JPH1140931A - Circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a circuit board which is superior in connection reliability. SOLUTION: This circuit board includes a mounting substrate, electronic components mounted on the substrate and adhesive with which the both are fixed. Connecting lands formed as associated with connection electrodes of the electronic components on a surface of the mounting substrate are electrically connected directly to the connection electrodes of the electronic components. The substrate has an insulating inner layer and an insulating outer layer for supporting the connecting lands. The residual stress percentage of the insulating outer layer at the temperature when fixedly mounting the electronic components on the substrate is in a range of 80-100%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a circuit board comprising a mounting board, an electronic component mounted thereon, and an adhesive for fixing the two.

[0002]

2. Description of the Related Art In general, a method of directly mounting a semiconductor chip on a mounting substrate by a face-down bonding method includes a flip chip method in which a solder bump is formed on an electrode portion of the semiconductor chip and soldered to the mounting substrate.
A connection method is used in which a conductive adhesive is applied to a protruding electrode provided on a semiconductor chip and bonded to a mounting substrate electrode.

As a method of electrically connecting a semiconductor chip or an electronic component to a mounting substrate by mechanical electrode connection, there is an anisotropic conductive adhesive in which conductive particles are dispersed.
This anisotropic conductive adhesive is provided with an adhesive film between an electronic component and an electrode or a circuit, and by forming a pressurizing or heating pressurizing means, both electrodes are electrically connected to each other, An electronic component and a circuit are bonded and fixed by providing insulation between adjacent electrodes. This mounting method by mechanical electrode connection is currently applied to a glass substrate, and studies are being made to apply it to a wiring board made of glass cloth reinforced resin having high versatility.

Further, as a method of electrically connecting an electronic component such as a semiconductor chip or the like to a mounting substrate by mechanical electrode connection, a gold bump is formed on an electrode of the semiconductor chip, and the gold electrode on the mounting substrate side is connected to a metal bump. A method of mechanically contacting and holding and fixing with a thermosetting or photocurable adhesive has also been proposed. A wiring board made of glass cloth reinforced resin used as a mounting substrate has excellent wiring density and can be economically multilayered, and is most commonly used as a wiring board material.

[0005]

Since a conventional FR-4 grade glass cloth reinforced resin wiring board contains glass cloth as a reinforcing material, the surface of the electrode formed on the surface is made of glass cloth. Had periodic irregularities along the weave. In addition, the connection electrodes (bumps and the like) of the electronic components had variations in height during manufacturing. Therefore, when these are connected, there is a problem that the heights of the connection electrodes and the surface of the wiring board vary, and the connection reliability is reduced. In particular, when a thermal shock or the like is applied, a gap may be formed at a connection portion between the electronic component and the circuit portion of the wiring board due to a difference in the coefficient of thermal expansion of the material, and a connection failure may occur.

In order to avoid this, it is preferable that a compressive stress always acts between the electronic component and the circuit board circuit, and it is conceivable to install a device that constantly presses the electronic component and the circuit board circuit. However, there is a problem that the cost increases and the mounting area increases.

An object of the present invention is to provide a circuit board having excellent connection reliability.

[0008]

A circuit board according to the present invention is a circuit board comprising a mounting board, an electronic component mounted on the mounting board, and an adhesive for fixing the both, and the electronic component is provided on the surface of the mounting board. The connection lands formed corresponding to the connection electrodes are electrically connected to the connection electrodes of the electronic component, and the mounting substrate has an inner insulation layer and an outer insulation layer supporting the connection lands. The residual stress ratio of the outer insulating layer at a temperature at which the mounting substrate and the electronic component mounted on the mounting substrate are bonded and fixed is in the range of 80% to 100%.

The residual stress ratio of the present invention can be measured as follows. (1) An insulating adhesive material film laminated to a thickness of 2 mm is cut into a width of 5 mm and a length of 6 cm. (2) A sample is fixed to a tensile tester so that the distance between chucks is 40 mm, and a load is applied at an elongation ratio of 5%. 1
The load after 36 seconds at 70 ° C. is measured as the initial load. (3) Measure the load one hour later. (4) The residual stress ratio was calculated from the measurement result by the following equation. Residual stress (%) = F1 / F0 × 100 F0: Load after 170 seconds at 170 ° C. (MPa) F1: Load after 1 hour at 170 ° C. (MPa)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION

(Outer insulating layer) The elastic modulus of the outer insulating layer of the mounting substrate of the present invention is preferably in a range of 0.1 MPa to 10000 MPa at a temperature at which the mounting substrate and the electronic component mounted thereon are fixed, When the pressure is less than 0.1 MPa, the insulating layer is deformed and the thickness becomes thin due to the pressure at the time of bonding and fixing the electronic component.
If the pressure exceeds 0000 MPa, the amount of deformation of the insulating layer due to the pressure at the time of bonding and fixing the electronic component is small, and the insulating layer does not follow the variation in the height of the bump, so that good contact between the bump and the wiring board circuit cannot be obtained. Therefore, the connection reliability between the bump and the substrate is not sufficient. The elastic modulus referred to in the present invention refers to a storage elastic modulus by a DVE stretching method. For example, the temperature of a rheologic DVE-4 (trade name) manufactured by Rheology Co., Ltd. is raised in a pulling mode at a frequency of 10 Hz and a temperature of 5 ° C./min. Can be measured.

Examples of such insulating materials include epoxy resin, high molecular weight epoxy resin, acrylic rubber, functional group-containing acrylic rubber, polyimide resin, polyamideimide resin, modified polyphenylene ether resin, phenoxy resin, amide epoxy resin, phenol resin, and the like. Mixtures and copolymers of these can be used, and polysulfone,
Films of heat-resistant thermoplastic engineering plastics such as polyethersulfone, polyetheretherketone, wholly aromatic liquid crystal polyester, and fluororesin can also be used.

Among them, epoxy resins and acrylic rubber-based adhesives include: a. 100 parts by weight of the epoxy resin and its curing agent in total,
b. 10 to 40 parts by weight of a high molecular weight component which is compatible with the epoxy resin and has an average molecular weight of 30,000 or more; c. Acrylonitrile is 18 to 40% by weight, glycidyl methacrylate is 2 to 6% by weight as a functional group monomer, and the balance is ethyl acrylate and butyl acrylate or a mixture of both, and has a Tg of -10 ° C or more and a weight average molecular weight of 800,000. 20 to 100 parts by weight of the above-mentioned epoxy group-containing acrylic elastomer, d. Add a curing accelerator to 0.
It is preferable to use an adhesive consisting of 1 to 5 parts by weight,
In particular, it is preferable to use a phenol resin as the curing agent a and use a phenoxy resin as a high molecular weight component having an average molecular weight of 30,000 or more, which is compatible with the epoxy resin b.

(Filler added to outer insulating layer) The purpose of the present invention is to improve the thermal conductivity, impart flame retardancy, adjust the melt viscosity, impart thixotropic properties, and improve the surface hardness. , Various fillers can be blended. To improve thermal conductivity,
Alumina, aluminum nitride, boron nitride, crystalline silica, and amorphous silica are preferred. Of these, alumina is preferred because it has good heat dissipation and good heat resistance and insulation properties.
Further, crystalline silica or amorphous silica is inferior to alumina in terms of heat dissipation, but has less ionic impurities. This is suitable because it has high insulation properties during the treatment, and has little corrosion of copper foil, aluminum wire, aluminum plate and the like. In order to provide flame retardancy, aluminum hydroxide and magnesium hydroxide are preferred. Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, for the purpose of adjusting melt viscosity and imparting thixotropic properties
Alumina, crystalline silica, and amorphous silica are preferred. For improving the surface hardness, short fiber alumina and aluminum borate whisker are preferable.

The shape of these fillers may be granular,
Disc-like or short-fiber fillers can be used. The compounding amounts of these fillers show the desired properties, and further additions will not improve the properties and will not be economical or will cause other problems. It is necessary to maximize the amount that does not cause the reaction to occur, and to conduct confirmation beforehand, but generally it is preferable that the amount be 50 parts by volume or less based on 100 parts by volume of the resin.

(Additive for Outer Insulating Layer) In addition to the above-mentioned filler, a coupling agent for improving interfacial bonding between different materials, an electrolytic corrosion inhibitor, and an ionic impurity are adsorbed to absorb moisture. May contain an ionic impurity adsorbent for improving the insulation reliability of copper or an additive such as a copper damage inhibitor.

As such a coupling agent, a silane coupling agent is preferable, and γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane are preferable. Ethoxysilane, N-β
-Aminoethyl-γ-aminopropyltrimethoxysilane and the like, and as commercially available products, γ-glycidoxypropyltrimethoxysilane is NUC A-187, γ
-Mercaptopropyltrimethoxysilane is NUC A
-189, γ-aminopropyltriethoxysilane is N
UC A-1100, γ-ureidopropyltriethoxysilane is NUC A-1160, N-β-aminoethyl-γ-aminopropyltrimethoxysilane is NUC
All are commercially available from Nihon Unicar Co., Ltd. under the trade name of A-1120.

As the inorganic ion adsorbent, a product containing a zirconium-based compound as a component IXE-100 and a product containing an antimony bismuth-based compound as a component IXE-600 are available from Toa Gosei Chemical Industry Co., Ltd. A product containing a magnesium aluminum-based compound as a component is commercially available under the trade name IXE-700. Further, there is a hydrotalcite that is commercially available from Kyowa Chemical Industry Co., Ltd. under the trade name of DHT-4A. The amount of the inorganic ion adsorbent is usually 1
The content is preferably 0% by weight or less, and if it is too large, heat resistance is reduced and cost is increased.

In addition, if necessary, a compound known as a copper damage inhibitor, for example, a triazine thiol compound or a bisphenol-based reducing agent may be blended in order to prevent copper from being ionized and dissolved. As the bisphenol-based reducing agent, 2,2′-methylene-bis- (4-methyl-
6-tert-butylphenol) and 4,4'-thio-bis- (3-methyl-6-tert-butylphenol). Among those commercially available as such, a copper harm inhibitor containing a triazine thiol compound is commercially available from Yoshitomi Pharmaceutical Co., Ltd. under the trade name Yoshinox BB, and also contains a bisphenol-based reducing agent as a component. A copper damage inhibitor is commercially available from Sankyo Pharmaceutical Co., Ltd. under the trade name Disnet DB.

(Adjustment of Outer Insulating Layer) In the outer insulating layer of the present invention, these components are dissolved and dispersed in a solvent to form a varnish, applied on a base film or a copper foil, and heated to remove the solvent. To use. As such a base film, a Teflon film, a release-treated polyethylene terephthalate film, a polyethylene terephthalate film, or the like is used, and the base film is peeled off at the time of use. Further, a metal with an adhesive can be obtained by applying the adhesive of the present invention using copper foil or aluminum foil as a base film. The metal foil is preferably subjected to a roughening treatment such as a matte surface treatment. In addition, such a varnished insulating adhesive material can be used by screen printing or coating on a wiring board.

The thickness of the outer insulating layer is from 25 μm to 20 μm.
When the thickness is less than 25 μm, the insulation between the layers is not sufficient. When the thickness exceeds 200 μm, the insulation between the layers is sufficient, but the workability with a drill or a laser is reduced, and the interlayer insulation is reduced. Through holes or interstitial via holes (hereinafter I
VH. ) Is difficult to form.

(Inner Insulating Layer) The linear expansion coefficient in the plane direction of at least one of the inner insulating layers is preferably 13 ppm / ° C. or less, and if it exceeds this, when a thermal shock or the like is applied, Due to the difference in the coefficient of thermal expansion between the electronic component such as a semiconductor chip and the inner insulating layer, cracks or voids may occur at the connection between the electronic component and the circuit portion of the mounting board, resulting in poor connection.

The inner insulating layer may be made of a resin reinforced with a glass substrate, such as a glass cloth-epoxy resin laminate, a glass cloth-polyimide resin laminate, or a glass cloth-phenol resin laminate. Etc. can be used.

(Adhesive) The adhesive used for bonding and fixing the electronic component in the present invention is not particularly limited, but an adhesive which can obtain good fluidity at the time of connection and high connection reliability can be used. An adhesive in which an acrylic rubber is mixed with a mixture of an epoxy resin and a latent curing agent such as an imidazole-based, hydrazide-based, boron trifluoride-amine complex, a sulfonium salt, an amine imide, a polyamine salt, and dicyandiamide can be used. In addition, a thermoplastic resin such as a phenoxy resin can be blended with the adhesive to make the film formability easier.In particular, the phenoxy resin has a similar structure to the epoxy resin, so Is preferred because it has characteristics such as excellent compatibility and adhesion.

The adhesive used for bonding and fixing the electronic parts contains dispersed conductive particles for the purpose of positively imparting anisotropic conductivity in order to absorb variations in height of chip bumps and circuit electrodes. As such conductive particles, for example, a metal particle such as Au, Ni, Ag, Cu, W or solder or a thin film such as gold or palladium formed on the surface of these metal particles by plating or vapor deposition Ni and C are added to metal particles and polymer spherical core material such as polystyrene.
Conductive particles provided with a conductive layer such as u, Au, and solder can be used. The particle size of such conductive particles needs to be smaller than the minimum distance between the electrodes of the substrate, and when there is a height variation of the electrodes, it is preferably larger than the height variation, preferably in the range of 1 μm to 10 μm. Preferably, there is. The amount of conductive particles dispersed in the adhesive is 0.1 to 0.1.
It is preferably in the range of 30% by volume, more preferably in the range of 0.2 to 15% by volume. If it is less than 0.1% by volume, the dispersion of the particles is large, the conductivity is reduced, and
If the content exceeds the volume percentage, short-circuit may occur due to contact with adjacent particles.

(Adjustment of Adhesive) The adhesive used in the present invention can be applied, but it is preferable to use it in the form of a film because it has good handleability during processing. Although a jig such as a plate is required, it is preferable to form a film because it can be cut and used in a necessary amount. To form the adhesive in the form of a film, the epoxy resin, acrylic rubber, phenoxy resin, an adhesive composition comprising a latent curing agent, or further conductive particles, dissolved or dispersed in an organic solvent, and liquefied, This 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. As the solvent used at this time, a mixed solvent of an aromatic hydrocarbon type and an oxygen-containing type is preferable because the solubility of the material is improved.

(Electronic Component) As the electronic component of the present invention, a chip resistor, a chip capacitor, a chip inductor, or a semiconductor chip for surface mounting can be used.
Also, the connection electrodes of such a semiconductor chip are plated with gold, nickel, solder, or the like, and are used as bump electrodes. In addition to ball bumps or stud bumps obtained by crimping the metal wires after being pressed onto the electrode pads of the semiconductor chip on which the terminals are formed, solder balls, molten solder formed bumps, and bump electrodes formed by soldering columns can be used.

[0027]

【Example】

(Preparation of Outer Insulating Layer) Varnishes A and B whose compositions are shown in Table 1.
Is applied on a copper foil with a comma coater so that the film thickness after drying becomes 50 μm, and dried at 110 ° C. for 10 minutes to obtain a semi-cured insulating adhesive material with a copper foil.

[0028]

[Table 1] -Epicoat 828: Bisphenol A type epoxy resin (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.)-ESCN-001: Cresol novolak type epoxy resin (trade name, manufactured by Sumitomo Chemical Co., Ltd.)-Pryofen LF2882: Bisphenol A novolak Resin (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) YP-50: phenoxy resin, molecular weight 50,000 (trade name, manufactured by Toto Kasei Co., Ltd.) HTR-860P-3: epoxy-containing acrylic rubber,
Molecular weight 1,000,000 (manufactured by Teikoku Chemical Industry Co., Ltd., trade name) 2PZ-CN: curing accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., trade name) NUC A-187: γ-glycidoxypropyltrimethoxysilane, silane Coupling agent (Nippon Unicar Co., Ltd., trade name) AL-160SG-1: Showa Denko Corporation, trade name AS-50: Showa Denko Corporation, trade name

Example 1 The coefficient of linear expansion in the X and Y directions was 16 ppm / ° C., and the Tg was about 1
MC, a glass-cloth / epoxy double-sided copper-clad laminate with 70 ° C., Tg or less and an elastic modulus of 1.8 × 10 ⁴ MPa
Unnecessary portions of the surface copper foil of LE-679 (trade name, manufactured by Hitachi Chemical Co., Ltd.) were removed by etching to form an inner layer circuit. The insulating adhesive material with copper foil using the varnish A of Table 1 was drilled, superimposed on the surface of the above-mentioned inner layer circuit, and press-laminated and bonded at 170 ° C., 40 kgf / cm ² , for 60 minutes. Holes were drilled, electroless copper plating was carried out, unnecessary copper was removed by etching, the outer layer circuit was processed, and solder coating was performed to obtain a mounting substrate.
At this time, the modulus of elasticity of the insulating adhesive material with copper foil used as the outer insulating layer was 100 MPa at 170 ° C., and the stress residual rate was 85% at 170 ° C. Thereafter, anisotropic conductive film ANISOLM (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an adhesive film, was transferred to a mounting substrate, and then the protrusions of the semiconductor chip were formed with solder balls as connection electrodes. Align the electrodes with the circuit for mounting the semiconductor chip on the mounting board,
The anisotropic conductive film was cured by heating and pressing at 0 ° C. under a pressure of 10 kgf / chip for 20 seconds. As a result, the protruding electrodes of the semiconductor chip and the circuit for mounting the semiconductor chip on the mounting substrate are electrically connected via the anisotropic conductive film, and at the same time, the semiconductor chip and the mounting substrate are cured by the curing of the anisotropic conductive film. , This connection state is maintained.

Example 2 The same as Example 1 except that a protruding electrode formed by a stud bump, which is a protruding electrode formed by bonding a gold wire to an electrode and cutting it, was used as a connection electrode of a semiconductor chip. I made it.

Example 3 The coefficient of linear expansion in the X and Y directions was 16 ppm / ° C., and the Tg was about 1
MC, a glass-cloth / epoxy double-sided copper-clad laminate with 70 ° C., Tg or less and an elastic modulus of 1.8 × 10 ⁴ MPa
LE-679 (manufactured by Hitachi Chemical Co., Ltd., trade name)
An unnecessary portion of the surface copper foil was removed by etching to form an inner layer circuit. As an outer insulating layer, an insulating adhesive material with copper foil using varnish B of Table 1 was drilled,
170 ℃, 40kgf / c
Pressing and laminating under conditions of m ² for 60 minutes, drilling through holes, performing electroless copper plating, removing unnecessary copper by etching, forming an outer layer circuit, performing electroless nickel / gold plating, and mounting substrate I got At this time, the elastic modulus of the outermost insulating adhesive film was 10 MPa at 170 ° C., and the stress residual rate was 83% at 170 ° C. Thereafter, anisotropic conductive film ANISOLM (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an adhesive film, was transferred to a mounting substrate, and then a projection of a semiconductor chip was formed with a solder ball as a connection electrode. Align the electrodes with the circuit for mounting the semiconductor chip on the mounting board,
The anisotropic conductive film was cured by heating and pressing at 70 ° C. under a pressure of 10 kgf / chip for 20 seconds. As a result, the protruding electrodes of the semiconductor chip and the circuit for mounting the semiconductor chip on the mounting substrate are electrically connected via the anisotropic conductive film, and at the same time, the semiconductor chip and the mounting substrate are cured by the curing of the anisotropic conductive film. , This connection state is maintained.

Examples 4 to 6 In Examples 1 to 3, the glass cloth / epoxy resin double-sided copper-clad laminate had a coefficient of linear expansion of 9 to 9 in the X and Y directions.
Semiconductor chips similar to those of Examples 1 to 3 were used except that MCL-E-679LD (trade name, manufactured by Hitachi Chemical Co., Ltd.), a glass cloth / epoxy resin double-sided copper-clad laminate of 11 ppm / ° C., was used. The semiconductor chip and the mounting substrate were connected under the same conductive film and mounting conditions.

(Stress Residual Rate of Insulating Adhesive Material) (1) A laminate of an insulating adhesive material film having a thickness of 2 mm is cut into a width of 5 mm and a length of 6 cm. (2) A sample is fixed to a tensile tester so that the distance between chucks is 40 mm, and a load is applied at an elongation ratio of 5%. 1
The load after 36 seconds at 70 ° C. is measured as the initial load. (3) Measure the load one hour later. (4) The residual stress ratio was calculated from the measurement result by the following equation. Residual stress (%) = F1 / F0 × 100 F0: Load after 170 seconds at 170 ° C. (MPa) F1: Load after 1 hour at 170 ° C. (MPa)

(Elastic Modulus of Insulating Adhesive Material) The insulating adhesive material was laminated to a thickness of 0.1 mm, cured at 170 ° C. for 1 hour, and cut out into a 30 mm long and 5 mm wide strip using a blade. A test piece was used. The measurement was carried out using Rheological DVE-4 manufactured by Rheology Co., Ltd. (pulling mode, frequency 10 Hz, temperature rising at 5 ° C./min).

(Test Method) The following test was performed on the semiconductor chip mounting board manufactured as described above. Table 2 shows the results. (Connection reliability) The semiconductor chip mounting substrate in which the semiconductor chip and the mounting substrate are connected is set to (-55 ° C., 30 minutes) / (125
(C, 30 minutes). The connection resistance between the protruding electrode of the semiconductor chip and the circuit for mounting the semiconductor chip on the mounting board after 1,000 cycles of the cooling / heating cycle test is as follows.
1Ω or less was evaluated as Δ, and 1Ω or more was evaluated as ×.

(Withstand voltage) Insulating adhesive material with copper foil (applied by a comma coater so that the film thickness becomes 50 μm,
30 mm × 30 mm cured at 170 ° C. for 1 hour after drying at 10 ° C. for 10 minutes and laminating two semi-cured insulating adhesive materials with copper foil) so that the insulating adhesive materials overlap.
Cut into squares. Further, a copper foil whose unnecessary portion was removed by etching so as to have a circular shape with a diameter of 20 mm was used as a test piece. Temperature 121 ° C., relative humidity 10
The test pieces before and after the treatment were immersed in insulating oil for 96 hours in a pressure cooker at 0% and an atmospheric pressure of 2026 hPa, and an AC voltage was applied between the copper foil and the aluminum plate at room temperature to measure the voltage at which dielectric breakdown occurred. . The unit of withstand voltage is k
V.

(Adhesion) A temperature of 121 ° C., a relative humidity of 100% and a pressure of 2026 hPa were applied to the semiconductor chip mounting substrate.
Before and after the treatment with a pressure cooker for 96 hours, samples with peeling between layers were evaluated as defective, and samples with no peeling between layers were evaluated as good.

[0038]

[Table 2]

[0039]

According to the present invention, a circuit board having excellent connection reliability between a semiconductor chip and a mounting substrate can be obtained.

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[Procedure amendment]

[Submission date] October 27, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

Among them , a combination of an epoxy resin and a functional group-containing acryl rubber is preferable because of its excellent insulating properties and moisture resistance. 100 parts by weight of the epoxy resin and its curing agent in total, b. 10 to 40 parts by weight of a high molecular weight component which is compatible with the epoxy resin and has an average molecular weight of 30,000 or more; c. 18 to 40% by weight of acrylonitrile, 2 to 6% by weight of glycidyl methacrylate as a functional group monomer, and the balance consisting of ethyl acrylate and butyl acrylate or a mixture of both;
20-100 parts by weight of the epoxy group-containing acrylic elastomer having a weight average molecular weight of 800,000 or more,
d. A composition comprising 0.1 to 5 parts by weight of a curing accelerator is used . In particular, a phenol resin is used as a curing agent of a, and b
It is preferable to use a phenoxy resin for a high molecular weight component having an average molecular weight of 30,000 or more, which is compatible with the epoxy resin.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

[0013] (added filler outer insulating layer) Further, to improve the thermal conductivity, giving flame retardancy, adjusting melt viscosity, to impart thixotropic properties, such as to improve the surface hardness Various fillers can be blended for the purpose. In order to improve the thermal conductivity, alumina, aluminum nitride, boron nitride, crystalline silica, and amorphous silica are preferable. Of these, alumina is preferred because it has good heat dissipation and good heat resistance and insulation properties. Further, crystalline silica or amorphous silica is inferior to alumina in terms of heat dissipation, but has less ionic impurities, and therefore is subjected to PCT treatment (temperature 121 ° C., relative humidity 100 ° C.).
%, 9 with a pressure cooker with an atmospheric pressure of 2026 hPa
This is preferable because it has high insulation properties at the time of 6 hours treatment) and has little corrosion of copper foil, aluminum wire, aluminum plate and the like. In order to provide flame retardancy, aluminum hydroxide and magnesium hydroxide are preferred. For the purpose of adjusting the melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide,
Preferred are calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, crystalline silica, and amorphous silica. For improving the surface hardness, short fiber alumina and aluminum borate whisker are preferable.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

[0015] (Additives outer insulating layer) Further, in addition to the above notated I <br/> error, coupling agents for improving the interfacial bonding between different materials, electric corrosion inhibitors, ionic impurities It may adsorb and contain an additive such as an ionic impurity adsorbent or a copper damage inhibitor for improving insulation reliability at the time of moisture absorption.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

As the inorganic ion adsorbent, a product containing a zirconium-based compound as a component IXE-100 and a product containing an antimony bismuth-based compound as a component IXE-600 are available from Toa Gosei Chemical Industry Co., Ltd. A product containing a magnesium aluminum-based compound as a component is commercially available under the trade name IXE-700. Hydrotalcite is commercially available from Kyowa Chemical Industry Co., Ltd. under the trade name DHT-4A.
You. The amount of the inorganic ion adsorbent is usually 10% by weight.
It is preferable that the content is below, and when the content is too large, the heat resistance decreases or the cost increases.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

(Adjustment of Outer Insulating Layer) In the outer insulating layer of the present invention, these components are dissolved and dispersed in a solvent to form a varnish, applied on a base film or a copper foil, and heated to remove the solvent. To use. As such a base film, a polytetrafluoroethylene film, a release-treated polyethylene terephthalate film, a polyethylene terephthalate film, or the like is used, and the base film is peeled off at the time of use. Further, a metal with an adhesive can be obtained by applying an adhesive as an outer insulating layer using copper foil or aluminum foil as a base film. The metal foil is preferably subjected to a roughening treatment such as a matte surface treatment. In addition, such a varnished insulating adhesive material can be used by screen printing or coating on a wiring board.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

(Adhesive) The adhesive used for bonding and fixing the electronic component in the present invention is not particularly limited, but an adhesive which can obtain good fluidity at the time of connection and high connection reliability can be used. epoxy resin and an imidazole-based, hydrazide-based, boron trifluoride - amine complexes, sulfonium salts, amine imides, polyamine salts, the latent curing agent with one or more of such dicyandiamide, using an adhesive compounded with the acrylic rubber Is preferred . In addition, a thermoplastic resin such as a phenoxy resin can be blended with the adhesive to make the film formability easier.In particular, the phenoxy resin has a similar structure to the epoxy resin, so Is preferred because it has characteristics such as excellent compatibility and adhesion.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

The adhesive used for bonding and fixing the electronic parts contains dispersed conductive particles for the purpose of positively imparting anisotropic conductivity in order to absorb variations in height of chip bumps and circuit electrodes. As such conductive particles, for example, metal particles such as Au, Ni , Ag, Cu, W and solder, or a thin film of gold or palladium is formed on the surface of these metal particles by plating or vapor deposition. Ni, metal particles, polymer spherical core material such as polystyrene
Conductive particles provided with a conductive layer such as Cu, Au, and solder can be used. The particle size of such conductive particles needs to be smaller than the minimum distance between the electrodes of the substrate, and when there is a height variation of the electrodes, it is preferably larger than the height variation, preferably in the range of 1 μm to 10 μm. Preferably, there is. The amount of the conductive particles dispersed in the adhesive is 0.1.
The range is preferably from 30 to 30% by volume, and more preferably from 0.2 to 15% by volume. When the content is less than 0.1% by volume, the dispersion of the particles is large, and the conductivity is reduced.
If the content exceeds 0% by volume, short-circuiting may occur due to contact with adjacent particles.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

Example 1 The coefficient of linear expansion in the X and Y directions was 16 ppm / ° C., and the Tg was about 1
MC, a glass-cloth / epoxy double-sided copper-clad laminate with 70 ° C., Tg or less and an elastic modulus of 1.8 × 10 ⁴ MPa
Unnecessary portions of the surface copper foil of LE-679 (trade name, manufactured by Hitachi Chemical Co., Ltd.) were removed by etching to form an inner layer circuit. The insulating adhesive material with copper foil using the varnish A of Table 1 was drilled, superimposed on the surface of the above-mentioned inner layer circuit, and press-laminated and bonded at 170 ° C., 40 kgf / cm ² , for 60 minutes. Holes were drilled, electroless copper plating was carried out, unnecessary copper was removed by etching, the outer layer circuit was processed, and solder coating was performed to obtain a mounting substrate.
At this time, the modulus of elasticity of the insulating adhesive material with copper foil used as the outer insulating layer was 100 MPa at 170 ° C., and the stress residual rate was 85% at 170 ° C. Thereafter, anisotropic conductive film ANISOLM (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an adhesive film, was transferred to a mounting substrate, and then a projection of a semiconductor chip was formed with a solder ball as a connection electrode. Align the electrodes with the circuit for mounting the semiconductor chip on the mounting board,
At 0 ° C., to cure the anisotropic conductive film was 20 seconds thermocompression bonding by the pressure of 10 kgf / chip. Thus, different Hoshirubeden of the film and the semiconductor chip mounting circuit of the mounting substrate and the bump electrode of the semiconductor chip through a is electrically connected at the same time between the semiconductor chip and the mounting substrate of the anisotropic conductive film This connection is maintained by curing.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

Example 3 The coefficient of linear expansion in the X and Y directions was 16 ppm / ° C., and the Tg was about 1
MC, a glass-cloth / epoxy double-sided copper-clad laminate with 70 ° C., Tg or less and an elastic modulus of 1.8 × 10 ⁴ MPa
LE-679 (manufactured by Hitachi Chemical Co., Ltd., trade name)
An unnecessary portion of the surface copper foil was removed by etching to form an inner layer circuit. As an outer insulating layer, an insulating adhesive material with copper foil using varnish B of Table 1 was drilled,
170 ℃, 40kgf / c
Pressing and laminating under conditions of m ² for 60 minutes, drilling through holes, performing electroless copper plating, removing unnecessary copper by etching, forming an outer layer circuit, performing electroless nickel / gold plating, and mounting substrate I got At this time, the elastic modulus of the outermost insulating adhesive film was 10 MPa at 170 ° C., and the stress residual rate was 83% at 170 ° C. Thereafter, anisotropic conductive film ANISOLM (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an adhesive film, was transferred to a mounting substrate, and then a projection of a semiconductor chip was formed with a solder ball as a connection electrode. Align the electrodes with the circuit for mounting the semiconductor chip on the mounting board,
At 70 ° C., to cure the anisotropic conductive film was 20 seconds thermocompression bonding by the pressure of 10 kgf / chip. Thus, between the semiconductor chip mounting board and the bump electrode and the semiconductor chip mounting circuit of the mounting substrate is at the same time the semiconductor chip when it is electrically connected through the different Hoshirubeden film is anisotropic conductive film properties This connection is maintained by curing.

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0032

[Correction method] Change

[Correction contents]

Examples 4 to 6 In Examples 1 to 3, the glass cloth / epoxy resin double-sided copper-clad laminate had a coefficient of linear expansion of 9 to 9 in the X and Y directions.
Semiconductor chips similar to those of Examples 1 to 3 were used except that MCL-E-679LD (trade name, manufactured by Hitachi Chemical Co., Ltd.), a glass cloth / epoxy resin double-sided copper-clad laminate of 11 ppm / ° C., was used. connecting the semiconductor chip and the mounting substrate Hoshirubeden films and mounting conditions.

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

(Test Method) The semiconductor fabricated in this manner
The following test was performed on the body chip mounting board. result
Are shown in Table 2. (Stress Residual Rate of Insulating Adhesive Material) (1) A 2 mm-thick laminated insulating adhesive material film is cut into a width of 5 mm and a length of 6 cm. (2) A sample is fixed to a tensile tester so that the distance between chucks is 40 mm, and a load is applied at an elongation ratio of 5%. 1
The load after 36 seconds at 70 ° C. is measured as the initial load. (3) Measure the load one hour later. (4) The residual stress ratio was calculated from the measurement result by the following equation. Residual stress (%) = F1 / F0 × 100 F0: Load after 170 seconds at 170 ° C. (MPa) F1: Load after 1 hour at 170 ° C. (MPa)

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction contents]

( Connection Reliability) A semiconductor chip mounting substrate in which a semiconductor chip and a mounting substrate are connected to each other (−55 ° C., 30
Min) / (125 ° C., 30 min). The connection resistance between the protruding electrode of the semiconductor chip and the circuit for mounting the semiconductor chip on the mounting substrate after 1,000 cycles of the cooling / heating cycle test is 50 mΩ or less.
The evaluation was as follows: o when mΩ or less; Δ when 1Ω or less;

[Procedure amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction contents]

(Withstand voltage) Insulating adhesive material with copper foil (applied by a comma coater so that the film thickness becomes 50 μm,
30 mm × 30 mm cured at 170 ° C. for 1 hour after drying at 10 ° C. for 10 minutes and laminating two semi-cured insulating adhesive materials with copper foil) so that the insulating adhesive materials overlap.
Cut into squares. Further, a copper foil whose unnecessary portion was removed by etching so as to have a circular shape with a diameter of 20 mm was used as a test piece. Temperature 121 ° C., relative humidity 10
The test pieces before and after the treatment are immersed in insulating oil for 96 hours in a pressure cooker of 0% and an atmospheric pressure of 2026 hPa, and an AC voltage is applied between the copper foil and the copper foil at room temperature to cause a dielectric breakdown. Measure. The unit of the withstand voltage is kV.

Continued on the front page (72) Inventor Naoyuki Urasaki 1500 Oji Ogawa, Shimodate City, Ibaraki Prefecture Inside the Shimodate Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Akishi Nakaso 1500 Oji Ogawa Shimodate City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Inside the research institute (72) Inventor ▲ Tsuru ▼ Yoshiyuki 1500, Oji, Shimodate-shi, Ibaraki Pref.Hitachi Kasei Kogyo Co., Ltd. (72) Inventor Izuo Watanabe 48 Wadai, Tsukuba-shi Ibaraki Pref.

Claims (8)

[Claims] 1. A circuit board comprising a mounting substrate, an electronic component mounted thereon, and an adhesive for fixing the both, and a connection formed on a surface of the mounting substrate corresponding to a connection electrode of the electronic component. The connection land and the connection electrode of the electronic component are electrically connected, the mounting board has an inner insulating layer and an outer insulating layer supporting the connection land, and the mounting board and the mounting board are A circuit board, wherein a stress residual ratio of the outer insulating layer at a temperature at which an electronic component to be mounted is bonded and fixed is in a range of 80% to 100%. 2. The elastic modulus of the outer insulating layer is 0.1 at a temperature at which a mounting substrate and an electronic component mounted thereon are fixed.
The circuit board according to claim 1, wherein the pressure is in a range of 1 MPa to 10,000 MPa. 3. The thickness of the outer insulating layer is from 25 μm to 200 μm.
The circuit board according to claim 1, wherein the circuit board has a range of m. 4. The circuit board according to claim 1, wherein a linear expansion coefficient in a plane direction of at least one of the inner insulating layers is 13 ppm / ° C. or less. 5. The circuit board according to claim 1, wherein the inner insulating layer is made of a resin reinforced with a glass substrate. 6. The circuit board according to claim 1, wherein the adhesive contains at least an epoxy resin, an acrylic rubber, and a latent curing agent. 7. The circuit board according to claim 6, wherein 0.1 to 30% by volume of conductive particles are dispersed in the adhesive. 8. The circuit board according to claim 1, wherein the electronic component is a semiconductor chip.