element 1 and the wiring circuit board The semiconductor element (flip chip) 1 is mounted on the wiring circuit board 2 with the connection electrode portion (solder pad) 5 provided on the wiring circuit 2 facing the wiring circuit board 2 and the wiring circuit board 2 and the semiconductor element (Flip Chip) An electronic component device in which the gap with the flip chip 1 is resin-sealed by the sealing resin layer 4 also having the above-mentioned liquid epoxy resin composition strength is manufactured.

On the other hand, for example, when the semiconductor component is a semiconductor device (semiconductor package), as shown in FIG. 2, the connection electrode portion (solder bump) 13 provided on the semiconductor package 11 and the wiring circuit board 12 The semiconductor package 11 is mounted on the printed circuit board 12 with the provided connection electrode portions (solder pads) 15 facing each other, and the gap between the printed circuit board 12 and the semiconductor package 11 is formed by the liquid epoxy. An electronic component device that is resin-sealed by the sealing resin layer 14 that also has a resin composition power is manufactured.

[0096] In the above manufacturing process, when the gap between the semiconductor element (flip chip) 1 and the wiring circuit board 2 or the gap between the semiconductor package 11 and the wiring circuit board 12 is filled with the liquid epoxy resin composition, First, after the liquid epoxy resin composition is filled in a syringe, the liquid epoxy resin composition is extruded and applied to one end of the semiconductor element (flip chip) 1 or the semiconductor package 11 by a needle cap, and a capillary phenomenon is caused. Use to fill. When filling using this capillary phenomenon, liquid viscosity decreases when filling and sealing on a hot plate heated to about 60 to 120 ° C, making it easier to fill and seal. Become. Furthermore, if the printed circuit boards 2 and 12 are inclined, the filling and sealing can be further facilitated. In the electronic component device thus obtained, when the semiconductor component is the semiconductor element (flip chip) 1, the gap distance between the semiconductor element (flip chip) 1 and the printed circuit board 2 is generally 30 It is about -300 μm.

When the semiconductor component is the semiconductor package 11, the gap distance between the semiconductor package 11 and the wiring circuit board 12 is generally about 200 to 300;

[0099] The cured epoxy resin composition in the resin-sealed portion of the electronic component device thus obtained swells with a specific organic solvent even after it is cured, and its adhesive strength is reduced. The component device can be repaired.

[0100] As the specific organic solvent, a ketone solvent, a glycol diether solvent, a nitrogen-containing solvent, and the like are preferable. These may be used alone or in combination of two or more.

[0101] Examples of the above ketone solvents include acetophenone, isophorone, ethyl n-butyl ketone, diisobutyl ketone, getyl ketone, cyclohexyl ketone, di-n-propyl ketone, methyl oxide, methyl n-amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, and methyl cyclohexane. Xanone, methyl n-heptyl ketone, and holone. These may be used alone or in combination of two or more.

[0102] Examples of the glycol ether-based solvents include ethylene glycol getyl ether, ethylene glycol dibutyl ether, ethylene glycolone resin methine oleate, ethylene glycol diole cholesterol methine oleate, and diethylene glycol oleone terephthalate. Athenole, ethylene glycolone dibutylbutyrene, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like. These may be used alone or in combination of two or more.

[0103] Examples of the nitrogen-containing solvent include N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, N, N'-dimethylsulfoxide, hexamethylphosphortriamide and the like. Is raised. These may be used alone or in combination of two or more.

As a method of repairing the electronic component device, for example, using a hot plate or the like, a semiconductor component (a semiconductor element such as a flip chip or a semiconductor package) or a repaired portion of a printed circuit board is heated to apply the semiconductor component. Is removed. The heating temperature at this time is The cured body of the epoxy resin composition of the present invention is heated at a temperature of about + 50 ° C or more from the glass transition temperature of the cured body of the epoxy resin composition of the present invention, and is heated at a temperature equal to or higher than the melting point of the joining metal such as solder. With cohesive failure or adhesion to one (semiconductor component or printed circuit board), both can be easily separated. Thereafter, the organic solvent is applied directly or the absorbent obtained by impregnating the organic solvent into absorbent cotton is brought into contact with the residual portion of the cured epoxy resin composition of the printed circuit board at room temperature, more preferably, glass transition. After contacting at the temperature or higher, if the swelling of the cured body is confirmed and the residue is removed, the printed circuit board and the mounting part can be reused. On the other hand, the semiconductor component to which the residue of the cured product of the liquid epoxy resin composition has adhered is immersed in the above-mentioned organic solvent taken in a predetermined container at room temperature to swell the cured product and remove the semiconductor component to thereby re-use the semiconductor component. Can be used.

[0105] Alternatively, the above organic solvent may be directly applied to the entire repaired portion of the printed circuit board or coated with absorbent cotton impregnated with the organic solvent, although the treatment requires a long time. Alternatively, the semiconductor component can be removed from the wiring circuit board after the cured product is swelled by gradually penetrating the organic solvent from the end of the semiconductor component to reduce the strength and adhesion of the cured product.

Next, examples will be described together with comparative examples.

[0107] First, the following components were prepared.

[Liquid epoxy resin a]

An epoxy resin represented by the following structural formula (a).

[Formula 6]

0 OH

CH ₂ -CH-CH ₂ † 0-<QVCH ₂ -0 CH ₂ -CH CH _2- | -0-(ΟΥ CH _2- *

i

0

*-) 0-CH ₂ -CH-CH ₂

[In the formula (a), n is a positive purity of 0 or more, 99%, and a viscosity of 22 dP a · s

(25¾), epoxy equivalent 1 65 g / eq]

[Liquid epoxy resin b] An aliphatic polyfunctional epoxy conjugate represented by the following structural formula (b).

[Formula 7]

CH _E- O— CH ₂ — CH— CH ₂

,,,, /

O

CH ₃ -CH ₂ -C-CH ₂ -OH (b)

CH ₂ -0-CH ₂ — CH— CH ₂

\ /

O

[In formula (b), the viscosity is 0.6 dPa · s :),

Epoxy equivalent 125g / e q] [Curing agent a]

A fluorine-containing aromatic diamine represented by the following structural formula (c).

[Formula 8]

[In the formula (c), the sensitivity point 182, active hydrogen equivalent 80 _g / eq] [Curing agent b]

2,2′-Ditrifluoromethyl-4, diaminobiphenyl represented by the above structural formula (c) was charged into a reaction vessel at a ratio of 1 mol and butyldaricidyl ether at a ratio of 0.5 mol, and the mixture was heated at 200 ° C. And a fluorine-containing aromatic diamine derivative represented by the following structural formula (d).

[Formula 9]

[In formula (d), four Rs are on average 3.5 hydrogens,

0.5 are — CH ₂ —CH (OH) CH ₂ — O— C ₄ Η _θ

It is. The average SfeK elemental equivalent is 110 g / eq. ] [0112] [Curing agent c]

A non-fluorinated aromatic diamine represented by the following structural formula (e).

[Formula 10]

L ^ J… ( _e )

[In the formula (e), Si ^ 64, iStt * elemental equivalent 27 gZeq]

[0113] [Curing agent d]

The following structural formula was obtained by charging 1 mol of m-phenylenediamine represented by the above structural formula (e) and 0.5 mol of butyldaricidyl ether into a reaction vessel and reacting at 200 ° C. A non-fluorinated aromatic diamine derivative represented by (f).

[Formula 11]

[In formula (f), four R's have an average of 3.5 hydrogen and an average of

0.5 is CH ₂ — CH (OH) CH ₂ 0— C ₄ H _Q

It is. The average S fc element equivalent is 49.4 g / eq. ]

[Prepolymer a (Fluorine-Containing)]

For 1 equivalent (80 g) of active hydrogen of the fluorinated aromatic diamine represented by the above structural formula (c), 0.5 equivalent (82.5 g) of the epoxy resin represented by the above structural formula (a) is added. Prevolimer a (active hydrogen equivalent: 325), a syrup-like viscous liquid obtained by reacting at 150 ° C for 15 minutes and cooling.

[Prepolymer b (fluorine-containing)]

1 mol of the fluorinated aromatic diamine derivative represented by the above structural formula (d) and 1.75 mol of the aliphatic polyfunctional epoxy conjugate represented by the above structural formula (b) are charged into a reaction vessel, and 100 Prevolimer b (viscosity 190 dPa's) obtained by reacting at ° C for 2 minutes.

[0116] [Inorganic filler a]

Spherical silica particles whose surface has been surface-treated by vapor atomization using 3-aminopropyltriethoxysilane (maximum particle diameter 6 μm, average particle diameter 2 μm, specific surface area 2. lm ² / g) o

[0117] [Inorganic filler b]

Spherical silica particles whose surface has been surface-treated by vapor spraying using isopropyl triisostearoyl titanate (organic titanium compound) (maximum particle diameter 6 μm, average particle diameter 2 m, specific surface area 2. lm ² / g).

[0118] [Organic additive al]

Spherical polymethylmetharylate particles (average particle diameter 4 μm, maximum particle diameter 10 μm, weight average molecular weight 3,000,000).

[0119] [Organic additive a2]

Spherical polymethylmetharylate particles (average particle diameter 3.3 m, maximum particle diameter 20 μm, weight average molecular weight 1,750,000).

[Organic additive bl]

Spherical polymethyl methacrylate particles (average particle diameter 4 μm, maximum particle diameter 10 μm, weight average molecular weight 400,000).

[0121] [Organic additive b2]

Spherical polymethyl methacrylate particles (average particle diameter 3.4 m, maximum particle diameter 20 μm, weight average molecular weight 400,000).

[0122] [Organic additive c]

Spherical crosslinked polymethyl methacrylate particles (average particle diameter 2.6 m, maximum particle diameter 5 μm, glass transition temperature 120 ° C).

Example

[0123] (1) Example using semiconductor element (flip chip) as semiconductor component

(Examples 1 to 18, Comparative Examples 1 to 3)

The above-prepared components are blended in the ratios shown in Tables 1 to 4 below, and are homogenously mixed and dispersed at room temperature (25 ° C) using three rolls to form a one-part solvent-free liquid epoxy resin composition. Was prepared.

[0124] [Table 1] (≤ volume part)

2]

(Parts by weight) Example

8 9 10 1 1 1 2 13 14 a 0.825 0.825 0.825 0.825 0, 825 0.825 0.825 ί ^ ίepoki, «} Jj

b 0.625 0.625 0.625 0.625 0.625 625 0.625 a 1 ― ―-―--b ― ―-―--

c-0.27--d 0.49 0.49 0.49 0, 9 --- 0.49 0.49 a-One--Prepolymer

b------a 1.03 1.90 1.54 2.86 1.22-b-----1.03 a 1 0.09 0.16 0,09 0.09 0- 11-0.09 b 1---0.09 one c---

- 3]

(Parts by weight) Example

15 16 17 18 a-0, 825 0.825 0.825 Epoxy

b 0.625-0, 625 0.625 a ―-―― b ― 1.10 1.10 Hard

c one--d-

a 1.625 ― ― Blepolymer

b-L725-a 1.61 1.82 L82 2.73 b-i1 0.16 0.18-b1---c-0.18 0 '18 m) Comparison example

2 3 a α 825 825 0.825 ί ^ Epoxy resin

b 0, 625 ― 0.625 a _-―― b 1,10-c ―-― d-0.49 a ―

Prebolima I

b-1.725-a

b ―-a 1--b 1 Using the thus obtained liquid epoxy resin compositions of Examples and Comparative Examples, the viscosity at 25 ° C. was measured using an EMD type rotational viscometer, and the needle inner diameter was 0.56 mm. Was filled into a polypropylene syringe having a needle.

[0129] Thereafter, the syringe was packed at 25 ° C, and the time until the viscosity doubled was measured to determine the pot life.

[0130] On the other hand, a silicon chip (thickness: 370 / ζπι, size: 10mm XI Omm) having 64 Sn—3Ag—0.5Cu solder bump electrodes with a diameter of 200 / zm was prepared, and copper wiring with a diameter of 300m was prepared. 1 mm thick FR-4 glass epoxy wiring circuit with 64 pads (board side electrodes) Copper wiring pads (board side electrodes) coated with 63Sn-37Pb solder paste on the board and soldering the silicon chip After mounting the chip on the substrate with the bump electrodes facing each other, the chip was soldered through a heating reflow furnace at 260 ° C for 5 seconds. The gap between the silicon chip and the circuit board was 210 μm.

[0131] Next, air pressure was applied to the syringe filled with the liquid epoxy resin composition, and the liquid epoxy resin composition was applied to one side of the gap between the silicon chip (flip chip) and the circuit board by as much as one dollar force. The liquid epoxy resin composition is heated and filled by capillary action on a 60 ° C hot plate, the filling time is measured, and after filling is completed, it is cured at 150 ° C for 4 hours. An electronic component device was manufactured by sealing with grease.

[0132] After the curing was completed, the temperature was gradually cooled to room temperature, and then the presence or absence of voids in the sealing resin layer that filled and sealed the gap between the printed circuit board and the semiconductor element was observed with an ultrasonic flaw detector. Then, a force when no void was observed was evaluated as 〇, a case where one or two voids were observed was evaluated as △, and a case where more voids were observed was evaluated as X.

[0133] Using each of the electronic component devices thus obtained, the conduction failure rate and the repairability were measured and evaluated according to the following methods. The results are shown in Tables 5 to 8 below together with the measurement of the properties of the liquid epoxy resin composition.

[Conduction Failure Rate]

The conduction failure rate of the electronic component device immediately after resin sealing was measured. After that, the above electronic component device was subjected to a temperature cycle test at 40 ° C for 10 minutes and 125 ° C for 10 minutes using a thermal test device, and the electrical continuity after 1000 cycles was examined. The conduction failure rate (%) was calculated for all 64 copper wiring pads (board-side electrodes) on the circuit board.

[Repairability]

After measuring the above continuity failure rate, the silicon chip was peeled off from the electronic component device on a hot plate heated to 200 ° C, and after returning to room temperature, the epoxy resin composition remaining at the connection was cured. Absorbent cotton containing a mixed solvent of equal amounts of N, N'-dimethylformamide and diethylene glycol dimethyl ether was allowed to stand in the residue of the body, and allowed to stand at 40 ° C for 1 hour. Thereafter, the absorbent cotton is removed, and the cloth is thoroughly wiped with methanol, and the cured epoxy resin composition is peeled off. The peelable electronic component device is supplied with the solder paste to the pad portion of the wiring circuit board again, and after melting the solder, In the same manner as above, a silicon chip was mounted on the wiring circuit board, and the electrical conductivity was examined. Thereafter, resin sealing was performed in the same manner as above, and the repairability (rework) property was evaluated.

[0136] In the case where the cured epoxy resin composition can be completely peeled off and the electrical connection is complete with the force ◎, the cured body can be slightly peeled off and the electrical connection is complete. In the case of (1), the cured product remains slightly and can be peeled off, but the electrical connection is incomplete. In the case of (2), the cured epoxy resin composition can hardly be peeled off and the electrical connection is incomplete. Is X.

[Table 5]

[Table 6] Example

8 9 10 11 12 13 1

Viscosity (at 25¾) 120 350 300 900 80 11S 130 (d Pas)

Bot life (at25U 4 4 4 3 5 4 4 (hours)

规 Time (min) 2 3 3 6 1.5 2 2.5 Conduction failure rate (%) 0 0 0 0 0 0 0 Void 0 O O 〇 O 〇〇

i) Pair H4 (22V.) 〇〇 O 〇〇〇〇

[Table 7]

[0141] As a result, the liquid epoxy resin compositions of all Examples had a long pot life and low viscosity. It can be seen that in combination with the degree, Voidless is excellent as a one-part, non-solvent type liquid epoxy resin composition. Moreover, it is clear that the fabricated electronic component device is excellent in repairability without generation of voids and poor conduction in the formed sealing resin layer. On the other hand, the liquid epoxy resin composition of the comparative example was void-free with no conduction failure, but was inferior in repairability as compared with the example product.

[0142] (2) Example using semiconductor device (semiconductor package) as semiconductor component

[Examples 19 to 29, Comparative Examples 4 to 6]

The above-prepared components are blended in the ratios shown in Tables 9 to 11 below, and homogenously mixed and dispersed at room temperature (25 ° C) using three rolls to form a one-part solvent-free liquid epoxy resin composition. Was prepared.

[0144] [Table 9]

(Weight part)

Example

[0145] [Table 10] (Weight parts)

[Table 11]

(Weight parts)

Using the thus obtained liquid epoxy resin compositions of Examples and Comparative Examples, measuring the viscosity at 25 ° C using an MD-type rotational viscometer, the needle having a needle inner diameter of 0.56 mm was used. Into a syringe made of polypropylene. [0148] Thereafter, the syringe was packed and left at 25 ° C to measure the time until the viscosity doubled, and this was defined as the pot life.

On the other hand, a CSP package (package height lmm, size 10 mm XI Omm) having 64 Sn—3Ag—0.5Cu solder bump electrodes with a diameter of 200 / zm was prepared, and copper wiring with a diameter of 300 m was prepared. The 63Sn-37Pb solder paste of FR-4 glass epoxy wiring circuit board of lmm thickness with 64 pads opened (board side electrode) is coated with copper wiring pad (board side electrode) and solder of above CSP package. After mounting the CSP package on the substrate with the bump electrodes facing each other, the CSP package was soldered through a heating reflow furnace at 260 ° C for 5 seconds. The gap between the CSP package and the circuit board is 250 μm.

[0150] Next, air pressure was applied to the syringe filled with the liquid epoxy resin composition.

The liquid epoxy resin composition is discharged and applied to one side of the gap between the CSP package and the circuit board with a force of one dollar, and the liquid epoxy resin composition is heated and filled by capillary action on a 60 ° C hot plate. Then, the filling time was measured, and after the filling was completed, the mixture was hardened at 150 ° C. for 4 hours and sealed with a resin to produce an electronic component device.

[0151] After the curing was completed, the temperature was gradually cooled to room temperature, and then the presence of voids in the sealing resin layer, which was filled and sealed with the gap between the printed circuit board and the CSP knockage, was observed using an ultrasonic flaw detector. Then, a force when no voids were observed was evaluated as 〇, a case where one or two voids were observed was evaluated as △, and a case where more voids were observed was evaluated as X.

[0152] Using each of the electronic component devices thus obtained, the conduction failure rate and the repairability were measured and evaluated according to the following methods. The results are shown in Tables 12 to 14 below together with the measurement of the properties of the liquid epoxy resin composition.

[0153] [Drop impact test]

Attach a lOOg weight to each end of the board after resin sealing of the above electronic component device, drop it on a wooden floor from a height of 1.2m, and count the number of times that the board with the above electronic component device has a conduction failure. I asked.

[Continuous defective rate]

The conduction failure rate of the electronic component device immediately after resin sealing was measured. After that, the thermal test Conduct a temperature cycle test of the above electronic component device at 40 ° C for 10 minutes and 125 ° C for 10 minutes using the device to check the electrical continuity after 1000 cycles. The conduction failure rate (%) for all 64 pads (substrate-side electrodes) was calculated.

[Repairability]

After measuring the conduction failure rate, the CSP package was also peeled off on a hot plate heated to 200 ° C, and the CSP package was peeled off and returned to room temperature, but a cured product of the epoxy resin composition remaining at the connection portion Absorbent cotton containing a mixed solvent of equal amounts of N, N'-dimethylformamide and diethylene glycol dimethyl ether was allowed to stand in the residue portion of, and allowed to stand at room temperature (22 ° C) for 1 hour. Thereafter, the cotton wool is removed, the well is thoroughly wiped with methanol, the cured epoxy resin composition is peeled off, and the peelable electronic component device is again supplied with the solder paste to the pad portion of the wiring circuit board, and after melting the solder, In the same manner as above, the CSP package was mounted on a printed circuit board and the electrical conductivity was examined. Thereafter, the resin was sealed in the same manner as described above, and the repairability (rework) property was evaluated.

In the case where the cured epoxy resin composition can be completely peeled off and the electrical connection is complete, the cured body can be peeled off with a small amount of the cured body, but the electrical connection is complete. In the case of (1), the cured product remains slightly and can be peeled off, but the electrical connection is incomplete. In the case of (2), the cured epoxy resin composition can hardly be peeled off and the electrical connection is incomplete. Is X.

[Table 15]

Example

19 20 21 22 23 24 25 Viscosity (at 25) 300 800 600 1400 200 280 305 (d P a

Pot life (at25t) 36 36 34 35 120 32 35 (hours)

Time (min) 1 1.5 1.5 3 0.8 1 1.3 rnrw (times) 5000 times 5000 times Leakage 5000 times 5000 times 5000 times 5000 times or more or more or more or more or more Conduction failure rate (%) 0 0 0 0 0 0 0 Void O o 〇〇〇 o 〇 Repair (22V) ◎ ◎ oooo

[Table 15]

[0159] [Table 14]

Comparative example

4 5 6

Viscosity (at 25 V,) 250 I 370 180

(d P a, s)

Pot life (at25O 37 24 12S

(Time)

Filling time (min) 0.8 1 1. 3 0.7

rn ^ rm (times) 5000 times 5000 times 5000 times

Over i over

Conduction failure rate (%) 0 0 0

Void 〇 O 0

Repair H * (2 2V.) X Δ X

[0160] The above results show that the liquid epoxy resin compositions of all Examples have a long pot life and, in combination with low viscosity, are excellent as one-part solventless liquid epoxy resin compositions of Voidless. . Moreover, in the manufactured electronic component device, the formed sealing resin layer is free from voids and poor conduction, has a good drop impact resistance test result, and has excellent repairability. it is obvious. On the other hand, the liquid epoxy resin composition of the comparative example was inferior in repairability as compared with the power example product in which there was no conduction failure and was voidless.

[0161] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. is there.

This application is based on a Japanese patent application filed on May 11, 2004 (Japanese Patent Application No. 2004-141583) and a Japanese patent application filed on December 9, 2004 (Japanese Patent Application No. 2004-357098), Its contents are incorporated herein by reference.

Industrial applicability

[0162] The present invention relates to a semiconductor package such as a BGA (ball-grid 'array) or CSP (chip-scale' package or chip-size 'package) or a connection electrode portion of a semiconductor component such as a semiconductor element. In the board mounting connection method that electrically connects the semiconductor component and the opposing electrode of the circuit board via bumps, the gap between the semiconductor package and the circuit board Provided is an electronic component device having good repairability, which is filled with a liquid epoxy resin composition and sealed with a resin.

Claims

Claims [1] A semiconductor component is mounted on the circuit board in a state where the connection electrode section provided on the semiconductor component and the connection electrode section provided on the circuit board face each other. An electronic component device in which a gap with a body component is sealed by a sealing resin layer, wherein the sealing resin layer contains the following components (A) to (C) and the following component (D): An electronic component device formed of a liquid epoxy resin composition. (A) Liquid epoxy resin. (B) Aromatic diamine curing agents. (C) an inorganic filler. (D) Organic additives. [2] The electronic component device according to claim 1, wherein the aromatic diamine curing agent as the component (B) is at least one of an aromatic diamine represented by the following general formula (1) and a derivative thereof.

[Chemical 1]

[In the formula (1), X is Mizunin and / or C „ _{Sn + i} (n is 1 to 10

Or monovalent ^ IS, which is the same or different,

Good. The electronic part according to claim 1, wherein the aromatic diamine curing agent as the component (B) is at least one of a fluorine-containing aromatic diamine represented by the following general formula (2) and a derivative thereof.

[Formula 2]

(Y) ™

[In the formula (2), Y is fluorine and / or, Fs, ^, (η is 1 to 10;

Or a monovalent organic group, which may be the same as or different from each other.

No. ]

[4] The aromatic diamine curing agent as the component (B) is a monoepoxy compound having one epoxy group in one molecule, and a 2,2′-ditrifluoromethyl—4,4 ′ -The electronic component device according to claim 1, which is a reaction product with diaminobiphenyl.

[5] The monoepoxy conjugate containing one epoxy group in one molecule of the above n-butyldaricidyl ether, arylglycidyl ether, 2-ethylhexylglycidylether, styrene oxide, phenylglycidylether, Cresyl glycidyl ether, lauryl glycidyl ether, ρ-sec-butylphenylglycidyl ether, norphenylphenylicidyl ether, glycidyl ether of carbinol, glycidyl methacrylate, bulcyclohexene monoepoxide and α-pinene 5. The electronic component device according to claim 4, wherein the device is at least one selected from the group consisting of oxides.

[6] The electron according to claim 2, which comprises a prepolymer obtained by reacting at least one of the aromatic diamine represented by the general formula (1) and a derivative thereof with a liquid epoxy resin as a component (ii). Parts equipment.

[7] A prepolymer which is obtained by reacting at least one of the fluorinated aromatic diamine represented by the general formula (2) and a derivative thereof with a liquid epoxy resin as the component (II). Electronic component device according to the above.

[8] The electronic component device according to any one of claims 1 to 7, wherein the inorganic filler as the component (C) is a spherical silica powder having an average particle size of 10 µm or less.

[9] The inorganic filler as the component (C) is a spherical silica powder having an average particle diameter of 10 m or less, the surface of which is coated with an organosilane conjugate represented by the following general formula (3). The electronic component device according to any one of claims 1 to 7. [Formula 3] '— oH ^ ~ s レ） _b …)

[In the formula (3), α 'is a monovalent other than hydrogen, and at least

1 amino group, epoxy group, vinyl group, styryl group, methacryloxy

And monovalent, including ureido groups. A, b is a + b = 4

Where each is a positive number between 1 and 3. ]

10. The electronic component device according to claim 9, wherein the organosilane conjugate represented by the general formula (3) is an organosilane conjugate represented by the following general formula (4).

[Formula 4]

(a ¹ -OH? S i—— y— ΝΉ _2- ■-(4)

[In the formula (4), is a monovalent valence other than hydrogen (S group, γ is a divalent valence S

It is. ]

[11] The inorganic filler as the component (C) is a spherical silica powder having an average particle diameter of 10 m or less, the surface of which is coated with an organotitanium conjugate represented by the following general formula (5). The electronic component device according to any one of claims 1 to 7.

[Formula 5]

(a ¹ -o ~ τ i—ίβ ¹ ) _b … (5)

[In equation (5), the hydrogen tu is monovalent and β ¹ is at least

1 amino group, epoxy group, butyl group, styryl group, methacryloxy

Group, ureido group is ^ «S with ^ tf" value. A, b is a + b = 4

And each is a positive number between 1 and 3. ]

[12] The organic additive as the component (D) is at least one of spherical thermoplastic resin particles having an average particle diameter of 10 μm or less and spherical crosslinked resin particles having an average particle diameter of 10 μm or less. Item 12. The electronic component device according to any one of Items 1 to 11.

13. The electronic component device according to claim 12, wherein at least one of the spherical thermoplastic resin particles and the spherical crosslinked resin particles is a spherical polymethylmetharylate particle.

[14] The weight average molecular weight of the spherical polymethyl methacrylate particles is from 100,000 to 5,000,

14. The electronic component device according to claim 13, wherein the range is 000.

15. The electronic component device according to claim 13, wherein the spherical polymethyl methacrylate particles are spherical crosslinked polymethyl methacrylate particles having a glass transition temperature of 100 ° C. or higher.

[16] The electronic component device according to any one of claims 1 to 15, wherein the semiconductor component is a semiconductor element.

[17] The electronic component device according to any one of claims 1 to 15, wherein the semiconductor component is a semiconductor device.