JP2000281916A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide resin compositions suitable as low-elastic, heat-resistant resin molded articles, particularly adhesives. SOLUTION: Resin compositions comprise (A) a resin composed of a structure represented by the formula, wherein R1 is hydrogen or 1-2C alkyl; R2 is 4-13C straight-chain or branched alkyl; and n and m are each an integer of 5-250 and (B) a three-dimensionally crosslinkable resin. Preferably, the resin (A) composed of a structure represented by the formula has a glass transition temperature of 80 deg.C-150 deg.C and is soluble in an aromatic hydrocarbon solvent or a mixed solvent of an aromatic hydrocarbon solvent with another organic 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 elasticity and heat resistance.

[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 In the field of encapsulants, over 90% of encapsulation systems have been replaced by resin encapsulation systems.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 that stress based on a difference in thermal expansion coefficient between a chip and a substrate to be connected is generated at a connection interface when exposed to various environments, 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 the temperature cycle condition, stress based on the difference in thermal expansion coefficient between the chip and the substrate is generated in the connection portion. Therefore, when a reliability test such as a thermal shock test, a PCT test, and a high temperature and high humidity test is performed, an increase in connection resistance may occur. 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 highly heat-resistant thermoplastic resin known as an 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 the kneading of the powder, it is difficult to form a fine powder of engineering plastic, and it is difficult to disperse it uniformly, and the physical properties are difficult depending on the location It is unsuitable for application to adhesives, such as poor uniformity. The present invention provides a low-elasticity and heat-resistant resin molded product, particularly a resin composition suitable as an adhesive.

[0004]

The present invention is a resin composition comprising a resin (A) having a structure represented by the following general formula (I) and a three-dimensional crosslinkable resin (B).

[0005]

Embedded image (Where 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 and m are integers of 5 to 250. is there.)

Further, according to the present invention, the resin (A) having a structure represented by the general formula (I) has a glass transition temperature of 80 to 15:
0 ° C., and is preferably a resin composition which is soluble in an aromatic hydrocarbon solvent or a mixed solvent of an aromatic hydrocarbon solvent and another organic solvent, wherein the three-dimensional crosslinkable resin (B) is at least epoxy The resin composition is preferably a resin and preferably contains a latent curing agent. Further, the present invention provides
It is a preferable resin composition that the three-dimensional crosslinkable resin (B) is at least a radical polymerizable substance and contains a curing agent that generates free radicals by light irradiation or heating. And
In the present invention, a resin (A) having a structure represented by the general formula (1) and a three-dimensionally crosslinkable resin (B) are dissolved in an aromatic hydrocarbon-based solvent and uniformly mixed in a solution state. It is preferable that the resin composition for a film adhesive obtained by removal is used. Further, the present invention provides a resin (A) having a structure represented by the general formula (I) and a three-dimensional crosslinkable resin (B)
Is preferably used for the circuit connecting member. Furthermore, in the present invention, it is preferable that 0.1 to 20% by volume of conductive particles is dispersed in the resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The resin (A) having a structure represented by the general formula (I) used in the present invention has a glass transition temperature of 8
0 ° C. to 150 ° C., and an aromatic hydrocarbon solvent or
It is preferable that it can be dissolved in a mixed solvent of an aromatic hydrocarbon solvent and another organic solvent, and exhibits properties of a thermoplastic resin. The resin (A) having the structure represented by the general formula (I) comprises a bisphenol compound and bis (p-hydroxyphenyl)
Synthesized from sulfones and their diglycidyl etherified products.

As the bisphenol compound for synthesizing the resin (A) having the structure represented by the general formula (I), 1,1- (4,4'-dihydroxydiphenyl)-
3-methylbutane (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 has 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 carbon atom 7
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 a linear alkyl group having 5 carbon atoms), 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 atom, R ₂ is A linear alkyl group having 6 carbon atoms), 1,1- (4,4'-dihydroxydiphenyl) octane (R1 is an alkyl group having 1 carbon atom, R2 is a linear alkyl group having 7 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; 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 atoms, 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 carbon atom 10
Linear alkyl group), 2,2- (4,4′-dihydroxydiphenyl) dodecane (R ₁ is an alkyl group having 1 carbon atom, R ₂ is a linear alkyl group having 10 carbon atoms), 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 is an alkyl group having 1 carbon atom, R ₂ is a straight-chain alkyl group having 11 carbon atoms), 1,1- (4,4′-dihydroxy) Diphenyl) 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 a carbon atom 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), 2,2- (4,4′-dihydroxydiphenyl) pentadecane (R ₁ is an alkyl group having 1 carbon atom, R ₂ is A straight-chain 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 atoms, R ₂ is a linear alkyl group having 6 carbon atoms), 1,1 (4,4 ' -Dihydroxydiphenyl) decane (R ₁ is an alkyl group having 1 carbon atom,
R ₂ is a linear alkyl group having 9 carbon atoms).

The diglycidyl ether compound can be obtained by mixing the above bisphenol compound and bis (p-hydroxyphenyl)
Diglycidyl ether of sulfone is used. Resin (A) having a structure represented by the general formula (I)
Can be synthesized by an ordinary solution polymerization method.
For example, in the case of the solution polymerization method, a bisphenol compound, bis (p-hydroxyphenyl) sulfone, and a diglycidyl etherified product thereof are dissolved in a solvent in which a polyhydroxyether resin as a reaction product is dissolved, for example, N-methyl-2-. Dissolved in pyrrolidone or the like, and added thereto a base such as sodium hydroxide, potassium carbonate or the like.
Then, a reaction is performed for 2 to 8 hours to synthesize a resin (A) having a structure represented by the general formula (I), which is a reaction product.
The resin (A) having a structure represented by the general formula (I) used in the present invention has a molecular weight of 10,000 or more and 100,000 or less in terms of polystyrene when measured by gel permeation chromatography using tetrahydrofuran as a solvent. preferable. If it is less than 10,000, the resin composition may become brittle,
If it is 100,000 or more, the fluidity of the resin composition decreases, and when the connection terminal of the electronic member is connected to the connection terminal of the circuit board, it becomes difficult to fill the electronic component with the adhesive between the circuit board and the circuit board.

[0010] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene and ethylbenzene. As the other organic solvent used by mixing with the aromatic hydrocarbon solvent, a solvent containing an oxygen atom in the molecule is preferable. As such an oxygen atom-containing organic solvent, an ester solvent such as ethyl acetate, acetone, etc. , Methyl ethyl ketone, ketone solvents such as cyclohexanone, ether solvents such as tetrahydrofuran and dioxane, solvents such as dimethyl sulfoxide, dimethylformamide, N-
Amide solvents such as methylpyrrolidone and N, N-dimethylacetamide. Among the above, those other than ketone solvents are particularly preferred.

The three-dimensional crosslinkable resin (B) used in the present invention
Examples thereof include an epoxy resin, a cyanate ester resin, an imide-based resin, an acrylate / methacrylate / maleimide compound as a radical polymerizable substance, and 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 A,
Bisphenol type epoxy resin derived from F, S, AD, etc., phenol novolak, epoxy novolak type resin derived from cresol novolak, naphthalene type epoxy resin having a naphthalene skeleton, glycidylamine type epoxy resin, glycidyl ether type epoxy resin, Various epoxy compounds having two or more glycidyl groups in one molecule, such as biphenyl and alicyclic, and other known epoxy resins may be used alone or as a mixture. It is preferable to use a high-purity product in which metal ions, alkaline earth metal ions, halogen ions, particularly chlorine ions and hydrolyzable chlorine, etc. are reduced to 300 ppm or less, in order to prevent electromigration and corrosion of circuit metal conductors.

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 amount of the metal-based reaction catalyst is preferably from 1 to 3000 ppm, more preferably from 1 to 1000 ppm, and 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 radicals. The radical polymerizable substance can be used in any state of a monomer and an oligomer, and a monomer and an oligomer can be used 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, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, dicyclopentenyl acrylate, tricyclodeca Nyl acrylate, tris (acryloyloxyethyl) isocyanurate and the like are exemplified. 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 is a compound containing 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-hexylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,
5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanate, t-hexylperoxy-2-ethylhexanonate , T-butylperoxy-2-ethylhexanonate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy Oxy-3,5,5-trimethylhexanonate, t-butylperoxylaurate, 2,5-dimethyl-2,5-
Di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t
-Hexylperoxybenzoate, t-butylperoxyacetate 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-butyl Cumyl 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 comprises a resin (A) having a structure represented by the general formula (I) and a three-dimensional crosslinkable resin (B)
(A) :( B) = 1: 99-99:
1, preferably from 10:90 to 9
0:10. The resin composition of the present invention can be obtained by dissolving (A) and (B) in an aromatic hydrocarbon-based solvent and uniformly mixing in a solution state. After mixing, the solvent is removed by drying to obtain a film-shaped resin composition. Obtainable. 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 because it has a similar structure to an epoxy resin and has characteristics such as excellent compatibility with an epoxy resin and excellent adhesiveness.

In order to form the resin composition of the present invention into a resin molded product, for example, a film, a resin (A) having a structure represented by the general formula (I), a three-dimensional crosslinkable resin (B) and It is performed by dissolving or dispersing a resin composition containing a curing agent and other compounding agents in an organic solvent, forming a varnish, applying the composition on a peelable substrate, and removing the solvent at or below the activation temperature of the curing agent. . The solvent used at this time is preferably an aromatic hydrocarbon-based solvent alone or a mixed solvent of an aromatic hydrocarbon-based solvent and another organic solvent, particularly an organic solvent containing an oxygen atom, for improving the solubility of the resin composition. In particular, a resin composition containing an epoxy resin as a three-dimensional crosslinkable resin, a latent curing agent, and a resin (A) having a structure represented by the general formula (I) is liquefied by dissolution or dispersion in an organic solvent to form a releasable group. It is carried out by coating on a material and removing the solvent at a temperature lower than the activation temperature of the curing agent. The resin composition of the present invention can be easily produced by dissolving or dispersing each component in an organic solvent, stirring and mixing by any method,
Further, a film can be formed 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 the resin composition of the present invention, conductive particles may be dispersed for the purpose of positively imparting anisotropic conductivity in order to absorb variations in the height of chip bumps and substrate electrodes. The conductive particles used in the present invention are, for example, A
Metal particles such as u, Ni, 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, and a spherical core material of a polymer such as polystyrene. Conductive particles provided with a conductive layer of Ni, Cu, Au, solder, or the like.
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 resin composition is 0.1 to
It is 20% by volume, preferably 0.2 to 15% by volume.

As described above, the resin composition of the present invention comprises:
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-shaped adhesive made of the resin composition is not particularly limited, but is preferably larger than the gap between the circuit members, and is generally preferably 5 μm or more with respect to the gap. .

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. (Example 1) 32 g of bis (p-hydroxyphenyl) sulfone, 52 g of bis (p-hydroxyphenyl) sulfone diglycidyl etherified product, 41.7 g of 1,1- (4,4′-dihydroxydiphenyl) undecane and 1,1 −
56 g of (4,4'-dihydroxydiphenyl) undecanediglycidyl etherate was dissolved in 1000 ml of N-methyl-2-pyrrolidone, and 51 g of potassium carbonate was added thereto.
Was added and stirred at 110 ° C. After stirring for 3 hours, the mixture is added dropwise to a large amount of methanol, and the resulting precipitate is collected by filtration. The target substance is a resin (A) having a structure represented by the general formula (1).
82 g was obtained. As a result of measurement by GPC, Mn = 10301, Mw = 17089, Mw / Mn in terms of polystyrene.
= 1.66. The resulting resin (A) having the structure represented by the general formula (I) 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,
Furthermore, after immersing in pure water for 24 hours, the weight was measured and the weight increase was calculated, thereby measuring the water absorption of the polyhydroxyether-based resin. As a result of the water absorption measurement, the water absorption of the produced polyhydroxyether resin was 1.5% by weight.
Met. The elastic modulus of the cast film was measured using a dynamic viscoelasticity measuring device (heating rate 5 ° C./min, 10H
z), as a result of measuring Tg by the peak value of tan δ, a peak was observed at 130 ° C.

10 g of the resin (A) having the structure represented by the general formula (I) is mixed with 1: 1 toluene: ethyl acetate.
(Weight ratio) in 30 g of a mixed solvent to obtain a 25% by weight solution. Next, a liquid epoxy containing a commercially available microcapsule-type latent curing agent (bisphenol F-type epoxy resin: epoxy equivalent: 185, imidazole-based curing agent encapsulated in bisphenol F-type epoxy resin) 18.
5 g was added to this solution and stirred, and a nickel layer having a thickness of 0.2 μm was provided on the surface of the polystyrene core (diameter: 5 μm).
The conductive particles on which the Au layer of m was formed were dispersed at 3% by volume 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, and dried at 100 ° C. for 10 minutes to produce an adhesive film made of a resin composition 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 device (temperature rising rate: 5 ° C./min,
As a result of measuring Tg by the peak value of tan δ, the temperature was 170 ° C. The storage modulus at 40 ° C. was 1.7 GPa. Using the produced adhesive film, gold bumps (area: 80 × 80 μm, space 3)
The connection between a chip (10 × 10 mm, thickness: 0.5 mm) with a Ni / Au plating Cu circuit printed circuit board (electrode height: 20 μm, thickness: 0.8 mm) with 0 μm, height: 15 μm, and bump number: 288) is as follows. Performed as shown. 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 pressurizing were performed from above the chip under the conditions of g / bump and 20 seconds, and the main connection was performed to obtain a circuit board.

The connection resistance of the circuit board after the actual connection is 5 mΩ at maximum per bump, 1.6 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. Connection resistance of the circuit board after connection is up to 7m per bump
Ω, the average was 1.7 mΩ, and the insulation resistance was 10 ⁸ Ω or more. A large number of the circuit boards were manufactured in the same manner, and a thermal shock test at −55 to 125 ° C. was performed in the same manner as in Example 1.
Cycled and processed. PCT test (121 ° C, 2
Pressure) for 200 hours and 260 ° C solder bath immersion for 10 hours.
The connection resistance was measured in the same manner as described above, and as a result, the maximum resistance per bump was 7 mΩ, the average was 1.7 mΩ, and the insulation resistance was 1
0 changing to ⁸ Omega or more values showed no good connection reliability.

Example 3 10 g of the resin (A) having the structure represented by the general formula (I) synthesized in Example 1 and then a bisphenol A diglycidyl ether methacrylic acid adduct (epoxy ester 3) as a radical polymerizable substance
000M, trade name, manufactured by Kyoeisha Chemical Co., Ltd.) 10 g, t-
1 g of butyl peroxy-2-ethylhexanoate was dissolved in a mixed solvent of toluene: ethyl acetate = 1: 1 so as to be 25% by weight. Further, the same conductive particles as in Example 1
The varnish solution for film coating was obtained by dispersing by volume%. Using this solution as a peelable substrate, a separator (silicon-treated polyethylene terephthalate film, thickness 40 μm) was used.
m) was applied by a roll coater and dried at 100 ° C. for 10 minutes to prepare an adhesive film made of a resin composition having a thickness of 40 μm. The adhesive film was cured at 150 ° C. for 3 hours, and the elasticity of the cured 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. , 120 ° C.

Comparative Example 1 10 g of a bisphenol S type epoxy resin (epoxy equivalent 308) was used instead of the resin (A) having the structure represented by the general formula (I), and 30 g of a mixed solvent of toluene: ethyl acetate = 1: 1 was used. To give a 25% by weight solution. Next, a liquid epoxy containing a commercially available microcapsule type latent curing agent (bisphenol F type epoxy resin: epoxy equivalent 185, imidazole type curing agent encapsulated in bisphenol F type epoxy resin)
18.5 g was added to this solution, and the solution was stirred. Further, a 0.2 μm thick polystyrene nucleus (diameter: 5 μm) was placed on the surface of the core.
A nickel layer having a thickness of 0.1 mm outside the nickel layer.
An attempt was made to obtain a varnish solution for film coating by dispersing 3% by volume of the conductive particles having the Au layer having a thickness of 04 μm, but the bisphenol S-type epoxy resin was not dissolved and a varnish solution could not be obtained.

Comparative Example 2 The solvent of Comparative Example 1 was toluene:
A varnish solution for film coating was obtained with the same formulation as in Comparative Example 1 except that the mixed solvent of ethyl acetate = 1: 1 was changed to a mixed solvent of methyl ethyl ketone: ethyl acetate = 1: 1 by weight. 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, 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 120 ° C. The storage modulus at 40 ° C. was 2.5 GPa. Using the produced adhesive film, gold bumps (area: 80 × 8) were formed in the same manner as in Example 1.
0 μm, space 30 μm, height: 15 μm, number of bumps 288) (10 × 10 mm, thickness: 0.5 m)
m) and a Ni / Au plated Cu circuit printed circuit board (electrode height: 20 μm, thickness: 0.8 mm) were connected as shown below. 12mm x adhesive film with separator
It is formed to 12 mm, and the adhesive film on the opposite side of the separator is overlaid on the Ni / Au-plated Cu circuit printed circuit board.
A temporary connection step was performed at 0.5 ° C. and 0.5 ° C. After the temporary connection step, the separator was peeled off. Chip bump and Ni / A
After positioning of the u-plated Cu circuit printed circuit board, heating and pressurizing were performed from above the chip under the conditions of 180 ° C., 100 g / bump, and 20 seconds, and the circuit was obtained by performing the main connection.

The connection resistance of the circuit board after connection is 6 mΩ at maximum per bump, 1.7 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.

(Comparative Example 4) The procedure of Example 3 was repeated except that 10 g of a phenoxy resin was used instead of the resin (A) having the structure represented by the general formula (I). A varnish solution was obtained. This solution was applied to a separator (silicone-treated polyethylene terephthalate film, thickness 40 μm) as a peelable substrate by a roll coater, and dried at 100 ° C. for 10 minutes to produce an adhesive film made of a resin composition 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 device (temperature rising rate: 5 ° C./min,
As a result of measuring Tg by the peak value of tan δ, the temperature was 90 ° C.

Comparative Example 1 uses a bisphenol S type epoxy resin containing the same structural unit as the repeating unit of the resin (A) having the structure represented by the general formula (I). The varnish solution for film coating cannot be obtained because it does not dissolve in the solvent. On the other hand, as shown in Comparative Example 2, when the solvent is methyl ethyl ketone: ethyl acetate, the solvent is dissolved, but the capsule of the microcapsule type latent curing agent is dissolved and the curing agent is eluted, so that the connection characteristics in the initial state are good. However, it is considered that the storage of the microcapsule-type latent curing agent was a coating of an epoxy resin and dissolved in methyl ethyl ketone, resulting in poor storage stability after storage for one month. On the contrary,
In Examples 1 and 2, heat resistance is improved by using the resin (A) having the structure represented by the general formula (I),
In addition, a varnish solution for film coating can be obtained without using a solvent that dissolves the capsule of the microcapsule-type latent curing agent, and is excellent in storage stability, heat resistance, and connection reliability. In addition, since the elasticity of the cured product is low, the stress caused by the difference in thermal expansion between the chip and the circuit board can be reduced, the connection resistance immediately after connection is relatively low, and the connection reliability after various processes is excellent. Can be provided.

[0036]

The resin composition of the present invention is a resin composition containing a resin (A) having a structure represented by the general formula (I) and a three-dimensionally crosslinkable resin (B), and has heat resistance and low elasticity. A resin molded product of the above can be provided, and by applying to an adhesive composition in the field of electronic materials, characteristics excellent in connection reliability can be provided.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 71/10 C08L 71/10 81/06 81/06 C09J 9/02 C09J 9/02 H05K 3/32 H05K 3/32 B (72) Inventor Akira Nagai 48 Wadai, Tsukuba, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd.Tsukuba R & D Co., Ltd. Reference) 4J002 AA02X BG03X BH02X CD00X CD04X CD05X CD06X CH08W CM02X CM04X CN03W DA077 DA087 DK008 EK006 EK016 EK036 EK056 EK066 EN008 EQ028 ER028 EU118 EV298 FB077 FD117 BF148 BA18BC084 FD156 AQ08 BF156 AQ18 BG03 BG09 4J040 EC002 EC061 EC171 HB03 JA01 JA02 JB08 JB10 KA03 KA16 KA23 KA32 LA02 LA06 LA08 NA20 5E319 BB11 BB13

Claims (7)

[Claims] 1. A resin composition comprising a resin (A) having a structure represented by the following general formula (I) and a three-dimensionally crosslinkable resin (B). Embedded image (Where 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 and m are integers of 5 to 250. is there.) 2. The resin (A) having a structure represented by the general formula (1) has a glass transition temperature of 80 to 150 ° C., and an aromatic hydrocarbon solvent or an aromatic hydrocarbon solvent and another organic solvent. The resin composition according to claim 1, wherein the resin composition is dissolved in a mixed solvent of 3. 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. 4. The three-dimensional crosslinkable resin (B) is at least a radical polymerizable substance, and contains a curing agent that generates free radicals by light irradiation or heating.
The resin composition according to any one of the above. 5. A resin (A) having a structure represented by the general formula (1) and a three-dimensionally crosslinkable resin (B) are dissolved in an aromatic hydrocarbon solvent and uniformly mixed in a solution state. The resin composition according to any one of claims 1 to 4, which is obtained by removing 6. A resin composition comprising a resin (A) having a structure represented by the general formula (1) and a three-dimensional crosslinkable resin (B) used for a circuit connecting member. 7. A resin composition comprising the resin composition according to claim 1 and 0.1 to 20% by volume of conductive particles dispersed therein.