JP2011225856A - Adhesive composition for electronic device and adhesive sheet for electronic device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive sheet with excellent thermal conductivity, insulation property, reflow resistance, and adhesion with an adherend and used for bonding a heat generation component in an electronic device with a heat discharging component such as a heat sink and a radiator plate, for electronic devices.SOLUTION: An adhesive composition for electronic devices comprises: (a) a thermoplastic resin; (b) an epoxy resin; (c) a curing agent, (d) boron nitride particles; and (e) inorganic spherical particles. An average primary particle diameter of the inorganic spherical particles (e) is 10 vol% particle diameter or less of a primary particle diameter distribution on a volume basis of the boron nitride particles (d).

Description

  The present invention relates to an adhesive composition for electronic devices. More specifically, a reinforcing plate (stiffener), a heat radiating plate (heat spreader), a tape automated bonding (TAB) pattern processing tape used when mounting a semiconductor integrated circuit for a semiconductor element or a wiring board (interposer), Semiconductor connection substrates such as ball grid array (BGA) package interposers, coverlays and copper-clad laminates in flexible printed boards (FPCs) and their reinforcing plates, interlayer adhesives in multilayer boards, and board components using them Adhesion between electronic components such as electronic device sealing materials, LEDs, power module interlayer adhesives, solder resists, lead frame fixing tapes, LOC fixing tapes, semiconductor elements, and support members such as lead frames and insulating support substrates Agent, ie die bonding material, Rudo material such as suitably an adhesive composition for electronic equipment used in the adhesive sheets for electronic devices.

  In recent years, the use of electronic devices has been increasing as the performance of electronic devices has increased. In the midst of this, devices are becoming smaller and thinner. When downsizing and thinning electronic equipment, the density of heat generated from the equipment increases, so the generation of heat is suppressed, and the use of electronic components such as semiconductor integrated circuit (IC) packages, transistors, diodes, and power supplies It is important to efficiently release the generated heat to the outside. In addition, as the operating frequency of a microchip processor (MPU) used in a personal computer or the like increases, the amount of heat generated from the MPU chip becomes very large. Further, since flat panel displays (FPD) represented by plasma panel displays and liquid crystal displays generate heat in the display panels, it is important to release this heat to the outside.

  Generally, in order to release the heat generated from the electronic components as described above, heat dissipation efficiency is improved by attaching components that have a larger heat dissipation area, such as heat sinks, metal plates, and electronic equipment casings, to the electronic components that serve as heat sources. I am letting. At this time, the interface where the electronic component and the heat radiating component are in contact with each other is a resistance in terms of heat transfer. For this reason, a grease having excellent thermal conductivity is filled between the electronic component and the heat radiating component (see, for example, Patent Document 1), or a thermal conductive sheet in which a thermoplastic resin is filled with a thermally conductive filler (see, for example, Patent Document 2). ) Has been proposed to assist heat transfer. However, the former method using grease is difficult to handle, and in some cases the grease may contaminate the surroundings. In addition, the grease itself does not have the effect of fixing electronic components and heat dissipation components. It was necessary to fix by screwing. Since a thermoplastic resin is used for the heat conductive sheet, it is only adhered even if the structure and molecular weight of the resin are controlled, and it is necessary to separately fix the heat radiating component by screwing or the like.

  For this reason, there has been a demand for a material that is excellent in thermal conductivity used at the interface between the electronic component and the heat dissipation component, has excellent handling properties, and has an effect of fixing the electronic component and the heat dissipation component. As a material that can meet such a requirement, an adhesive sheet obtained by processing an adhesive composition in which a thermosetting resin contains a filler having high thermal conductivity into a sheet shape can be given.

  Among these, in Patent Document 3, the heat conductive adhesive composition is applied on a substrate, and the heat generation of 10 to 40% of the total curing heat generation amount when the degree of curing is measured using DSC is finished. However, the thermal conductivity is not sufficient, and the adhesiveness is not sufficient. As described above, the conventional heat conductive adhesive sheet has insufficient adhesion, and there is a problem that the electronic component and the heat dissipation component are not sufficiently fixed during use.

  In addition, the development of high-performance equipment used at high withstand voltage has progressed, and the demand for insulation has increased in recent years, and heat resistance and long-term reliability for solder reflow originally used for mounting electronic equipment is required. Therefore, it was a problem to be able to achieve both of these characteristics.

Japanese Patent No. 3142800 (paragraphs 2 to 12) Japanese Patent No. 3092699 (paragraphs 2 to 11) Japanese Patent No. 3559137 (Claim 1)

  As described above, conventional heat conductive adhesive sheets have insufficient heat conductivity, insulating properties, heat resistance and adhesiveness. An object of this invention is to provide the adhesive sheet for electronic devices excellent in the said various property balance in view of the subject of this prior art.

  In order to solve the above problems, the present invention mainly has the following configuration. That is, an adhesive composition for electronic equipment comprising (a) a thermoplastic resin, (b) an epoxy resin, (c) a curing agent, (d) boron nitride particles, and (e) inorganic spherical particles, e) The adhesive composition for electronic equipment, wherein the primary average particle size of the inorganic spherical particles is 10% by volume or less of the primary particle size distribution on the volume basis of the (d) boron nitride particles.

  The adhesive composition for electronic equipment of the present invention is excellent in heat conductivity, insulation and reflow resistance, and also has excellent adhesion to the adherend. An adhesive sheet for electronic equipment for adhering heat dissipation components can be obtained. Furthermore, an electronic device having excellent heat dissipation characteristics can be obtained by bonding the heat-generating component and the heat-dissipating component using this adhesive sheet or by stacking the printed circuit boards.

It is sectional drawing of the one aspect | mode of the adhesive agent sheet for electronic devices of this invention.

  Hereinafter, the configuration of the present invention will be described in detail. The adhesive composition of the present invention is an adhesive composition for electronic equipment containing (a) a thermoplastic resin, (b) an epoxy resin, (c) a curing agent, (d) boron nitride particles, and (e) inorganic spherical particles. And (e) the primary average particle size of the inorganic spherical particles is (d) 10% by volume or less of the primary particle size distribution on the volume basis of the boron nitride particles.

  The adhesive composition for electronic parts of the present invention contains (a) at least one thermoplastic resin, but the type is not particularly limited. The thermoplastic resin has functions such as flexibility, relaxation of thermal stress, and adhesiveness. Examples of the thermoplastic resin include acrylonitrile-butadiene copolymer (NBR), acrylonitrile-butadiene-styrene resin (ABS), polybutadiene, styrene-butadiene-ethylene resin (SEBS), and acrylic acid having 1 to 8 carbon side chains. And / or methacrylic acid ester resin (acrylic rubber), polyvinyl butyral, polyamide, polyester, polyimide, polyamideimide, polyurethane and the like. In addition, these thermoplastic resins preferably have a functional group capable of reacting with (b) an epoxy resin or (c) a curing agent described later. Specific examples include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, a hydroxyalkyl group, a vinyl group, and an isocyanate group. These functional groups are preferable because the bond with the thermosetting resin becomes strong and the heat resistance and insulation are improved. From the viewpoint of flexibility and thermal stress relaxation effect, a copolymer having acrylic acid and / or methacrylic acid ester having a side chain having 1 to 8 carbon atoms as an essential polymerization component can be particularly preferably used. The functional group content described above is preferably 0.07 to 2.0 eq / kg, more preferably 0.1 to 1.8 eq / kg in the thermoplastic resin (a). Further, from the viewpoint of adhesiveness and flexibility under long-term high temperature conditions, the weight average molecular weight (Mw) of the (a) thermoplastic resin is preferably 10,000 or more. Particularly preferably, it is 400,000 or less, and even when the inorganic particles are highly filled, the adhesive bonding process can be easily controlled. When using 2 or more types of thermoplastic resins, it is sufficient that at least one of them satisfies this range. The weight average molecular weight is measured by a GPC (gel permeation chromatography) method and calculated in terms of polystyrene.

  Although the adhesive composition for electronic components of this invention contains at least 1 type of (b) epoxy resin, the kind is not specifically limited. (B) By including an epoxy resin, it is possible to achieve a balance of physical properties such as heat resistance, insulation at high temperature, chemical resistance, and strength when formed into an adhesive layer. The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule, but bisphenol F, bisphenol A, bisphenol S, biphenyl, resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, dicyclopentadiene diene. Diglycidyl ethers such as xylenol, epoxidized phenol novolac, epoxidized cresol novolac, epoxidized trisphenylol methane, epoxidized tetraphenylol ethane, epoxidized metaxylene diamine, cyclohexane epoxide and other cycloaliphatic epoxies, phenoxy resins, etc. Can be mentioned. Halogenated epoxy resins are also mentioned from the viewpoint of flame retardancy, but flame retardant type epoxy resins that do not contain barogen from the viewpoint of environmental impact, specifically phosphorus-containing epoxy resins and nitrogen-containing epoxy resins may also be used. These may be used alone or in combination of two or more.

  Among these (b) epoxy resins, those that are preferably used in the present invention are excellent in adhesiveness and film-forming properties when forming an adhesive composition, and are bisphenol F type epoxy resin and bisphenol A. Among them, bisphenol A type epoxy resins having a low molecular weight and liquid at room temperature are particularly preferable.

The amount of (b) epoxy resin contained in the adhesive substance of the present invention is preferably 3 to 20 parts by weight with respect to (d) boron nitride particles (e) 100 parts by weight of inorganic spherical particles. Adequate adhesiveness is obtained when the amount is 3 parts by weight or more, and thermal conductivity is improved when the amount is 20 parts by weight or less.
Among these, in order to increase the crosslinking density of the adhesive composition, a polyfunctional epoxy resin having three or more epoxy groups in one molecule is preferably used. By increasing the crosslinking density using such a group, an adhesive composition having excellent heat resistance, reflow resistance, film strength, and solvent resistance can be obtained.

  The adhesive composition of the present invention contains (c) a curing agent. By containing a functional group of (a) a thermoplastic resin and (b) a curing agent that undergoes a crosslinking reaction with an epoxy resin, the adhesive strength after curing, heat resistance, and the like are improved. Examples of curing agents include 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3, 3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 2,2 ′, 3,3′-tetrachloro-4, 4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, Aromatic polyamines such as 4,4′-diaminobenzophenone and 3,4,4′-triaminodiphenylsulfone, boron trifluoride tri Boron trifluoride amine complexes such as tilamine complex, dicyandiamide, phenol, cresol phenol, alkyl-substituted phenols such as p-tBu phenol, p-phenylphenol, cyclic alkyl-modified phenols such as terpene and dicyclopentadiene, nitro groups, halogens Resins comprising polyfunctional phenols such as those having functional groups containing hetero atoms such as cyano groups, cyano groups and amino groups, those having skeletons such as naphthalene and anthracene, bisphenol F, bisphenol A, bisphenol S, resorcinol and pyrogallol Is mentioned. Further, a resol resin in which a methylol group is added to these various phenols or a polymerized novolak resin can be used. Other examples include urea resin, maleimide resin, cyanate resin, and acetal resin. These may be used alone or in combination of two or more. (C) The addition amount of a hardening | curing agent is 10-200 weight part with respect to 100 weight part of total amounts of (a) thermoplastic resin and (b) epoxy resin, Preferably it is 20-180 weight part.

  (D) Boron nitride particles are one of inorganic fillers having thermal conductivity, and there are two types, cubic crystals having an isotropic structure similar to diamond and hexagonal crystals having a layered structure similar to black smoke. The boron nitride particles have a scaly shape, and the surface direction of the scaly has two orders of magnitude higher thermal conductivity than the thickness direction, and has thermal conductivity anisotropy. Therefore, by orienting the surface direction of the boron nitride particles in the thickness direction of the adhesive layer, the thermal conductivity between the electronic components bonded to the adhesive layer can be enhanced.

  (D) The primary average particle diameter of boron nitride particles is preferably 3 to 20 μm. In the present invention, the primary average particle diameter means a primary particle diameter (d50) corresponding to a cumulative volume of 50% in the primary particle diameter distribution. The particle size distribution of the boron nitride particles is a particle size distribution in the scale-shaped surface direction (hereinafter referred to as the particle surface direction).

  When the boron nitride is 20 μm or less, the heat resistance is improved, so that the reflow resistance is excellent. More preferably, it is 15 μm or less. Moreover, it is preferable that an aspect ratio is the range of 6-19, and 8-15 are more preferable. (D) The boron nitride particles have a scale shape, and the aspect ratio indicates the length / particle thickness in the particle plane direction. When the aspect ratio is 19 or less, (d) the boron nitride particles are easily oriented in the thickness direction of the adhesive layer, so that the thermal conductivity is improved. On the other hand, when the aspect ratio is 6 or more, the ratio of the surface in the particle surface area is increased, which is advantageous for thermal conductivity. Further, (d) the boron nitride particles preferably contain an aggregate of boron nitride particles. The aggregate of boron nitride particles is a high-order aggregation of at least 100 primary particles of boron nitride particles, and includes regular spherical shapes (perfect spheres, ellipsoids, hemispheres, and cylinders) without orientation. ) Or a polygonal shape in which the length of the agglomerates in the major axis direction is 3 times or more of the primary average particle diameter (d50) of boron nitride particles. It is preferable that the aggregate of boron nitride particles is 50% by volume or more in all (d) boron nitride particles. By using the agglomerate, a certain degree of agglomeration is maintained even after physical agitation or dispersion by mixing and dissolving in a resin, a solvent, etc., so that high thermal conductivity can be obtained.

  The average particle size of the aggregate is preferably 30 μm or more, and 90% by volume of the particle size distribution on the volume basis of the aggregate is preferably equal to or less than the single layer thickness of the adhesive layer. The particle size distribution indicates the relationship between the particle size of the particles and the content thereof, and the average particle size of the aggregate is a particle size (aggregate d50) corresponding to a cumulative volume of 50% in the particle size distribution. The 90 volume% particle diameter of the particle size distribution of the aggregate indicates a particle diameter (aggregate d90) corresponding to a cumulative volume of 90%. When the average particle size of the aggregate is 30 μm or more, the above-described high thermal conductivity is obtained. In addition, since the 90 volume% particle size of the particle size distribution on the volume basis of the aggregate is less than the single layer thickness of the adhesive layer, the single layer thickness of the adhesive layer after film formation is stabilized, and high dielectric breakdown A voltage is obtained.

  (D) The amount of boron nitride particles added is preferably 40 to 1900 parts by weight with respect to 100 parts by weight as a total of (a) thermoplastic resin (b) epoxy resin (c) curing agent. If it is 40 parts by weight or more, the thermal conductivity is improved, and if it is 1900 parts by weight or less, the dielectric breakdown voltage is excellent. More preferably, it is 60-1100 weight part, and 100-900 weight part is the most preferable.

  Next, it is important to use (e) inorganic spherical particles in combination. That is, (d) the surface direction of the boron nitride particles is stable by being oriented in the same direction as the adhesive layer. (E) The boron nitride particles are obtained by interposing the inorganic spherical particles between the boron nitride particles. Is oriented in the thickness direction of the adhesive layer, so that the thermal conductivity is improved. However, on the other hand, since the adhesion between the boron nitride particle surface and the resin is small, the dielectric breakdown voltage in the adhesive thickness direction is lowered when oriented in the thickness direction, resulting in a trade-off with thermal conductivity. Here, (e) spherical inorganic particles are spherical particles having a thermal conductivity of 5 W / mK or more, specifically, silica, alumina, magnesium oxide, aluminum nitride, zinc oxide, silver, gold, silicon nitride, Examples thereof include silicon carbide, beryllium oxide, titanium oxide, boron carbide, titanium carbide, carbon black, diamond powder, etc., and at least one selected from these is required. It is important to have a spherical shape, and (d) the orientation of boron nitride particles can be easily controlled.

  Therefore, what is important in selecting the inorganic spherical particles (e) to be used is (d) having a primary average particle size of 10% by volume or less of the primary particle size distribution on the volume basis of boron nitride.

  The primary particle size distribution indicates the relationship between the particle size of the primary particles and the content thereof, and the 10% by volume particle size of the primary particle size distribution is the primary particle size (d10) corresponding to a cumulative volume of 10%. Is the primary particle size (d50) corresponding to a cumulative volume of 50% in the primary particle size distribution.

  (E) When the primary average particle size of the inorganic spherical particles is 10% by volume or less of the primary particle size distribution of boron nitride, the thermal conductivity and insulating balance are excellent. Preferably it is 5 vol% or less, more preferably 0 vol% or less, that is, it is more preferred that the particle size distributions do not overlap. Among them, the primary average particle diameter is preferably in the range of 0.1 μm to 10 μm. If it is larger than 0.1 μm, it has a stress relaxation effect, so that it has excellent adhesion and thermal shock resistance, and if it is 10 μm or less, it has excellent insulation. More preferably, it is 1 micrometer-5 micrometers.

  The amount of (e) inorganic spherical particles added is preferably 5 to 50% by weight based on the total amount of (d) boron nitride particles and particles and (e) inorganic spherical particles. If it is 5% by weight or more, the dielectric breakdown voltage is excellent, and if it is 50% by weight or less, (d) contact inhibition between the boron nitride particles is reduced, so that the thermal conductivity is improved. More preferably, it is 15 to 35% by weight, and the balance between thermal conductivity and dielectric breakdown voltage is improved.

  In the adhesive composition of the present invention, a catalyst can be used from the viewpoint of improving the curing promoting action. For example, when (b) an epoxy resin or (c) a phenol resin is used as a curing agent, an amine complex of boron trifluoride such as boron trifluoride triethylamine complex, 2-alkyl-4-methylimidazole, 2-phenyl-4 -Imidazole derivatives such as alkylimidazole, organic acids such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, triphenylphosphine, dicyandiamide, triethylamine, benzyldimethylamine, α-methylbenzylmethylamine, 2- (dimethyl Aminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, tertiary amine compounds such as 1,8-diazabicyclo (5,4,0) undecene-7, zirconium tetramethoxide, zirconium tetrapropoxide , Tetrakis (A Chiruasetonato) zirconium, tri (acetylacetonato) can be used an organometallic compound such as aluminum hexamine and the like.

  The addition amount of the curing catalyst is preferably in the range of 0.3 to 5.0 parts by weight with respect to 100 parts by weight of the (b) epoxy resin. By setting it to 0.3 parts by weight or more, a curing accelerating action is obtained, and by setting it to 5.0 parts by weight or less, storage stability is improved.

  In addition to the above components, the inclusion of fine organic components, corrosion inhibitors that suppress circuit corrosion and migration phenomena, antioxidants, ion scavengers, etc. is not limited as long as the properties of the adhesive are not impaired. It is not something.

  In addition to (d) boron nitride particles (e) inorganic spherical particles, other inorganic fillers can be used in combination. For example, non-spherical particles such as graphite and carbon fiber, aluminosilicate (natural zeolite, synthetic zeolite, etc.), hydroxide or hydrous oxide (hydrous titanium oxide, hydrous bismuth oxide, etc.), acid salt (zirconium phosphate, phosphorus Titanium oxide, etc.), basic salts, complex hydrous oxides (hydrotalcite, etc.), heteropolyacids (ammonium molybdate, etc.), hexacyanoiron (III) salts, etc. (hexacyanozinc, etc.), etc. Product names include IXE-100, IXE-300, IXE-500, IXE-530, IXE-550, IXE-600, IXE-633, IXE-700, IXE-700F, IXE-800 from Toa Gosei Co., Ltd. Inorganic ion exchangers such as

  (D) Boron nitride particles (e) Inorganic spherical particles and the like and (f) a polymer dispersant for better dispersion in the resin composition can be used. For example, Ajispa-PB-821, 822, 881, PN-411, PA-111 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Hinoact KF-1500, T-6000, T-8000, T-8000E Planact AL-M (and above) Kawaken Fine Chemical Co., Ltd.), DISPERBYK-2001, ANTI-TERRA203, BYK-P104, DISPERBYK-111, DISPERBYK-180, DISPERBYK-182 (manufactured by Big Chemie), homogenol L-18, L-1820, L-95, Examples thereof include polymer dispersants such as L-100 (manufactured by Kao Chemical Co., Ltd.), and these may be used alone or in combination of two or more. In particular, those having an amino group as a functional group are preferable and act on (d) boron nitride particles, (e) inorganic spherical particles and the like, and (d) boron nitride particles (e) inorganic spherical particles and the like are improved in dispersibility. . In addition, (b) it also acts with an epoxy resin to form a three-dimensional chemical bond with the resin matrix, so that the additive alone can be prevented from being released from the adhesive composition. As a result, the dielectric breakdown voltage is improved. (F) The amine value of the polymer dispersant is preferably 10 or more, and more preferably 30 or more. Here, the amine value indicates the number of mg of an equivalent amount of potassium hydroxide corresponding to the amount of hydrochloric acid necessary to neutralize 1 g of the sample. The addition amount is preferably 0.3 to 5 parts by weight or more, more preferably 0.5 to 3 parts by weight or more with respect to 100 parts by weight of the total amount of (d) boron nitride particles (e) inorganic spherical particles.

  (D) Boron nitride particles (e) Surface of inorganic spherical particles for the purpose of preventing alteration such as surface oxidation and hydrolysis, improving the wettability of the filler and the resin composition, and improving the physical properties of the adhesive sheet Specifically, coating with silica, phosphoric acid, etc., oxide film application treatment, silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconate coupling agent And surface treatment with a silane compound or the like. Specific examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyltrimethoxy. Silane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltri Toxisilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-tri Ethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. is there. These surface treatment agents may be used alone or in combination of two or more kinds, and the amount used for the treatment is 0.3 to 2 weights with respect to 100 parts by weight of the total amount of (d) boron nitride particles and (e) inorganic spherical particles. Part is preferred.

  The adhesive sheet for electronic equipment of the present invention (hereinafter referred to as an adhesive sheet) is a composition having an adhesive layer made of the adhesive composition of the present invention and one or more peelable protective film layers. Say. For example, a two-layer structure of protective film layer / adhesive layer or a three-layer structure of protective film layer 1 / adhesive layer 2 / protective film layer 1 shown in FIG. Moreover, you may have another layer other than an adhesive bond layer and a protective film layer. For example, a metal foil or a metal plate / adhesive layer / protective film layer structure, a composite structure in which a heat-conductive material such as a carbon fiber cloth and a ceramic plate is laminated inside the adhesive layer, and a polyimide inside the adhesive layer A composite structure in which insulating films such as the above are laminated corresponds to this.

  Also, one or both sides of the adhesive layer may be roughened in order to reduce the adhesiveness of the adhesive itself and to prevent the entrapment of bubbles when adhering to an adherend such as a copper foil or a reinforcing plate. . Even if the adhesive layer itself has high adhesiveness, the adhesiveness is reduced by dispersing the contacts to the object to be bonded by roughening the surface. The surface roughening method of the adhesive is not particularly limited, but a coating solution obtained by dissolving the adhesive composition in a solvent is applied onto a film having irregularities on the surface by embossing or sand mat processing. Drying, producing a semi-cured adhesive sheet, transferring film irregularities to the surface of the adhesive sheet, as a protective film for the adhesive sheet, laminating using uneven film, and then uneven the adhesive sheet A method of transferring to the surface is mentioned. However, since the adhesive is embedded in the unevenness of the film surface, it may be difficult to peel off the film during actual use. Therefore, what is particularly preferably used in the present invention as a film to be used is excellent in controlling releasability. , A film which has been subjected to mold release treatment of silicone or a fluorine-containing compound. In addition, the surface of the adhesive sheet can be roughened with an uneven rubber roll or the like. Moreover, it is also possible to obtain a lower adhesive sheet by combining a method of reducing the adhesiveness by thinly laminating a low adhesive layer on a normal adhesive layer and surface roughening. Specific examples of the low-adhesive adhesive layer include an adhesive having a composition in which the amount of inorganic particles is increased, or an adhesive whose thickness is controlled by heat aging a thin adhesive sheet.

  Although the thickness of an adhesive bond layer can be suitably selected by the relationship with an elastic modulus and a linear expansion coefficient, 10-500 micrometers is preferable, More preferably, it is 20-300 micrometers.

  The ratio (d90 / t) of 90 volume% particle size (d90; unit μm) of the primary particle size distribution on the volume basis of (d) boron nitride particles to the single layer thickness (t; unit μm) of the adhesive layer is It is preferable from the point of an insulation reliability improvement that it is 0.7 or less. The 90% by volume particle size (d90) of the primary particle size distribution indicates a primary particle size (d90) corresponding to a cumulative volume of 90%. The single-layer thickness of the adhesive layer refers to the thickness of the adhesive before lamination when laminating a plurality of adhesive layers, and refers to the thickness of the adhesive layer as it is when not laminated. When a potential is applied in the thickness direction of the adhesive layer under high temperature and high humidity for a long time, a leakage current is generated at the interface defect portion between (d) boron nitride particles and the resin composition caused by deterioration. However, if it is 0.7 or less as described above, (d) the adhesive resin layer suppresses leakage current even if the plane direction of the boron nitride particles is oriented perpendicularly to the thickness direction of the adhesive layer. It is possible to suppress the deterioration of the property. Preferably it is 0.5 or less, More preferably, it is 0.4 or less.

  The protective film layer is formed in the form of an adhesive layer before the adhesive layer is bonded to a wiring board layer (TAB tape or the like) composed of an insulator layer and a conductor pattern or a layer (stiffener or the like) where no conductor pattern is formed. And if it can peel without impairing a function, it will not specifically limit. For example, plastic films such as polyester, polyolefin, polyphenylene sulfide, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, polycarbonate, polyamide, polyimide, polymethyl methacrylate, etc. Examples thereof include films coated with a release agent such as silicone or fluorine compound, paper laminated with these films, and paper impregnated or coated with a releasable resin. The protective film layer may be colored with a pigment so as to have good visibility during processing. Thereby, since the protective film of the side which peels previously can be recognized easily, misuse can be avoided.

When the protective film layers are provided on both surfaces of the adhesive layer, when the peeling force of each protective film layer to the adhesive layer is F ₁ and F ₂ (F ₁ > F ₂ ), F ₁ -F ₂ is preferably It is 5 Nm ⁻¹ or more, more preferably 15 Nm ⁻¹ or more. By setting F ₁ -F ₂ to 5 Nm ⁻¹ or more, the target protective film layer can be stably peeled off, so that workability is good. Further, the peeling forces F ₁ and F ₂ are preferably ¹ to 200 Nm ⁻¹ , more preferably 3 to 100 Nm ⁻¹ . If it is this range, troubles, such as omission of a protective film layer and damage to an adhesive bond layer, can be prevented.

  Here, the example of the manufacturing method of the adhesive composition of this invention is demonstrated.

  (A) a thermoplastic resin, (b) an epoxy resin, (c) a curing agent, (d) boron nitride particles, (e) inorganic spherical particles, a curing catalyst, an additive, and the like, and a solid content concentration of 30 to 60 A mixed solvent is added so that it may become weight%, and it stirs and melt | dissolves at 40 degreeC, and produces a coating material. Solvents are not particularly limited, but aromatic solvents such as toluene, xylene and chlorobenzene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, aprotic polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone or mixtures thereof may be used. Is preferred.

  Next, the example of the manufacturing method of the adhesive sheet using the adhesive composition of this invention is demonstrated.

  (I) The coating material which melt | dissolved the adhesive composition of this invention obtained above in a solvent is apply | coated and dried on the polyester film which has mold release property, and the laminated body of an adhesive bond layer and a polyester film is obtained. It is preferable to apply so that the thickness of the adhesive layer is 10 to 300 μm. The drying conditions are preferably 100 to 200 ° C. and 1 to 5 minutes.

  (II) A polyester or polyolefin-based protective film layer having a releasability with a weaker peel strength than that described above is applied to the laminate obtained in (I) at 30 to 200 ° C. and 0.1 to 1 MPa. To obtain an adhesive sheet for electronic equipment of the present invention. In order to further increase the thickness of the adhesive layer, the adhesive layer laminated by heating and pressing may be laminated a plurality of times. Specifically, it is possible to obtain a thick film as many as the number of layers by peeling off the protective film layer on one side and laminating the exposed adhesive surfaces at 40 to 200 ° C. and 0.1 to 1 MPa. Become. The adhesion at the laminated interface is improved by laminating the thick adhesive sheet for electronic equipment obtained here at 40 to 200 ° C. and 1 to 10 MPa. What is important here is to combine a multi-step laminating process. In the first step, low-pressure lamination is performed, so that it is possible to laminate a protective film layer or an adhesive layer with a protective film layer without wrinkles. As a result, adhesion at the laminated interface can be improved. As a result, adhesion, insulation, etc. are improved. Processing is performed at a temperature and pressure conditions such that 0.1 to 1% of the adhesive layer exudes to the width of one adhesive layer in the heat and low pressure laminate, and 1 to 10% adhesive layer in the heat and high pressure laminate. It is preferable to perform the processing using as an index the temperature and pressure conditions at which the oozing occurs. The laminating method includes an in-line processing method using a metal roll and / or a rubber roll, an off-line processing method using a heating press machine, and the like, and any of them may be used.

  The adhesive sheet can be applied to, for example, a substrate for connecting a semiconductor integrated circuit.

  The substrate for connecting a semiconductor integrated circuit is for connecting an isolated semiconductor integrated circuit (bare chip) after an element is formed on a semiconductor substrate such as silicon. (A) A wiring composed of an insulator layer and a conductor pattern The shape, material, and manufacturing method are not particularly limited as long as each of the substrate layer, (B) the layer on which the conductor pattern is not formed, and (C) one or more adhesive layers. Therefore, the most basic one is an A / C / B configuration, but a multilayer structure such as A / C / B / C / B is also included.

  (A) A wiring board layer composed of an insulator layer and a conductor pattern is a layer having a conductor pattern for connecting an electrode pad of a semiconductor element and the outside of a package (printed board, etc.), and one or both sides of the insulator layer A conductor pattern is formed on the substrate.

  The insulator layer here is made of a composite material such as polyimide, polyester, polyphenylene sulfide, polyethersulfone, polyetheretherketone, aramid, polycarbonate, polyarylate, or a plastic or epoxy resin-impregnated glass cloth. A 125 μm flexible insulating film or a ceramic substrate such as alumina, zirconia, soda glass, or quartz glass is suitable, and a plurality of layers selected from these may be laminated. If necessary, the insulator layer can be subjected to surface treatment such as hydrolysis, corona discharge, low temperature plasma, physical roughening, and easy adhesion coating treatment.

  The formation of the conductor pattern is generally performed by either the subtractive method or the additive method, but either method may be used.

  In the subtractive method, a metal plate such as copper foil is bonded to the insulator layer with an insulating adhesive, or a precursor of the insulator layer is laminated on the metal plate, and the insulator layer is formed by heat treatment or the like. A pattern is formed by etching the material produced in (1) by chemical treatment. Specific examples of the material include rigid or copper-clad material for flexible printed circuit boards, TAB tape, and the like. Among them, a copper-clad material for a flexible printed board and a TAB tape are preferably used in which at least one polyimide film is an insulator layer and a copper foil is a conductor pattern.

  In the additive method, a conductor pattern is directly formed on the insulator layer by electroless plating, electrolytic plating, sputtering, or the like. In either case, the formed conductor may be plated with a metal having high corrosion resistance to prevent corrosion. Further, via holes may be formed in the wiring board layer as necessary, and conductor patterns formed on both surfaces may be connected by plating.

  (B) The layer in which the conductor pattern is not formed is a uniform layer substantially independent of the wiring substrate layer (C) or the adhesive layer (C) composed of the (A) insulator layer and the conductor pattern. Reinforcing and dimensional stabilization of connection substrates (referred to as reinforcement plates or stiffeners), external and IC electromagnetic shielding, IC heat dissipation (referred to as heat spreaders, heat sinks), semiconductor integrated circuit connection substrates It carries functions such as imparting flame retardancy and imparting distinctiveness due to the shape of the substrate for connecting a semiconductor integrated circuit. Therefore, the shape is not limited to the layer shape, and may have a fin structure for heat dissipation, for example. Any material may be used as long as it has the above functions, and the material is not particularly limited. Metals include copper, iron, aluminum, gold, silver, nickel, titanium, and stainless steel, inorganic materials include alumina, zirconia, soda glass, quartz glass, and carbon, and organic materials include polyimide, polyamide, and polyester. , Vinyl-based, phenol-based, and epoxy-based polymer materials. Moreover, the composite material by these combination can also be used. Examples thereof include a thin metal plated shape on a polyimide film, a polymer kneaded with carbon to give conductivity, and a metal plate coated with an organic insulating polymer. In addition, various surface treatments are not limited as in the case of the insulator layer included in the (A) wiring board layer.

  (C) The adhesive layer is obtained by peeling off the protective film layer of the adhesive sheet for electronic devices of the present invention. One adhesive layer surface is (B) a layer on which no conductor pattern is formed and the other surface is bonded. On the surface of the agent layer, (A) a wiring substrate layer composed of an insulator layer and a conductor pattern is heated and laminated, and then (C) the adhesive layer is heat-cured to obtain a semiconductor connection substrate. In addition, the adhesive layer (C) can be heated and cured while applying pressure with a hot press machine or the like as necessary.

  The semiconductor integrated circuit connecting substrate and IC can be connected by any of TAB gang bonding and single point bonding, wire bonding used for lead frames, resin sealing in flip chip mounting, anisotropic conductive film connection, etc. Good. A package called CSP is also included in the electronic component of the present invention.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, the evaluation methods performed in Examples 1 to 27 and Comparative Examples 1 to 5 will be described.

(1) Adhesive strength:
One protective film of an adhesive sheet having an adhesive layer of 3 mm × 3 mm square and 80 μm thickness on a 5 mm × 20 mm square copper plate of 0.5 mm thickness was peeled off and laminated under the conditions of 130 ° C. and 1 MPa. Thereafter, the other protective film layer of the adhesive sheet obtained by laminating the copper plate of the same size on the previous copper plate is peeled off and further laminated under the conditions of 130 ° C. and 1 MPa, and then under a pressure of 3 MPa, 150 to 180 ° C. for 1 hour. A heat treatment was performed to prepare a sample for evaluation. The sample was set in Tensilon, the shear load was measured at a speed of 50 mm / min in the 180 ° direction, and the adhesive force was measured from the adhesive area at that time.

(2) Reflow resistance:
One protective film of the adhesive sheet having a 30 mm square and 80 μm thick adhesive layer was peeled off, and then the adhesive layer was placed on a 30 mm square 0.25 mm thick SUS304. A 30 mm square semiconductor connection in which a dummy pattern with a conductor width of 100 μm and a distance between conductors of 100 μm was formed by roll laminating under conditions of 130 ° C., 0.4 MPa, 1 m / min, and then peeling off the other protective film of the adhesive sheet The substrate for use was roll-laminated under conditions of 130 ° C., 2 MPa, and 1 m / min. Thereafter, a heat treatment was performed at 180 ° C. for 1 hour under a pressure of 3 MPa to prepare an evaluation sample. An ultrasonic flaw detector was used to determine whether or not swell occurred after 20 samples of 30 mm square were absorbed by moisture for 168 hours under conditions of 30 ° C / 70% RH and then immediately passed through an infrared reflow oven whose temperature was set. Observed. The maximum temperature of the infrared reflow furnace is 260 ° C., and the holding time is 10 seconds each. The number of samples in which swelling occurred in 20 evaluation samples was counted.

(3) Thermal conductivity:
The protective film on one side of the adhesive sheet having a 30 mm square and 80 μm thick adhesive layer was peeled off, and the adhesive layers were laminated and laminated under the conditions of 130 ° C. and 0.4 MPa. After repeating this to form an adhesive layer having a thickness of 1 mm, heating was performed at 180 ° C. for 1 hour under a pressure of 3 MPa, and a sample cut into a φ10 mm cylinder was used as an evaluation sample. The thermal diffusivity was measured in irradiation light: ruby laser light and in a vacuum atmosphere with a thermal constant measuring device TC-7000 manufactured by ULVAC-RIKO. Moreover, the density of the adhesive composition was measured by Archimedes method, the specific heat was measured by DSC method, and the thermal conductivity was calculated from these parameters.

(4) Dielectric breakdown voltage:
Both protective films of the adhesive sheet having an adhesive layer of 70 mm × 100 mm square and 80 μm thickness were peeled off, and subjected to heat treatment at 180 ° C. for 1 hour under 3 MPa pressure to prepare a sample for evaluation. An aluminum foil was placed on one surface and a φ25 mm electrode was placed on the other surface, and measurement was performed using an AC withstand voltage measuring device at room temperature at an AC boosting rate of 0.5 kV / sec. The dielectric breakdown voltage was obtained by dividing the withstand voltage obtained here by the thickness of the adhesive layer after the heat treatment.

(5) Thermal cycle (cold shock) properties:
One protective film of the adhesive sheet having an adhesive layer of 3 mm × 3 mm square and 80 μm thickness is peeled off, and the adhesive layer is placed on aluminum (A6061A) of 0.5 mm thickness at 130 ° C. Lamination was performed at 4 MPa. Thereafter, the other protective film layer of the adhesive sheet obtained by laminating a 20 mm × 20 mm square copper plate having a thickness of 0.5 mm on the previous aluminum plate is peeled off and further laminated under conditions of 130 ° C. and 1 MPa. At 180 ° C. for 1 hour, a heat treatment was performed to prepare an evaluation sample. In a heat cycle tester (Tabba Espec Co., Ltd., PL-3 type), treatment was performed at −40 ° C. to 150 ° C. at the minimum and maximum temperatures for 30 minutes each, and the occurrence of peeling was evaluated. A sample was taken out at a cycle of 50 cycles, and the number of cycles until peeling occurred by an ultrasonic short-scratch device was defined as thermal cycle property.
(6) (d) Boron nitride particles, (e) Primary average particle size and volume% particle size of inorganic spherical particles (d) Boron nitride particles, (e) Scanning electron microscope (SEM, Hitachi High-Technologies) Observation was carried out at a magnification of 800 times with S-3000N (manufactured by Sangyo Co., Ltd.), and 100 primary particles were randomly sampled and numbered in ascending order of particle diameter. When the cross section of the particle is an ellipse, the average value of the major axis and the minor axis was taken as the particle size. For each numbered particle, the volume of each particle was determined from the particle diameter, and 50% of the total volume of 100 primary particles was determined. For each numbered particle, the sum of the volume of each particle from the smallest particle size is obtained, and the particle size of the particle when the value exceeds 50% of the total volume of 100 primary particles is calculated. The primary average particle diameter (d50) was used.

  In addition, (d) boron nitride particles were numbered in the same manner, and the particle sizes of the particles when the volume exceeded 5%, 10%, and 90% of the total volume of 100 primary particles were respectively determined. d05, d10, and d90 were set.

(7) Cohesiveness:
(D) Boron nitride particles were observed with a scanning electron microscope (SEM, S-3000N manufactured by Hitachi High-Technologies Corporation) at a magnification of 800 times, 10 higher-order aggregates were randomly sampled, and the long axis of the aggregates The length of the direction and the primary average particle diameter (d50) of the boron nitride particles are compared, the higher-order aggregate units per one are averaged, and the average length in the major axis direction of the aggregate is the primary average particle of the boron nitride particles Those having a diameter (d50) of 3 times or more were regarded as cohesive, and those less than 3 times were regarded as non-aggregating.

(8) Average particle diameter of aggregate, 90 volume% particle diameter of particle size distribution:
The adhesive layer was stirred and dissolved at 40 ° C. in a mixed solvent of DMF / monochlorobenzene / MIBK = 1/1/3 (weight ratio) so that the solid component concentration would be 40% by weight. The particle size distribution was measured with Microtrac HRA).

(9) Insulation reliability:
One protective film of the adhesive sheet having an adhesive layer of 30 mm × 30 mm square and 80 μm thickness was peeled off on a 0.5 mm thick 30 mm × 30 mm square copper plate and laminated under the conditions of 130 ° C. and 1 MPa. Next, a 35 μm-thick electrolytic copper foil of the same size was peeled off from the protective film layer on the other side of the adhesive and laminated, and then heat-treated at 150 to 180 ° C. for 1 hour under 3 MPa pressure to prepare a sample for evaluation. . Next, the electrolytic copper foil side was etched so as to have a diameter of 10 mm to prepare a sample for evaluation. A voltage was applied to the evaluation sample from the upper and lower electrodes under the conditions of 85 ° C., 85% RH and 100 V, and the initial resistance value was measured. Subsequently, the resistance value was measured every 100 hours up to 500 hours, and the lowest resistance value among them was taken as the minimum resistance value. Here, the retention rate of the minimum resistance value with respect to the initial resistance value was defined as the resistance retention rate (%).

(10) Single layer thickness of the adhesive layer:
Measurement was performed using a thickness gauge (Nikon MFC-101).

(11) Aspect ratio:
(D) Boron nitride particles are observed with a scanning electron microscope (SEM, S-3000N manufactured by Hitachi High-Technologies Corporation) at a magnification of 3000 times, 20 primary particles are randomly sampled, and the maximum length in the particle plane direction / The aspect ratio was calculated by measuring the particle thickness.

  The raw materials used in the examples are as follows.

<Thermoplastic resin>
Thermoplastic resin 1: AS-7EK20 (manufactured by Nagase ChemteX Corp.): carboxyl group mainly composed of butyl acrylate, hydroxyl group-containing acrylic rubber, 350,000 molecular weight thermoplastic resin 2: SGP-3 (Nagase ChemteX Corp. ) Made): Epoxy group-containing acrylic rubber mainly composed of butyl acrylate, molecular weight 850,000 <epoxy resin>
Bisphenol A type epoxy resin (Epicoat 828, epoxy equivalent 190, manufactured by Japan Epoxy Resins Co., Ltd.)
<Curing agent>
Phenol novolac resin (PSM4326, hydroxyl group equivalent 105, manufactured by Gunei Chemical Industry Co., Ltd.)
<Curing catalyst>
2-Ethyl-4-methylimidazole (EMI24, manufactured by Japan Epoxy Resin Co., Ltd.)
Reference Example 1 Preparation of Alumina (e-7) Alumina particles A34 (primary average particle diameter φ4 μm) manufactured by Nippon Light Metal Co., Ltd. were sieved to obtain a primary average particle diameter φ1.7 μm.

Examples 1-22, Comparative Examples 1-5
Boron nitride particles shown in Table 1, inorganic spherical particles shown in Table 2, (a) thermoplastic resin, (b) epoxy resin, (c) curing agent, (d) boron nitride particles, (e) inorganic spherical particles Particles, curing catalyst, and (f) polymer dispersant shown in Table 3 are blended so as to have the compositions shown in Tables 4 to 8, respectively, so that the solid content concentration is 40% by weight. The mixture was stirred and dissolved in a mixed solvent of benzene / MIBK = 1/1/3 (weight ratio) at 40 ° C. to prepare an adhesive solution.

  Next, after dispersion with a bead mill, the adhesive solution is applied to a 38 μm thick polyethylene terephthalate film (“Film Vina” GT manufactured by Fujimori Kogyo Co., Ltd.) with a silicone release agent with a bar coater so that the dry thickness is 80 μm. It applied (henceforth an adhesive coating film). It dried at 120 degreeC for 5 minute (s), the protective film was bonded together at 50 degreeC and 0.3 MPa, and the adhesive agent sheet of this invention was produced. Next, adhesion strength, thermal conductivity, dielectric breakdown voltage, insulation reliability, reflow resistance, and thermal cycle performance tests were performed. The results are shown in Tables 4-8. In Example 6, when the aggregate state of d-3 (boron nitride particles) was observed using the obtained adhesive sheet, the average particle size of the aggregate was 40 μm, and the volume distribution of the aggregate was 90 volumes. The% particle size was 75 μm. The results are shown in Table 10.

Example 23
An adhesive coating film obtained in the same manner as in Example 10 was prepared by laminating two sheets at 50 ° C. and 0.4 MPa, and the adhesive strength, withstand voltage, dielectric breakdown voltage, insulation reliability were the same as in Example 10. , Reflow resistance, and thermal cycle performance were evaluated. The thickness of the laminated adhesive layer was 160 μm.

  In addition, the thermal conductivity measurement was performed except that the adhesive layers were laminated at 50 ° C. and 0.4 MPa instead of laminating the adhesive layers at 130 ° C. and 0.4 MPa. The measurement was performed in the same manner as described in (3) Thermal conductivity. These results are shown in Table 9.

Example 24
An adhesive coating film obtained in the same manner as in Example 10 was prepared by laminating two sheets at 130 ° C. and 0.4 MPa, and the adhesive strength, withstand voltage, dielectric breakdown voltage, insulation reliability were the same as in Example 10. , Reflow resistance, and thermal cycle performance were evaluated. The thickness of the laminated adhesive layer was 160 μm.

  The thermal conductivity was measured in the same manner as in Example 23. These results are shown in Table 9.

Example 25
An adhesive coating film obtained in the same manner as in Example 10 was laminated at 130 ° C. and 0.4 MPa, and then laminated again by heating and pressing at 150 ° C. and 2 MPa, as in Example 10. Adhesion strength, withstand voltage, dielectric breakdown voltage, insulation reliability, reflow resistance, and thermal cycle performance were evaluated. The thickness of the laminated adhesive layer was 160 μm.

  The thermal conductivity was measured in the same manner as in Example 23. These results are shown in Table 9.

Example 26
An evaluation sample was prepared in the same manner as in Example 10 except that the dry thickness of the adhesive was 40 μm and two sheets were laminated at 130 ° C. and 0.4 MPa (adhesive layer thickness 80 μm). The results are shown in Table 9.

Example 27
An evaluation sample was prepared in the same manner as in Example 17 except that boron nitride d-6 shown in Table 1 was ground to have an aspect ratio of 4 was used. When the thermal conductivity was evaluated, it was 2.8 W / m · K.

Example 28
The composition of bisphenol A type epoxy resin, phenol novolac resin, d-3 (boron nitride particles) shown in Table 1, e-5 (inorganic spherical particles) shown in Table 2, and the curing catalyst are as shown in Table 10. Then, the mixture was stirred and dissolved at 40 ° C. in a mixed solvent of DMF / monochlorobenzene / MIBK = 1/1/3 (weight ratio) so as to obtain a solid concentration of 40% by weight. Next, the thermoplastic resin 2 was added so that it might become the composition shown in Table 10, and it stirred, and produced the adhesive solution.

  Next, after further dispersion in a bead mill, the adhesive solution is dried with a bar coater to a thickness of 80 μm on a 38 μm-thick polyethylene terephthalate film with a silicone release agent (“Film Vina” GT manufactured by Fujimori Kogyo Co., Ltd.). It was applied to. It dried at 120 degreeC for 5 minute (s), the protective film was bonded together at 50 degreeC and 0.3 MPa, and the adhesive agent sheet of this invention was produced. Next, adhesion strength, thermal conductivity, dielectric breakdown voltage, insulation reliability, reflow resistance, and thermal cycle performance tests were performed. Moreover, when the aggregation state of d-3 (boron nitride particles) was observed using the obtained adhesive sheet, the average particle size of the aggregates was 20 μm, and the 90% by volume particle size distribution of the aggregates was 75 μm. there were. The results are shown in Table 10.

Example 29
An adhesive sheet of the present invention was produced in the same manner as in Example 6 except that the dispersion was performed with a homogenizer at a peripheral speed of 60 m / s for 10 minutes instead of using a bead mill. Moreover, when the aggregation state of d-3 (boron nitride particles) was observed using the obtained adhesive sheet, the average particle size of the aggregates was 40 μm, and the 90% by volume particle size distribution of the aggregates was 120 μm. there were. The results are shown in Table 10.

  As is clear from Tables 4 to 10, the adhesive sheet obtained by the present invention is excellent in adhesive strength, thermal conductivity, dielectric breakdown voltage, insulation reliability, and reflow resistance.

  The present invention relates to a pattern processing tape of a tape automated bonding (TAB) method used when mounting a semiconductor integrated circuit for a reinforcing plate (stiffener), a heat radiating plate (heat spreader), a semiconductor element or a wiring board (interposer), Semiconductor connection substrates such as ball grid array (BGA) package interposers, coverlays and copper-clad laminates in flexible printed boards (FPCs) and their reinforcing plates, interlayer adhesives in multilayer boards, and board components using them Adhesion between electronic components such as electronic device sealing materials, LEDs, power module interlayer adhesives, solder resists, lead frame fixing tapes, LOC fixing tapes, semiconductor elements, and support members such as lead frames and insulating support substrates Agent, die bonding material, sheet Electronics adhesive composition suitable for use in de material or the like, can be effectively applied to an electronic equipment field using the same adhesive sheet and electronics.

1 Protective film layer 2 Adhesive layer

Claims (8)

An adhesive composition for electronic equipment comprising (a) a thermoplastic resin, (b) an epoxy resin, (c) a curing agent, (d) boron nitride particles, and (e) inorganic spherical particles, wherein (e) inorganic An adhesive composition for electronic equipment, wherein the primary average particle size of the spherical particles is (d) 10% by volume or less of the primary particle size distribution on the volume basis of the boron nitride particles. 2. The adhesive composition for electronic equipment according to claim 1, wherein the (d) boron nitride particles have a primary average particle size based on volume of 3 to 20 [mu] m. 2. The adhesive composition for electronic equipment according to claim 1, wherein the (e) inorganic spherical particles have a primary average particle size based on volume of 0.1 μm to 10 μm. The electronic device according to any one of claims 1 to 3, wherein the (e) inorganic spherical particles are 5 to 50% by weight based on the total amount of (d) boron nitride particles and (e) inorganic spherical particles. Adhesive composition. The aspect ratio of said (d) boron nitride particle is 6-19, The adhesive composition for electronic devices in any one of Claims 1-4 characterized by the above-mentioned. The adhesive composition for electronic equipment according to any one of claims 1 to 5, wherein the (d) boron nitride particles contain an aggregate of boron nitride particles. The adhesive agent sheet for electronic devices which has an adhesive bond layer which consists of an adhesive composition for electronic devices in any one of Claims 1-6, and one or more peelable protective film layers. The ratio (d90 / t) of 90 volume% particle size (d90) of the primary particle size distribution on the volume basis of (d) boron nitride particles to the single layer thickness (t) of the adhesive layer is 0.7 or less. The adhesive sheet for electronic devices according to claim 7.

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