JP2000281914A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide resin compositions suited for use in low hygroscopic resin molded articles, particularly adhesives and circuit connecting members for electronic parts. SOLUTION: Resin compositions comprise (A) a thermoplastic resin having a water absorption of 0.05-0.25 wt.% and a glass transition temperature of 110 deg.C-160 deg.C and (B) a three-dimensionally crosslinkable resin. The thermoplastic resin is preferably a polysulfone resin represented by the formula (wherein R1 is hydrogen or 1-2C alkyl; R2 is 4-13C straight-chain or branched alkyl; and n is an integer of 5-750) and further, is preferably soluble in an aromatic hydrocarbon solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which gives a resin molded article having low moisture absorption, and is particularly suitable for use as a circuit connecting member for electronic parts.

[0002]

2. Description of the Related Art At present, organic materials such as epoxy resins are widely used in the semiconductor field. In the field of encapsulants, over 90% of encapsulation systems have been replaced by resin encapsulation systems. The sealing material is a composite material composed of an epoxy resin, a curing agent, various additives, an inorganic filler, and the like. As the epoxy resin, a cresol novolac epoxy resin is often used. However, cresol novolak type epoxy resin does not have the required characteristics to satisfy the characteristics such as low water absorption and low elastic modulus,
It is difficult to respond to the surface mounting method. For this reason, many new high-performance epoxy resins have been proposed and commercialized. Further, as a conductive adhesive for die bonding, a silver paste obtained by kneading silver powder with an epoxy resin is often used. However, as the mounting method of the semiconductor element on the wiring board shifts to the surface mounting method, there is an increasing demand for improving the solder reflow resistance of the silver paste.
In order to solve this problem, improvements have been made to the voids, peel strength, water absorption, elastic modulus, and the like of the cured die bonding adhesive layer. In the semiconductor packaging field, cost reduction
Flip-chip mounting, in which an IC chip is directly mounted on a printed circuit board or a flexible wiring board, has attracted attention as a new mounting mode corresponding to high definition. As a flip-chip mounting method, a method of providing a solder bump on a terminal of a chip and performing solder connection or a method of performing electrical connection via a conductive adhesive is known. In these systems, there is a problem in that when exposed to various environments, stress based on the difference in thermal expansion coefficient between the chip and the substrate to be connected is generated at the connection interface and connection reliability is reduced. For this reason, a method of injecting an epoxy resin-based underfill material into a gap between a chip and a substrate is generally studied for the purpose of reducing stress at a connection interface. However, the underfill injection step has a problem that the process is complicated and disadvantageous in productivity and cost. In order to solve such a problem, flip-chip mounting using an anisotropic conductive adhesive having anisotropic conductivity and a sealing function has recently attracted attention from the viewpoint of process simplicity.

[0003]

When a chip is mounted on a substrate via an anisotropic conductive adhesive, the adhesive force between the adhesive and the chip or between the adhesive and the substrate decreases under moisture absorbing conditions.
Furthermore, under temperature cycling conditions, stress based on the difference in thermal expansion coefficient between the chip and the substrate occurs at the connection part, and when reliability tests such as thermal shock tests, PCT tests, and high-temperature and high-humidity tests are performed, the connection resistance increases. There is a problem that peeling of the adhesive occurs. In addition, since the semiconductor package is subjected to a solder reflow temperature test after absorbing moisture in a high-temperature and high-humidity test, the moisture absorbed in the adhesive rapidly expands, thereby causing an increase in connection resistance and peeling of the adhesive. There's a problem. In general, a technique of dispersing a liquid rubber, a crosslinked rubber, and core-shell type rubber particles for the purpose of relaxing the internal stress of the epoxy resin and increasing the toughness is known.
However, it is known that a cured product obtained by dispersing a rubber in an epoxy resin has a lower softening point temperature (or glass transition temperature, hereinafter referred to as Tg) than a cured product of an epoxy resin alone, and has a high heat resistance. In fields where is required, reliability may be reduced. On the other hand, increasing the crosslink density of the epoxy resin to improve Tg in the rubber dispersion system reduces the effect of rubber dispersion, increases the brittleness of the cured product, increases the water absorption rate, and decreases the reliability. This can cause As a method for toughening an epoxy resin without lowering Tg, blending with a high heat-resistant thermoplastic resin known as engineering plastic is known. However, in general, these engineering plastics are soluble in a solvent. Because it is poor, the compounding with the epoxy resin is based on kneading of the powder, it is difficult to form a fine powder of engineering plastic, and it is difficult to uniformly disperse it, It is unsuitable to develop it for use in adhesives, such as poor uniformity. The present invention provides a resin composition which is suitable for use in a resin molded article having low moisture absorption, particularly an adhesive, and a circuit connecting member for electronic components.

[0004]

According to the present invention, a water absorption rate of 0.0
5 to 0.25% by weight and glass transition temperature 110 ° C to 16
It is a resin composition containing a thermoplastic resin (A) at 0 ° C. and a three-dimensionally crosslinkable resin (B). The present invention is a resin composition in which the thermoplastic resin (A) is preferably a polysulfone resin represented by the following general formula (I).

[0005]

Embedded image (Here, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a linear or branched alkyl group having 4 to 13 carbon atoms, and n is an integer of 5 to 750. )

Further, the present invention is a resin composition in which the thermoplastic resin (A) is preferably dissolved in an aromatic hydrocarbon solvent, and the three-dimensional crosslinkable resin (B) is at least an epoxy resin, It is a preferable resin composition to contain a curing agent, and the three-dimensional crosslinkable resin (B) is at least a radical polymerizable substance, and preferably contains a curing agent that generates free radicals by light irradiation or heating. is there. The present invention relates to a resin composition obtained by dissolving a thermoplastic resin (A) and a three-dimensionally crosslinkable resin (B) in an aromatic hydrocarbon-based solvent, uniformly mixing in a solution state, and removing the solvent after mixing. It is preferably an object. In this case, generally, the adhesive film can be obtained in the form of a film. The resin composition of the present invention is preferably used for a circuit connecting member. A connection member for connecting a first circuit member having a first connection terminal and a second circuit member having a second connection terminal. The resin composition of the present invention preferably contains 0.1 to 20% by volume of conductive particles dispersed therein, and is suitable as a circuit connecting member.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The water absorption used in the present invention is 0.05 to
0.25% by weight and glass transition temperature 110 ° C to 160 ° C
As the thermoplastic resin, it is preferable to use a polysulfone resin represented by the general formula (I) and soluble in an aromatic hydrocarbon solvent. The above-mentioned polysulfone resin,
For example, it can be synthesized from a bisphenol compound and bis (4-halogenated phenyl) sulfone. As the bisphenol compound, 1,1- (4,4′-dihydroxydiphenyl) -3-methylbutane (general formula (I)
Wherein R ₁ is a hydrogen atom, R ₂ is a branched alkyl group having 4 carbon atoms), 2,2- (4,4′-dihydroxydiphenyl)
-4-methylpentane (R ₁ is an alkyl group having 1 carbon atom,
R ₂ is a branched alkyl group having 4 carbon atoms), 1,1-
(4,4′-dihydroxydiphenyl) -3-ethylhexane (R ₁ is a hydrogen atom, R ₂ is a branched alkyl group having 7 carbon atoms), 3,3- (4,4′-dihydroxydiphenyl) pentane (R ₁ is an alkyl group having 2 carbon atoms, R ₂ is an alkyl group having 2 carbon atoms), 2,2- (4,4′-dihydroxydiphenyl) heptane (R ₁ is an alkyl group having 1 carbon atom, R ₂ is an alkyl group having 1 carbon atom) 5 linear alkyl groups), 1,1-
(4,4′-dihydroxydiphenyl) heptane (R ₁
Is a hydrogen atom, R ₂ is a linear alkyl group having 6 carbon atoms),
2,2- (4,4'-dihydroxydiphenyl) octane (R ₁ is an alkyl group having 1 carbon atoms, R ₂ is a linear alkyl group having 6 carbon atoms), 1,1 (4,4-dihydroxy Diphenyl) octane (R ₁ is an alkyl group having 1 carbon atom, R ₂
Is a linear alkyl group having 6 carbon atoms), 2,2 (4,4′-
Dihydroxydiphenyl) nonane (R ₁ is an alkyl group having 1 carbon atom, R ₂ is a linear alkyl group having 7 carbon atoms), 1,
1- (4,4'-dihydroxydiphenyl) nonane (R
₁ is an alkyl group having 1 carbon atom, R ₂ is a linear alkyl group having 8 carbon atoms), 2,2- (4,4′-dihydroxydiphenyl) decane (R ₁ is an alkyl group having 1 carbon atom, R ₂ Is a linear alkyl group having 8 carbon atoms), 1,1- (4,4′-dihydroxydiphenyl) decane (R ₁ is a hydrogen atom, R ₂ is a linear alkyl group having 9 carbon atoms), 2,2 -(4,4′-dihydroxydiphenyl) undecane (R ₁ is an alkyl group having 1 carbon atom, R ₂ is a linear alkyl group having 9 carbon atoms), 1,
1- (4,4′-dihydroxydiphenyl) undecane (R ₁ is a hydrogen atom, R ₂ is a linear alkyl group having 10 carbon atoms), 2,2- (4,4′-dihydroxydiphenyl)
Dodecane (R ₁ is an alkyl group having 1 carbon atom, R ₂ is an alkyl group having 1 carbon atom
0, a linear alkyl group), 1,1- (4,4′-dihydroxydiphenyl) dodecane (R ₁ is a hydrogen atom, R ₂ is a linear alkyl group having 11 carbon atoms), 2,2- (4 , 4'-
Dihydroxydiphenyl) tridecane (R ₁ has ₁ carbon atom
An alkyl group, R ₂ is a linear alkyl group having 11 carbon atoms), 1,1- (4,4′-dihydroxydiphenyl)
Tridecane (R ₁ is a hydrogen atom, R ₂ is a linear alkyl group having 12 carbon atoms), 2,2- (4,4′-dihydroxydiphenyl) tetradecane (R ₁ is an alkyl group having 1 carbon atom,
R ₂ is a linear alkyl group having 12 carbon atoms), 1,1-
(4,4′-dihydroxydiphenyl) tetradecane (R ₁ is a hydrogen atom, R ₂ is a linear alkyl group having 13 carbon atoms), and 2,2- (4,4′-dihydroxydiphenyl) pentadecane (R ₁ is An alkyl group having 1 carbon atom and R ₂ is a linear alkyl group having 13 carbon atoms), and two or more of these may be mixed. Preferably, 2,2
-(4,4'-dihydroxydiphenyl) octane (R
₁ is an alkyl group having 1 carbon atom, R ₂ is a straight-chain alkyl group having 6 carbon atoms), 1,1- (4,4′-dihydroxydiphenyl) decane (R ₁ is a hydrogen atom, R ₂ is 9 carbon atoms) Linear alkyl group) is used. As the bis (4-halogenated phenyl) sulfone for synthesizing the polysulfone resin, bis (4-chlorophenyl) propane is exemplified. Furthermore, it can be synthesized from a bisphenol compound halide and bis (4-hydroxyphenyl) sulfone.

The polysulfone resin can be synthesized by a usual method such as a solution polymerization method. For example, in the case of the solution polymerization method, a solvent in which the produced polysulfone resin is dissolved,
For example, a bisphenol compound and bis (4-halogenated phenyl) are dissolved in dimethylacetamide or the like, and the solution is dissolved at 130 ° C. in the presence of a base such as sodium hydroxide or potassium carbonate.
The reaction is carried out at -180 ° C for 10-12 hours to synthesize the desired polysulfone resin.

The polysulfone resin of the present invention preferably has a molecular weight of 20,000 to 300,000 in terms of polystyrene as measured by gel permeation chromatography using tetrahydrofuran as a solvent for the purpose of imparting toughness to the adhesive. . If it is less than 20,000, the cured product may not be brittle, and if it is more than 300,000, the fluidity of the resin composition decreases. Therefore, when the connection terminal of the electronic member is connected to the connection terminal of the circuit board, the electronic component and the circuit are connected. Filling with an adhesive resin between the substrates becomes difficult.

[0010] The three-dimensional crosslinkable resin used in the present invention comprises:
Epoxy resins, cyanate ester resins, imide resins, acrylate / methacrylate / maleimide compounds, and the like are used together with a curing agent. In the case of an epoxy resin, a known imidazole-based, hydrazide-based, boron trifluoride-amine complex, sulfonium salt, amine imide, polyamine salt, dicyandiamide, or other curing agent or a mixture thereof is used as a curing agent. Bisphenol type epoxy resin derived from bisphenol A, F, S, AD, etc., phenol novolak, epoxy novolak type resin derived from cresol novolak, naphthalene type epoxy resin having naphthalene skeleton, glycidylamine type epoxy resin, glycidyl ether type Epoxy resins, various epoxy compounds having two or more glycidyl groups in one molecule, such as biphenyl and alicyclic, and other known epoxy resins are used alone or as a mixture. It is necessary to use a high-purity product in which alkali metal ions, alkaline earth metal ions, halogen ions, especially chloride ions and hydrolyzable chlorine, etc. are reduced to 300 ppm or less to prevent electromigration and corrosion of metal conductor circuits. preferable.

As the cyanate ester resin, bis (4-cyanatophenyl) ethane, 2,2-bis (4-
Cyanatophenyl) propane, 2,2-bis (3,5-
Dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3
-Hexafluoropropane, α, α'-bis (4-cyanatophenyl) -m-diisopropylbenzene, a cyanate esterified product of a phenol-added dicyclopentadiene polymer, or the like, or a prepolymer thereof alone or as a mixture. Used. Among them, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) and the like are preferable because the cured product has particularly good dielectric properties. Metal-based reaction catalysts are used as a curing agent for the cyanate ester resin, and metal catalysts such as manganese, iron, cobalt, nickel, copper, and zinc are used. Specifically, 2-ethylhexanoate and naphthenic acid are used. It is used as an organic metal salt compound such as a salt and an organic metal complex such as an acetylacetone complex.

The compounding amount of the metal-based reaction catalyst is preferably from 1 to 3000 ppm, more preferably from 1 to 1000 ppm, even more preferably from 2 to 300 ppm, based on the cyanate ester compound.
If the blending amount of the metal-based reaction catalyst is less than 1 ppm, the reactivity and curability tend to be insufficient, and if it exceeds 3000 ppm, the control of the reaction becomes difficult, or the curing tends to be too fast. Absent.

The radically polymerizable substance such as an acrylate / methacrylate / maleimide compound of the three-dimensional crosslinkable resin used in the present invention is a substance having a functional group which is polymerized by a radical. Radical polymerizable substances are monomers,
It is possible to use any state of the oligomer,
It is also possible to use monomers and oligomers in combination. Specific examples of acrylate (methacrylate) include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylol methanetetraacrylate, and 2-hydroxy-1. , 3-Diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane,
Examples thereof include 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, dicyclopentenyl acrylate, tricyclodecanyl acrylate, and tris (acryloyloxyethyl) isocyanurate. These can be used alone or in combination. If necessary, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be appropriately used. In addition, it is preferable to have a dicyclopentenyl group and / or a tricyclodecanyl group and / or a triazine ring, since heat resistance is improved.

The maleimide compound contains at least two maleimide groups in the molecule, for example, 1-methyl-2,4-bismaleimidebenzene,
N, N'-m-phenylenebismaleimide, N, N'-
p-phenylenebismaleimide, N, N'-m-toluylenebismaleimide, N, N'-4,4-biphenylenebismaleimide, N, N'-4,4- (3,3'-dimethylbiphenylene) bis Maleimide, N, N'-4,4
-(3,3'-dimethyldiphenylmethane) bismaleimide, N, N'-4,4- (3,3'-diethyldiphenylmethane) bismaleimide, N, N'-4,4-diphenylmethanebismaleimide, N, N '-4,4-diphenylpropanebismaleimide, N, N'-4,4-diphenyletherbismaleimide, N, N'-3,3'
-Diphenylsulfonebismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-s-butyl-4,8- (4-maleimidophenoxy) phenyl) propane, 1,1-bis (4- (4-maleimidophenoxy) phenyl) decane, 4,4′-cyclohexylidene-bis (1- (4-
(Maleimidophenoxy) -2-cyclohexylbenzene, 2,2-bis (4- (4-maleimidophenoxy)
Phenyl) hexafluoropropane and the like. These can be used alone or in combination.

As a curing agent for a radical polymerizable substance such as an acrylate / methacrylate / maleimide compound, a mixture of a curing agent that generates free radicals by heat or light is used. Specifically, it is selected from peroxyesters, dialkyl peroxides, hydroperoxides, and silyl peroxides, and is more preferably selected from peroxyesters having high reactivity.
The above-mentioned curing agents can be appropriately mixed and used.

Examples of the peroxyester include cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxynodecanoate,
t-hexylperoxy neodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate, 2,5
-Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanonate, t-hexylperoxy-2-ethylhexanonate, t-butylperoxy-2-ethylhexanonate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy -3,5,5-trimethylhexanonate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-
Hexyl peroxybenzoate, t-butyl peroxyacetate and the like can be used. Examples of the dialkyl peroxide include α, α′-bis (t-butylperoxy)
Diisopropylbenzene, dicumyl peroxide,
2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide and the like can be used.

Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide. Examples of the diacyl peroxide include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, and 3,5,5-trimethylhexaoxide. Noyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoylperoxytoluene, benzoyl peroxide and the like can be used. As peroxydicarbonate, di-
n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, di (2-ethylhexylperoxy) dicarbonate , Dimethoxybutyl peroxydicarbonate, di (3-methyl-3-
(Methoxybutylperoxy) dicarbonate and the like can be used.

Examples of the peroxyketal include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (T-butylperoxy) -3,3,5-trimethylcyclohexane,
1,1- (t-butylperoxy) cyclododecane,
2,2-bis (t-butylperoxy) decane and the like can be used. Examples of the silyl peroxide include t-butyltrimethylsilyl peroxide, bis (t-butyl) dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis (t-butyl) divinylsilyl peroxide, and tris (t-butyl) vinyl. Silyl peroxide, t-butyl triallyl silyl peroxide, bis (t-butyl) diallylsilyl peroxide, tris (t-butyl) allylsilyl peroxide and the like can be used.

These hardeners generating free radicals can be used alone or in admixture.
Inhibitors and the like may be mixed and used. A microcapsule obtained by coating the above-mentioned curing agent with a polyurethane-based or polyester-based polymer substance or the like is preferable because the pot life is extended.

The resin composition of the present invention can be used in a mixing ratio of the thermoplastic resin (A) and the three-dimensional crosslinkable resin (B) of 1:99 to 99: 1 by weight, and is preferably used. Is from 10:90 to 90:10. The resin composition of the present invention may contain a rubber component such as an acrylic rubber for the purpose of reducing the elastic modulus of the cured product. In addition, a thermoplastic resin such as a phenoxy resin can also be blended with the resin composition of the present invention in order to make the film formability easier. In particular, a phenoxy resin is preferable when an epoxy-based resin is used as a base resin, because the phenoxy resin has features such as excellent compatibility with the epoxy resin and excellent adhesiveness since the structure is similar to the epoxy resin.

In order to form the resin composition of the present invention into a film, a resin composition containing a three-dimensionally crosslinkable resin, a curing agent thereof, and a thermoplastic resin is dissolved or dispersed in an organic solvent to form a varnish. It is performed by applying the composition on a peelable substrate and removing the solvent at a temperature lower than the activation temperature of the curing agent. In particular, a resin composition containing an epoxy resin and a latent curing agent as a three-dimensional crosslinkable resin, and a polysulfone resin represented by the general formula (1) as a thermoplastic resin is dissolved or dispersed in an organic solvent to be liquefied, and the resin is peelable. This is carried out by applying the composition on a substrate and removing the solvent at a temperature lower than the activation temperature of the curing agent. As the solvent used at this time, an aromatic hydrocarbon solvent is preferable for improving the solubility of the adhesive composition, but an aromatic hydrocarbon solvent and another solvent may be used in combination.

In the resin composition of the present invention, conductive particles can be dispersed for the purpose of positively imparting anisotropic conductivity in order to absorb variations in height of chip bumps and substrate electrodes. In the present invention, the conductive particles are, for example, Au, N
Metal particles such as i, Ag, Cu, and solder, or metal particles formed by plating or vapor-depositing a thin film of gold or palladium on the surface of these metals. Conductive particles provided with a conductive layer of Cu, Au, solder, or the like can be used. It is necessary that the particle size is smaller than the minimum distance between the electrodes of the substrate, and if there is a height variation of the electrodes, it is preferably larger than the height variation, and preferably larger than the average particle size of the inorganic filler. 1 to 10 μm is preferred. The amount of the conductive particles dispersed in the adhesive is 0.1 to 20% by volume.
And preferably 0.2 to 15% by volume.

As described above, the resin composition of the present invention
It can be easily manufactured by dissolving or dispersing each component in an organic solvent, stirring and mixing by an arbitrary method, and further, is applied on a peelable substrate, and the solvent is removed below the activation temperature of the curing agent. By doing so, a film can be formed. At that time, besides the above composition,
Additives used in the preparation of ordinary epoxy resin compositions may be added. The thickness of the film-like adhesive is not particularly limited, but is preferably larger than the gap between the first and second circuit members, and is generally preferably 5 μm or more larger than the gap.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. Example 1 29.8 g of 1,1- (4,4'-dihydroxydiphenyl) undecane, 57.4 g of bis (4-chlorophenyl) sulfone and 34.5 g of potassium carbonate were stirred in 500 ml of dimethylacetamide under a nitrogen atmosphere. The oil was refluxed at an oil bath temperature of 180 ° C. while heating. After stirring for 12 hours, the mixture was dropped into 3000 ml of acetone, and the formed precipitate was collected by filtration. The precipitate was dissolved in tetrahydrofuran, and the insolubles were filtered off.
ml. The resulting precipitate was collected by filtration to obtain 83 g of a polysulfone resin. As a result of GPC measurement, Mn = 46341, Mw = 300000, Mw /
Mn = 6.58. The resulting polysulfone resin was dissolved in toluene, applied to a petri dish, and the solvent was evaporated to produce a cast film. The cast film was cut into 2 cm squares, dried at 100 ° C. under reduced pressure, weighed, further immersed in pure water for 24 hours, and then weighed to calculate the weight increase. Was measured for water absorption. As a result of the water absorption measurement, the water absorption of the produced polysulfone resin was 0.1%.
It was 12% by weight. Further, the elastic modulus of the cast film was measured using a dynamic viscoelasticity measuring device (heating rate 5 ° C /
Min, 10 Hz), and Tg was measured by the peak value of tan δ. Dissolve 10 g of the produced polysulfone resin in 30 g of toluene, and add 25% by weight.
A solution was obtained. Next, 18.5 g of a liquid epoxy resin containing a commercially available microcapsule-type latent curing agent (bisphenol F-type epoxy resin, imidazole-based curing agent encapsulated in bisphenol F-type epoxy resin, epoxy equivalent: 185) was added to this solution. In addition, a conductive layer having a nickel layer having a thickness of 0.2 μm provided on the surface of a polystyrene core (diameter: 5 μm) and an Au layer having a thickness of 0.04 μm formed outside the nickel layer was mixed with 3 μm. The varnish solution for film coating was obtained by dispersing by volume%. Using this solution as a peelable substrate, a separator (silicone-treated polyethylene terephthalate film, thickness 40 μm)
Was coated with a roll coater and dried at 100 ° C. for 10 minutes to prepare an adhesive film having a thickness of 40 μm. 1 adhesive film
The cured film was cured at 50 ° C. for 3 hours, the elastic modulus of the cured film was measured using a dynamic viscoelasticity measuring apparatus, and Tg was measured by the peak value of tan δ. As a result, Tg was 157 ° C.

Using the produced adhesive film, gold bumps (area: 80 × 80 μm, space 30 μm, height: 1)
Chip with 5 μm, 288 bumps (10 × 10 m)
m, thickness: 0.5 mm) and Ni / Au plated Cu circuit printed circuit board (electrode height: 20 μm, thickness: 0.8 mm)
Was connected as shown below. An adhesive film with a separator was formed in a size of 12 mm × 12 mm, the adhesive film on the opposite side of the separator was laminated on a Ni / Au plated Cu circuit printed board, and a temporary connection step was performed at 60 ° C. and 0.5 MPa. After the temporary connection step, the separator was peeled off. After aligning the bumps on the chip with the Ni / Au-plated Cu circuit printed circuit board, heating and pressing are performed from above the chip under the conditions of 180 ° C., 100 g / bump, and 20 seconds, and the circuit board is formed by the main connection. Obtained.

The connection resistance of the circuit board after the main connection is 5 mΩ at maximum per bump, 1.5 mΩ on average, and the insulation resistance is 1
Was 0 ⁸ Ω or more. A large number of such circuit boards were prepared in the same manner, and subjected to a thermal shock test test at −55 to 125 ° C. for 1000 cycles. In addition, a PCT test (121 ° C., 2 atm) was performed for 200 hours, and a solder bath immersion at 260 ° C. was performed for 10 seconds, and the connection resistance was measured in the same manner as described above. 10
There was no change in the value of ⁸ Ω or more, indicating good connection reliability.

(Example 2) The adhesive film with a separator obtained in Example 1 was stored at room temperature for one month.
A chip and a substrate were connected in the same manner as in the above to obtain a circuit board. The connection resistance of the circuit board after connection is up to 7.5 per bump
mΩ, the average was 1.7 mΩ, and the insulation resistance was 10 ⁸ Ω or more. A large number of such circuit boards were produced in the same manner, and
Similarly, the thermal shock test at -55 to 125 ° C was performed for 100 times.
Processing was performed for 0 cycles. PCT test (121 ° C,
2 atm) for 200 hours and 260 ° C solder bath immersion for 1 hour.
The connection resistance was measured in the same manner as above for 0 second, and as a result, the maximum was 8 mΩ / bump, the average was 1.9 mΩ, and the insulation resistance was not changed to a value of 10 ⁸ Ω or more, indicating good connection reliability.

Comparative Example 1 As in Example 1, 10 g of bisphenol S type epoxy resin (epoxy equivalent 306) was used.
18.5 g of a liquid epoxy resin containing a microcapsule-type latent curing agent and 30 g of toluene were added, and 3% by volume of conductive particles having an Au layer formed on the surface of a polystyrene core (average diameter: 5 μm) were mixed and dispersed. However, the bisphenol S-type epoxy resin did not dissolve and a varnish solution for film coating could not be obtained.

Comparative Example 2 As in Comparative Example 1, a liquid epoxy resin 18.5 containing 10 g of bisphenol S type epoxy resin and a microcapsule type latent curing agent was used.
g and 30 g of methyl ethyl ketone, and 3% by volume of conductive particles having an Au layer formed on the surface of a polystyrene core (average diameter: 5 μm) were dispersed and mixed to obtain a varnish solution for film coating. This solution was applied to a separator (silicone-treated polyethylene terephthalate film, thickness: 40 μm) as a peelable substrate by a roll coater in the same manner as in Example 1, and dried at 100 ° C. for 10 minutes to produce an adhesive film having a thickness of 40 μm. The adhesive film was cured at 150 ° C. for 3 hours, and the elastic modulus of the cured film was measured using a dynamic viscoelasticity measuring apparatus. Tg was measured based on the peak value of tan δ.

Example 1 Using the Adhesive Film Produced
Similarly to the above, a chip (10 × 10 mm, thickness: 0.5 mm) with gold bumps (area: 80 × 80 μm, space: 30 μm, height: 15 μm, number of bumps: 288) and Ni / Au
The connection of a plated Cu circuit printed circuit board (electrode height: 20 μm, thickness: 0.8 mm) was performed as shown below. An adhesive film with a separator is formed in a size of 12 mm × 12 mm, and the adhesive film on the opposite side of the separator is laminated on a Ni / Au plated Cu circuit printed board, and the temperature is 60 ° C. and 0.5 MPa.
A temporary connection step was performed. After the temporary connection step, the separator was peeled off. After aligning the bumps on the chip with the Ni / Au plated Cu circuit printed circuit board,
Heating and pressing were performed from above the chip under the conditions of g / bump and 20 seconds, and the circuit connection was obtained by performing the main connection.

The connection resistance of the circuit board after connection is 6 mΩ at maximum per bump, 1.6 mΩ on average, and the insulation resistance is 10 mΩ.
It was ⁸ Ω or more. A large number of such circuit boards were prepared in the same manner, and subjected to a thermal shock test test at −55 to 125 ° C. for 1000 cycles. In addition, a PCT test (121 ° C., 2 atm) was performed for 200 hours, and a solder bath immersion at 260 ° C. was performed for 10 seconds, and the connection resistance was measured in the same manner as described above. Peeling occurred, resulting in poor conduction.

Comparative Example 3 After storing the adhesive film with a separator obtained in Comparative Example 2 at room temperature for one month, a chip and a substrate were connected in the same manner as in Example 1 to obtain a circuit board. During storage of the adhesive, the curing of the adhesive film progressed, and the fluidity was insufficient, resulting in partial conduction failure.

In Comparative Example 3, it is considered that the capsule of the microcapsule-type latent curing agent was a coating of an epoxy resin and was dissolved in methyl ethyl ketone, resulting in poor storage stability. On the other hand, toluene, which is an aromatic hydrocarbon solvent used in Examples 1 and 2, dissolves the polysulfone resin and can be formed into a film to make the composition uniform. In addition, since the capsule is not dissolved, it is stored at room temperature for one month. After that, the storage stability is excellent as in Example 1, and the heat resistance is excellent as shown in the thermal shock test and the solder heat resistance.
As shown in the CT test, the results showed excellent hygroscopicity and heat resistance.

[0034]

The resin composition of the present invention has a water absorption of 0.05
０．２0.25% by weight and glass transition temperature 110 ° C.〜160
By containing the thermoplastic resin (A) at 3 ° C. and the three-dimensionally crosslinkable resin (B), it is possible to give a resin molded article having low hygroscopicity. As a result, a cured product having good moisture resistance and heat resistance can be obtained. It is possible to significantly improve connection reliability and storage stability. Therefore, the resin composition of the present invention can be applied to a low-hygroscopic adhesive composition in the field of electronic materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 63/00 C08L 63/00 A 81/06 81/06 // C09J 4/00 C09J 4/00 163 / 00 163/00 181/06 181/06 (72) Inventor Akira Nagai 48 Wadai, Tsukuba, Ibaraki Prefecture Within Tsukuba Development Laboratory, Hitachi Chemical Co., Ltd. (72) Kenzo Takemura 48 Wadai, Tsukuba, Ibaraki Hitachi Chemical F-term in Tsukuba Development Laboratories Co., Ltd. (reference) 4J002 BG042 BG052 BH022 CD022 CD042 CD052 CD062 CD132 CM022 CN031 DA077 DA087 EK016 EK036 EK046 EK056 EK066 EK086 EQ026 ER026 EU116 FD117 GQ02 4J036 DC07 AF07 DC07 GA22 JA15 4J040 EC021 EC022 EC061 EC062 EC071 EC072 EC121 EC122 EC171 EC172 EC251 EC252 EJ031 EJ032 FA141 FA142 FA151 FA152 FA161 FA162 FA181 FA182 GA08 HA0 66 HA076 HB03 HB24 HB27 HB41 HC16 HD43 JA02 JB02 KA12 KA13 KA14 KA16 KA23 KA32 LA02 LA03 LA09 LA11 MA02 MA10 NA20 4J100 AL03P AL62P AL63P AL66P AL67P AM55P BA02P BA03P BA05P BA58P BB17P BC23P BCBC BCBC BCBC BCBC BCBC

Claims (8)

[Claims] 1. A thermoplastic resin (A) having a water absorption of 0.05 to 0.25% by weight and a glass transition temperature of 110 ° C. to 160 ° C.
And a three-dimensionally crosslinkable resin (B). 2. The resin composition according to claim 1, wherein the thermoplastic resin is a polysulfone resin represented by the following general formula (I). Embedded image (Here, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a linear or branched alkyl group having 4 to 13 carbon atoms, and n is an integer of 5 to 750. ) 3. The resin composition according to claim 1, wherein the thermoplastic resin (A) is dissolved in an aromatic hydrocarbon solvent. 4. The resin composition according to claim 1, wherein the three-dimensional crosslinkable resin (B) is at least an epoxy resin and contains a latent curing agent. 5. The method according to claim 1, wherein the three-dimensional crosslinkable resin (B) is at least a radical polymerizable substance and contains a curing agent that generates free radicals upon irradiation with light or heating. Resin composition. 6. The thermoplastic resin (A) and the three-dimensionally crosslinkable resin (B) are dissolved in an aromatic hydrocarbon solvent and uniformly mixed in a solution state, and the solvent is removed after mixing. The resin composition according to claim 5. 7. A resin composition characterized in that the thermoplastic resin (A) and the three-dimensionally crosslinkable resin (B) are used for a circuit connecting member. 8. A resin composition comprising the resin composition according to claim 1 and 0.1 to 20% by volume of conductive particles dispersed therein.