JP2002060464A - Electronic component equipment - Google Patents

Abstract

(57) [Summary] [Problem] To provide an electronic component device capable of repairing even an electronic component device having a defect in electrical connection once underfilled. Kind Code: A1 Abstract: Wiring is performed in a state where a connection electrode portion (solder bump) 3 provided on a semiconductor element (flip chip) 1 and a connection electrode portion (solder pad) 5 provided on a printed circuit board 2 face each other. This is an electronic component device in which a semiconductor element (flip chip) 1 is mounted on a circuit board 2. A gap between the printed circuit board 2 and the semiconductor element (flip chip) 1 is sealed with a sealing resin layer 4 made of a liquid epoxy resin composition containing the following components (A) to (C) as essential components. Has been stopped. (A) Liquid epoxy resin. (B1) At least one of a fluorinated aromatic diamine and a derivative thereof. (C) an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flip-chip electronic component device for electrically connecting a semiconductor element and an opposing electrode of a circuit board via connection electrode portions (bumps). The present invention relates to an electronic component device having reliability and good repairability.

[0002]

2. Description of the Related Art In recent years, a direct chip attach method using a bare chip such as a flip chip of a semiconductor device has been attracting attention. In the flip-chip connection method, the "C4 technology" for forming a high melting point solder bump on the chip side and performing metal-to-metal bonding with the solder on the ceramic circuit board side is famous.

However, when a resin-based substrate such as a glass-epoxy resin printed circuit board is used in place of the ceramic circuit board, the solder bump bonding portion caused by the difference in the coefficient of thermal expansion between the chip and the resin-based substrate. Are destroyed and connection reliability is not sufficient. As a countermeasure for such a problem, a technology for improving reliability by dispersing thermal stress by sealing a gap between a semiconductor element and a resin-based circuit board using, for example, a liquid resin composition,
It is common to perform so-called underfill.

[0004]

However, since the liquid resin composition used for the underfill is generally a thermosetting resin composition mainly composed of an epoxy resin or the like, the liquid resin composition is cured by heating. Thereafter, there is a problem that repair cannot be easily performed in terms of not melting, having high adhesive strength, not decomposing, and being insoluble in a solvent. 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, while recycling is required for global environmental protection, it is necessary to avoid waste as much as possible.
It is required that repair be possible even after underfill.

The present invention has been made in view of such circumstances, and provides an electronic component device which can repair even an electronic component device having a defective electrical connection once underfilled. For that purpose.

[0006]

In order to achieve the above-mentioned object, the present invention provides a method for manufacturing a semiconductor device, comprising the steps of: connecting a connection electrode provided on a semiconductor element to a connection electrode provided on a circuit board; An electronic component device in which a semiconductor element is mounted on a substrate and a gap between the circuit board and the semiconductor element is sealed by a sealing resin layer, wherein the sealing resin layer has the following (A) to (C). A first gist is an electronic component device formed of a liquid epoxy resin composition containing the component (1) as an essential component. (A) Liquid epoxy resin. (B1) At least one of a fluorinated aromatic diamine and a derivative thereof. (C) an inorganic filler.

Further, the present invention provides a semiconductor device, comprising: mounting a semiconductor element on the circuit board in a state where the connection electrode section provided on the semiconductor element faces the connection electrode section provided on the circuit board; Electronic device in which a gap between a semiconductor element and a semiconductor element is sealed by a sealing resin layer, wherein the sealing resin layer comprises the following components (A) to (C) as essential components: The electronic component device formed by the above is a second gist. (A) Liquid epoxy resin. (B2) A prepolymer obtained by reacting at least one of a fluorinated aromatic diamine and a derivative thereof with a liquid epoxy resin. (C) an inorganic filler.

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 element in order to achieve the above object. As a result, when at least one of a fluorinated aromatic diamine and a derivative thereof as a curing agent of the liquid epoxy resin, or a prepolymer obtained by reacting the same with the liquid epoxy resin, solvation with a specific solvent and subsequent swelling are performed. Occurs, and as a result,
The present inventors have found that the film strength and the adhesive strength of the cured body, which is the sealing resin, are reduced and the cured body can be mechanically peeled, and the semiconductor element (flip chip) can be repaired. The fluorine-containing aromatic diamine,
Generally, as compared with non-fluorinated aromatic diamine, the higher the ionization potential (reverse sign of the HOMO orbit),
It is known that the activity as an electron donor tends to decrease, and as a result, the pot life near room temperature after mixing with a liquid epoxy resin is sufficiently long because the basicity is low, so that one-component And the solubility parameter of the cured product (Solubility
Parameter (SP)] was found to be repairable as described above in order to lower the value.

Further, when a prepolymer [component (B2)] obtained by reacting at least one of a fluorinated aromatic diamine and a derivative thereof with the liquid epoxy resin is used as a curing agent for the liquid epoxy resin. The curing speed can be improved. Moreover,
Since it can be formed in a state from liquefaction to viscous paste in advance, the liquid epoxy resin composition can be easily obtained without the need for complicated steps in the measurement at the time of blending and the subsequent dispersion step.

[0010] In particular, when the compound represented by the above-mentioned specific formula (1) is used as at least one of the above-mentioned fluorinated aromatic diamine and its derivative, a sufficiently long pot life can be ensured and a rapid swelling property can be obtained. This is preferable because it has the effect that both ease of repair can be achieved.

In the above component (B2), when a polyfunctional aliphatic liquid epoxy resin is used as the liquid epoxy resin to be reacted with at least one of the fluorinated aromatic diamine and its derivative, the viscosity of the prepolymer can be further reduced. Will be able to

[0012]

Next, embodiments of the present invention will be described in detail.

As shown in FIG. 1, the electronic component device of the present invention has a connection electrode portion (solder bump) 3 provided on a semiconductor element (flip chip) 1 and a connection electrode portion provided on a printed circuit board 2. With the parts (solder pads) 5 facing each other,
A semiconductor element (flip chip) 1 is mounted on a printed circuit board 2. A gap between the printed circuit board 2 and the semiconductor element (flip chip) 1 is resin-sealed by a sealing resin layer 4 made of a liquid epoxy resin composition.

In the above-mentioned electronic component device, the connection electrode portion 3 provided on the semiconductor element 1 is formed in a bump shape. However, the present invention is not limited to this. The connection electrode portion 3 provided on the printed circuit board 2 is not limited to this. The electrode unit 5 may be provided in a bump shape.

The liquid epoxy resin composition as the material for forming the sealing resin layer 4 comprises a liquid epoxy resin (component A), a specific curing agent (component B), and an inorganic filler (component C) as essential components. It is obtained by using. In the liquid epoxy resin composition of the present invention, the term “liquid” refers to a liquid that exhibits fluidity at 25 ° C. That is, the viscosity at 25 ° C. is in the range of 0.01 mPa · s to 10000 Pa · s. The measurement of the viscosity can be performed using an EMD type rotational viscometer.

The liquid epoxy resin (component A) is not particularly limited as long as it is a liquid epoxy resin containing two or more epoxy groups in one molecule. Examples thereof include bisphenol A type and bisphenol F type. Liquid epoxy resins such as hydrogenated bisphenol A type, bisphenol AF type, phenol novolak type, and derivatives thereof, liquid epoxy resins derived from polyhydric alcohol and epichlorohydrin and derivatives thereof, glycidylamine type, hydantoin type, aminophenol type Glycidyl-type liquid epoxy resin such as aniline type, toluidine type, etc. and its derivatives (edited by the Practical Plastic Dictionary Editing Committee, “Practical Plastic Dictionary Dictionary Material”, 3rd printing of the first edition, 1st edition)
(Published on April 20, 996, pages 211 to 225) and liquid mixtures of these liquid epoxy resins with various glycidyl-type solid epoxy resins. These may be used alone or in combination of two or more.

As the specific curing agent (component B), at least one of the fluorine-containing aromatic diamines and derivatives thereof (component B1) is used, and at least one of the fluorine-containing aromatic diamines and derivatives thereof is mixed with a liquid. Prepolymer prepared by reacting with epoxy resin (B2 component)
There are two cases in which is used.

The fluorinated aromatic diamine in at least one of the fluorinated aromatic diamines and derivatives thereof (component B1) 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-3-aminophenyl) hexafluoropropane, , 4'-bis [2- (4-carboxyphenyl)
Hexafluoroisopropyl] diphenyl ether,
4,4'-bis [2- (4-aminophenoxyphenyl) hexafluoroisopropyl] diphenyl ether and the like, and these can be used alone or in combination of two or more.

As at least one of the fluorine-containing aromatic diamines and derivatives thereof (component B1), a fluorine-substituted or fluorinated alkyl-substituted diaminobiphenyl represented by the following general formula (1) can be used at room temperature. It is preferably used because the pot life becomes long.

[0020]

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In the above formula (1), R ^{1 to} R ⁴ are hydrogen or a monovalent organic group, and at least two of R ^{1 to} R ⁴ must be hydrogen. Examples of the organic group of the monovalent, for _{example, -C n H 2n + 1 (} n is a positive number of 1 to 10.) Saturated alkyl groups represented by, an aryl group, -C
_{H 2 CH (OH) -OC n} H 2n + 1 2- alkoxy-substituted-2-hydroxyethyl group represented by, -CH ₂ CH (O
H) -R ⁵ (R ⁵ is an aryl group.) 2 represented by
-Aryl-substituted-2-hydroxyethyl group and the like. And R ^{1 to} R ⁴ may be the same or different from each other.

Among them, in the present invention, the use of 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, which has the smallest active hydrogen equivalent, as the B1 component can reduce the compounding amount. It is preferable from the viewpoint that the viscosity of the one-component solventless epoxy resin composition can be reduced.

Further, in the present invention, at least one of the above-mentioned fluorine-containing aromatic diamine and its derivative (B)
A non-fluorinated aromatic diamine may be used together with (1 component) as long as the repairability of the present invention is not impaired. Such non-fluorinated aromatic diamines include, for example, p-phenylenediamine, m-phenylenediamine, 2,5-toluenediamine, 2,4-toluenediamine, 4,6-dimethyl-m-phenylenediamine,
Aromatic mononuclear diamine such as 2,4-diaminomesitylene, 4,4′-diaminodiphenyl ether, 3,3 ′
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylmethane, 4,4'-
Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,
Aromatic binuclear diamines such as 4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3
Aromatic trinuclear diamines such as -aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, and 1,3-bis (3-aminophenoxy) benzene;
4'-di- (4-aminophenoxy) diphenylsulfone, 4,4'-di- (3-aminophenoxy) diphenylsulfone, 4,4'-di- (4-aminophenoxy)
Diphenylpropane, 4,4'-di- (3-aminophenoxy) diphenylpropane, 4,4'-di- (4-aminophenoxy) diphenylether, 4,4'-di-
And aromatic tetranuclear diamines such as (3-aminophenoxy) diphenyl ether. The non-fluorinated aromatic diamine generally has a higher reactivity as a primary amine than the fluorinated aromatic diamine, and thus has the advantage of a faster curing reaction. However, the amount of the solvent used is limited due to the drawback that the solvent hardly swells and repair becomes difficult. Specifically, the usage ratio of the non-fluorinated aromatic diamine is 50% of the total amount of the non-fluorinated aromatic diamine and at least one of the fluorine-containing aromatic diamine and its derivative.
It is preferable to set so as to be not more than weight%.

The mixing ratio of at least one of the above-mentioned fluorinated aromatic diamine and its derivative (component B1) is based on 1 equivalent of the epoxy group of the above liquid epoxy resin (component A). It is preferable that at least one of the active hydrogen equivalents is set in the range of 0.5 to 1.2 equivalents. More preferably, it is set in the range of 0.6 to 1.0 equivalent number. That is, when the active hydrogen equivalent number of at least one of the fluorinated aromatic diamine and the derivative thereof exceeds 1.2 equivalent number, the compounding amount of at least one of the fluorinated aromatic diamine and the derivative thereof naturally increases, so that the liquid epoxy This is because the viscosity of the resin composition tends to increase, which is not preferable, and when it is less than 0.5, the glass transition temperature of the liquid epoxy resin composition cured product tends to decrease, which is not preferable.

Next, at least one of the above-mentioned fluorine-containing aromatic diamine and its derivative, which is another curing agent (component B), is reacted with a liquid epoxy resin to obtain a prepolymer (component B2). As at least one of the fluoroaromatic diamine and the derivative thereof, the same one as the component B1 described above is used.

As the liquid epoxy resin to be reacted with at least one of the above-mentioned fluorine-containing aromatic diamine and its derivative, the same as the above-mentioned liquid epoxy resin (component A) is used. In addition, a polyfunctional aliphatic liquid epoxy resin is used. As the polyfunctional aliphatic liquid epoxy resin, specifically, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl aniline, trimethylolpropane diglycidyl Examples include aliphatic diols and triols such as ether, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, and glycerin triglycidyl ether, and polyfunctional glycidyl ethers of aliphatic polyfunctional alcohols. In particular, it is preferable to use the above polyfunctional aliphatic liquid epoxy resin from the viewpoint of lowering the viscosity of the prepolymer as the B2 component.

The ratio of at least one of the fluorinated aromatic diamines and derivatives thereof and the liquid epoxy resin in preparing the prepolymer as the component B2 is based on 1 equivalent of the epoxy group of the liquid epoxy resin. The active hydrogen equivalent number of at least one of the fluoroaromatic diamine and the derivative thereof is 0.15 to 1.0 equivalent number or 1.25.
It is preferable to set the range of any one of the number of equivalents to 3.34. That is, the content of at least one of the fluorine-containing aromatic diamine and the derivative thereof is 0.1%.
When the amount is less than 5 equivalents, the glass transition temperature of the liquid epoxy resin composition finally obtained in the present invention tends to decrease, which is not preferable. The cross-linking reaction of the resulting prepolymer itself proceeds, which tends to cause gelation, which is not preferable. On the other hand, if it is larger than 3.34 equivalents, the obtained prepolymer tends not to exhibit a liquid state.

The ratio of at least one of the fluorinated aromatic diamines and derivatives thereof and the liquid epoxy resin in the preparation of the prepolymer as the component B2 is based on 1 equivalent of the epoxy groups of the liquid epoxy resin. When the active hydrogen equivalent number of at least one of the fluoroaromatic diamine and its derivative is 0.15 to 1.0 equivalent number, the molecular weight of the prepolymer is set to about 400 to 5000 in terms of polystyrene equivalent weight average molecular weight. It is preferable to use a prepolymer which is effective in preventing the generation of voids in the underfill sealing resin layer due to the evaporation and volatilization of the volatile low boiling point low molecular weight compound. .

The above-mentioned prepolymer (component B2) is prepared by mixing at least one of the above-mentioned fluorinated aromatic diamine and its derivative and the liquid epoxy resin at the above-mentioned predetermined ratio, and generally mixing the mixture at about 80 to 160 ° C. By reacting with

The mixing ratio of the prepolymer (component B2) obtained as described above is in accordance with the liquid epoxy resin (A
Component) and at least one of a fluorinated aromatic diamine and a derivative thereof before the prepolymer reaction with respect to 1 equivalent of the total epoxy groups of the epoxy group of the liquid epoxy resin before the reaction of the prepolymer (component B2) with the epoxy group. It is preferable to set the blending amount of the prepolymer (component B2) so that the number of active hydrogen equivalents in the above ranges from 0.15 to 1.2 equivalents. More preferably, it is set in the range of 0.2 to 1.0 equivalent number. That is, if the active hydrogen equivalent number of at least one of the fluorinated aromatic diamine and the derivative thereof before the reaction of the prepolymer (B2 component) is less than 0.15 equivalent number, the glass transition temperature of the liquid epoxy resin composition cured product decreases. This is because the tendency tends to be unfavorable, and if it exceeds 1.2 equivalents, the amount of the compound increases, and the viscosity of the liquid epoxy resin composition tends to increase, which is not preferable.

The inorganic filler (component C) used together with the liquid epoxy resin (component A) and the specific curing agent (component B) includes silica powder such as synthetic silica and fused silica, alumina, silicon nitride, and 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. And it is preferable to use a thing with a maximum particle diameter of 24 micrometers or less as said inorganic filler. Further, those having an average particle diameter of 10 μm or less as well as the above-mentioned maximum particle diameter are preferably used, and those having an average particle diameter of 1 to 8 μm are particularly preferably used. The maximum particle size and the average particle size can be measured using, for example, a laser diffraction / scattering type particle size distribution analyzer.

The amount of the inorganic filler is preferably set in the range of 10 to 80% by weight, particularly preferably 40 to 70% by weight, based on the whole liquid epoxy resin composition. That is, 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 is small, and if it exceeds 80% by weight, the viscosity of the liquid epoxy resin composition tends to increase. This is because it is not preferable.

In the present invention, various known curing accelerators can be used to shorten the curing time. Specifically, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7 and triethylenediamine;
Imidazoles such as methylimidazole; phosphorus-based curing accelerators such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate; and acidic catalysts such as salicylic acid. These may be used alone or in combination of two or more. In particular, in the present invention, it is preferable to use a phosphonium salt such as tetraphenylphosphonium tetraphenylborate as the curing accelerator, because the stability of the liquid epoxy resin composition is not impaired.

The amount of the curing accelerator is not particularly limited, but a desired curing speed can be obtained with respect to the mixture of the liquid epoxy resin (component A) and the specific curing agent (component B). It is preferable to appropriately set the ratio so as to be a certain ratio. For example, as an index of the curing speed, the amount used can be easily determined while measuring the gel time with a hot platen. As an example, it is preferable to set the amount in a range of 0.01 to 3% by weight in the whole liquid epoxy resin composition.

In the present invention, in addition to the liquid epoxy resin (component A), the specific curing agent (component B), the inorganic filler (component C), and the curing accelerator, the liquid epoxy resin composition comprises A silane coupling agent may be used in combination for the purpose of promoting adhesion to the adherend, strengthening interfacial adhesion with various inorganic fillers, and the like. The silane coupling agent is not particularly limited, for example, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like.

Further, in addition to the above components, a reactive diluent may be appropriately blended for the purpose of lowering the viscosity. The reactive diluent is not particularly limited and includes, for example, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, lauryl glycidyl ether, p -Sec-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, glycidyl ether of carbinol, glycidyl methacrylate, vinylcyclohexene monoepoxide, α-pinene oxide, glycidyl ether of tertiary carboxylic acid,
Diglycidyl ether, glycidyl ether of (poly) ethylene glycol, glycidyl ether of (poly) propylene glycol, propylene oxide adduct of bisphenol A, partial adduct of bisphenol A type epoxy resin with polymerized fatty acid, polyglycidyl ether of polymerized fatty acid And diglycidyl ether of butanediol, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, diglycidyl aniline, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether and the like. Can be These may be used alone or in combination of two or more.

In the present invention, the liquid epoxy resin composition contains, in addition to the above components, antimony trioxide,
Flame retardants and flame retardants such as antimony pentoxide and brominated epoxy resin, low-stress agents such as silicone, coloring agents, and the like can be appropriately compounded without departing from the spirit of the present invention.

[0038] Such a liquid epoxy resin composition can be produced, for example, as follows. That is, a predetermined amount of each component such as the liquid epoxy resin (A component), a specific curing agent (B component), an inorganic filler (C component), and, if necessary, a curing accelerator is blended, and the three components are rolled. By mixing and dispersing under a high shearing force such as a mixer or a homomixer, and optionally defoaming under reduced pressure, the desired one-part solvent-free liquid epoxy resin composition can be produced.

An electronic component device obtained by sealing a semiconductor element (flip chip) and a printed circuit board with a resin using the liquid epoxy resin composition thus obtained is manufactured, for example, as follows. That is, a semiconductor element having a connection electrode portion (solder bump) in advance and a printed circuit board provided with a solder pad facing the solder bump are connected by solder metal. Next, using a capillary phenomenon in a gap between the semiconductor element and the wiring circuit board, a liquid epoxy resin composition of a one-component non-solvent is filled and thermally cured to form a sealing resin layer, thereby sealing the resin. . In this manner, as shown in FIG. 1, the connection electrode portion (solder bump) 3 provided on the semiconductor element 1 and the connection electrode portion (solder pad) 5 provided on the printed circuit board 2 are opposed to each other. In this state, the semiconductor element (flip chip) 1 is mounted on the printed circuit board 2, and the printed circuit board 2 and the semiconductor element (flip chip) are mounted.
An electronic component device is manufactured in which the gap with 1 is sealed with the sealing resin layer 4 made of the liquid epoxy resin composition.

When filling the gap between the semiconductor element (flip chip) 1 and the wiring circuit board 2 with the liquid epoxy resin composition, first, the liquid epoxy resin composition is filled into a syringe, and then the semiconductor element ( A liquid epoxy resin composition is extruded from a needle onto one end of a flip chip (1), applied, and filled using a capillary phenomenon. When filling using this capillary phenomenon, liquid viscosity is reduced by filling and sealing on a hot plate heated to about 60 to 120 ° C., so that filling and sealing can be performed more easily. . Furthermore, if the printed circuit board 2 is inclined, the filling and sealing becomes easier.

The electronic component device thus obtained is
The gap distance between the semiconductor element (flip chip) 1 and the printed circuit board 2 is generally about 30 to 300 μm.

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

As the above-mentioned specific organic solvent, ketone solvents, glycol diether solvents, nitrogen-containing solvents and the like are preferable.

Examples of the above ketone solvents include acetophenone, isophorone, ethyl-n-butyl ketone, diisobutyl ketone, diethyl ketone, cyclohexyl ketone,
Di-n-propyl ketone, methyl oxide, methyl-n
-Amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, methyl cyclohexanone, methyl-n-heptyl ketone, holone and the like. These may be used alone or in combination of two or more.

Examples of the glycol diether solvents include ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. . These may be used alone or in combination of two or more.

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

As a method of repairing the above electronic component device, for example, a semiconductor element (flip chip) or a repaired portion of a printed circuit board is heated using a hot plate or the like to remove the semiconductor element. As the heating temperature at this time,
By further heating 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, the cured body is cohesively broken or adhered to one (semiconductor element or wiring circuit board). Can be easily peeled off. Thereafter, the organic solvent is directly applied or the organic solvent is impregnated in absorbent cotton, and the remaining portion of the cured body of the epoxy resin composition of the printed circuit board is heated to room temperature or about 40 to 70 ° C. After contact, the printed circuit board can be reused by confirming the swelling of the cured body and removing the residue. On the other hand, the semiconductor element (flip chip) to which the residue of the cured body of the liquid epoxy resin composition adheres is immersed in the above-mentioned organic solvent taken in a predetermined container at room temperature or at a heated state of 40 to 100 ° C. By swelling and removing, the semiconductor element (flip chip) can be reused.

Alternatively, although a long-time process is required, the entire repaired portion of the printed circuit board is
The above organic solvent is directly applied or covered with absorbent cotton impregnated with the organic solvent, and the organic solvent is gradually penetrated from the end of the semiconductor element to swell the cured body, thereby strengthening and bonding the cured body. Then, the semiconductor element can be removed from the printed circuit board.

Next, examples will be described together with comparative examples.

First, the following components were prepared.

[Liquid epoxy resin a] An epoxy resin having a repeating unit represented by the following structural formula (2).

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[Liquid epoxy resin b] An epoxy resin having a repeating unit represented by the following structural formula (3).

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[Liquid epoxy resin c] An epoxy resin having a repeating unit represented by the following structural formula (4).

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[Fluorine-containing aromatic diamine a] A fluorine-containing aromatic diamine represented by the following structural formula (5).

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[Fluorine-Containing Aromatic Diamine Derivative a] 1 mol of the fluorinated aromatic diamine represented by the above structural formula (5) and 0.5 mol of butyl glycidyl ether are charged into a reaction vessel and heated at 200 ° C. A fluorine-containing aromatic diamine derivative represented by the following structural formula (5 ′) obtained by the reaction.

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[Fluorine-containing aromatic diamine b] A fluorine-containing aromatic diamine represented by the following structural formula (6).

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[Non-fluorinated aromatic diamine a] A non-fluorinated aromatic diamine represented by the following structural formula (7).

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[Non-fluorinated aromatic diamine derivative a] The non-fluorinated aromatic diamine 1 represented by the above structural formula (7)
A non-fluorinated aromatic diamine derivative represented by the following structural formula (7 '), obtained by charging a mole and 0.5 mole of butyl glycidyl ether into a reaction vessel and reacting the mixture at 200 ° C.

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[Non-fluorinated aromatic diamine b] Non-fluorinated aromatic diamine represented by the following structural formula (8).

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[Prepolymer a (fluorine-containing)] The repeating unit represented by the above structural formula (2) is repeated for 1 equivalent (80 g) of active hydrogen of the fluorinated aromatic diamine represented by the above structural formula (5). 0.5 equivalent of epoxy resin having units (8
2.8 g) was reacted at 150 ° C. for 15 minutes, and cooled to obtain a syrupy viscous liquid prepolymer a (active hydrogen equivalent: 325).

[Prepolymer b (fluorine-containing)] Fluorine-containing aromatic diamine derivative 1 represented by the above structural formula (5 ')
Moles and 4 moles of the aliphatic polyfunctional epoxy resin represented by the above structural formula (3) were charged into a reaction vessel, and 1
Prepolymer b obtained by reacting for 0 minutes
(Viscosity 10 dPa · s, weight average molecular weight 560).

[Prepolymer c (non-fluorine-containing)] The repeating unit represented by the above structural formula (2) per 1 equivalent of active hydrogen of the non-fluorinated aromatic diamine represented by the above structural formula (7) Prepolymer c (active hydrogen equivalent 2), which is a syrup-like viscous liquid obtained by reacting 0.5 equivalents of an epoxy resin having
19).

[Prepolymer d (non-fluorine-containing)] 1 mol of a non-fluorine-containing aromatic diamine derivative represented by the above structural formula (7 ') and an aliphatic polyfunctional epoxy represented by the above-mentioned structural formula (3) A prepolymer d obtained by charging 4 moles of resin into a reaction vessel and reacting at 100 ° C. for 2 minutes.
(Viscosity 13 dPa · s, weight average molecular weight 510).

[Inorganic Filler] Spherical silica particles (maximum particle size)
Particle diameter 12 μm, average particle diameter 4 μm, specific surface area 3.0 m ^Two
/ G)

[0065]

Examples 1 to 24 and Comparative Examples 1 to 6 The components prepared above were blended in the ratios shown in Tables 1 to 6 below and homogeneously mixed and dispersed at room temperature (25 ° C.) using three rolls. Thus, a one-part solvent-free liquid epoxy resin composition was prepared.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

[0071]

[Table 6]

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 0.5%.
It was filled into a polypropylene syringe having a 6 mm needle.

Then, at 25 ° C. with the above-mentioned syringe packed.
, And the time until the viscosity doubled was measured, and it was defined as the pot life.

The gel time at 150 ° C. was measured as follows. That is, the specified temperature (150
C)), place the sample (200 to 500 mg) on a hot plate
The time from when the film was thinly stretched on a hot plate with stirring to the time when the film was hardened was read as the gelation time.

On the other hand, a silicon chip (thickness: 370 μm, size: 10 mm × 10 mm) having 64 solder bump electrodes having a diameter of 200 μm was prepared, and a copper wiring pad having a diameter of 300 μm was opened by opening 64 (board-side electrodes) 1 mm thick.
The chip is mounted on the board by aligning the copper wiring pad (board side electrode) of the FR-4 glass epoxy wiring circuit board on which the solder paste is applied with the solder bump electrode of the silicon chip. After doing this,
Soldering was performed through a heating reflow furnace at 0 ° C. for 10 seconds. The gap between the silicon chip and the circuit board
Was 210 μm.

Then, air pressure is applied to the syringe filled with the liquid epoxy resin composition, and the liquid epoxy resin composition is discharged from a needle onto one side of the gap between the silicon chip and the circuit board to apply the liquid. And then cured at 150 ° C. for 4 hours and sealed with a resin to produce an electronic component device.

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 7 to 12 below together with the measurement of the properties of the liquid epoxy resin composition.

[Conduction Failure Rate] The conduction failure rate was measured immediately after resin sealing of the electronic component device. Then, the above electronic component device was cooled at -30 ° C./10 min.
A temperature cycle test of 5 ° C./10 minutes was conducted to check the electrical continuity after 1000 cycles, and the continuity defect rate (%) for all 64 of the copper wiring pads (board-side electrodes) of the glass epoxy wiring circuit board was determined. Was calculated.

[Repairability] After measuring the conduction failure rate, the silicon chip was peeled off from the electronic component device on a hot plate heated to 200 ° C. and returned to room temperature, but the epoxy resin remaining at the connection portion was restored. Absorbent cotton in which an equivalent mixed solvent of N, N'-dimethylformamide and diethylene glycol dimethyl ether was added to the residue of the cured product of the composition was allowed to stand.
C. for 12 hours and Examples 19 to 24 and Comparative Examples 5 to 6 for 12 hours at room temperature. Thereafter, the absorbent cotton is removed, the wipe is thoroughly wiped with methanol, and the cured epoxy resin composition is peeled off. The peelable electronic component device is mounted on the wiring circuit board again with a silicon chip in the same manner as described above, and the electrical conductivity is reduced. Was examined. Thereafter, the resin sealing was performed in the same manner as described above, and the repairability was evaluated.

When the cured body of the epoxy resin composition can be completely peeled off and the electrical connection is complete, ◎ indicates that the cured body can be peeled off with a small amount of the cured body. The case where the cured product was slightly remaining and could be peeled off, but the electrical connection was incomplete was rated as Δ, and the case where the cured product of the epoxy resin composition could hardly be peeled off and the electrical connection was incomplete was rated as x.

[0081]

[Table 7]

[0082]

[Table 8]

[0083]

[Table 9]

[0084]

[Table 10]

[0085]

[Table 11]

[0086]

[Table 12]

From the results shown in Tables 7 to 12, it can be seen that the liquid epoxy resin compositions of all Examples are excellent as one-part solvent-free liquid epoxy resin compositions combined with long pot life and low viscosity. Moreover, it is clear that there is no conduction failure and the repairability is excellent. In Examples 19 to 24, the repairability was good even at room temperature. On the other hand, the liquid epoxy resin composition of Comparative Example is excellent in electrical conductivity, but has a short pot life,
Also, it is understood that the repairability is poor.

[0088]

As described above, according to the present invention, the gap between the circuit board and the semiconductor element is formed by a liquid epoxy resin (A component),
A liquid epoxy resin is reacted with at least one of a fluorinated aromatic diamine and its derivative (B1 component) or at least one of a fluorinated aromatic diamine and its derivative to be a specific curing agent (B component). This is an electronic component device sealed with a sealing resin layer made of a liquid epoxy resin composition containing a prepolymer (component B2) and an inorganic filler (component C) as essential components. The liquid epoxy resin composition swells after being cured by solvation with a specific organic solvent. As a result, the strength of the cured body is significantly reduced, and the cured body can be easily separated from the adherend (such as an electrode). Therefore, an electronic component device obtained by resin sealing using the liquid epoxy resin composition has excellent connection reliability, and even when a connection failure occurs due to a positional shift between electrodes, the electronic component device itself. An electronic component device having excellent repairability can be obtained without discarding the electronic component.

When a prepolymer (component (B2)) obtained by reacting at least one of a fluorinated aromatic diamine and a derivative thereof with the liquid epoxy resin is used as a curing agent for the liquid epoxy resin, it is even more effective. The curing speed can be improved. Moreover,
Since it can be formed in a state from a liquefaction to a viscous paste in advance, it is possible to easily obtain a desired liquid epoxy resin composition without requiring complicated steps in the measurement at the time of compounding and the subsequent dispersion step. .

In particular, when the compound represented by the above-mentioned specific formula (1) is used as at least one of the above-mentioned fluorinated aromatic diamine and its derivative, it is possible to ensure a sufficiently long pot life and obtain a rapid swelling property. This is particularly preferable because an effect that both ease of repair can be achieved is achieved.

In the component (B2), when a polyfunctional aliphatic liquid epoxy resin is used as the liquid epoxy resin to be reacted with at least one of the fluorinated aromatic diamine and its derivative, the viscosity of the prepolymer can be further reduced. Will be able to

[Brief description of the drawings]

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Semiconductor element (flip chip) 2 Wiring circuit board 3 Connection electrode part of semiconductor element (solder bump) 4 Sealing resin layer 5 Connection electrode part of wiring circuit board (solder pad)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/10 C09K 3/10 Z H01L 21/60 311 H01L 21/60 311S 23/29 23/30 R23 / 31 (72) Inventor Ichiro Hashiyama 5-7-1 Shiba, Minato-ku, Tokyo Inside NEC Corporation (72) Inventor Masahiro Kubo 5-7-1 Shiba, Minato-ku, Tokyo Inside NEC Corporation (72) Inventor Kazumasa Igarashi 1-2-1, Shimohozumi, Ibaraki-shi, Osaka F-term in Nitto Denko Corporation (reference) 4H017 AA04 AA27 AA31 AB08 AD06 AE05 4J002 CD041 CD051 CD131 CD202 DE077 DE137 DE147 DF017 DJ007 DJ017 EN076 FD017 FD146 GQ05 4J036 AA01 CB05 CB07 DC03 DC07 DC10 FA01 FA05 JA07 4M109 AA01 BA03 CA26 DB16 DB17 EA03 EB02 EB13 5F044 KK01 LL13 LL15 QQ03 RR16

Claims (6)

[Claims] A semiconductor element is mounted on a circuit board in a state where a connection electrode section provided on a semiconductor element and a connection electrode section provided on a circuit board face each other. Wherein the sealing resin layer is formed of a liquid epoxy resin composition containing the following components (A) to (C) as essential components. An electronic component device, comprising: (A) Liquid epoxy resin. (B1) At least one of a fluorinated aromatic diamine and a derivative thereof. (C) an inorganic filler. 2. A semiconductor element is mounted on the circuit board in a state where the connection electrode section provided on the semiconductor element and the connection electrode section provided on the circuit board face each other. Wherein the sealing resin layer is formed of a liquid epoxy resin composition containing the following components (A) to (C) as essential components: An electronic component device, comprising: (A) Liquid epoxy resin. (B2) A prepolymer obtained by reacting at least one of a fluorinated aromatic diamine and a derivative thereof with a liquid epoxy resin. (C) an inorganic filler. 3. The electronic component device according to claim 2, wherein in the component (B2), the liquid epoxy resin reacted with at least one of the fluorinated aromatic diamine and a derivative thereof is a polyfunctional aliphatic liquid epoxy resin. 4. The electronic component device according to claim 1, wherein at least one of the fluorinated aromatic diamine and a derivative thereof is a compound represented by the following general formula (1). Embedded image 5. The method according to claim 1, wherein at least one of said fluorinated aromatic diamine and its derivative is 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl.
The electronic component device according to any one of claims 1 to 4. 6. The inorganic filler as the component (C),
The electronic component device according to any one of claims 1 to 5, wherein the electronic component device is a spherical silica powder having an average particle diameter of 10 µm or less.