JP2008063551A - Adhesive composition for electronic device, adhesive sheet for electronic device, and electronic component and device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition for an elecronic device excellent in long term resistance to high temperature and an adhesive sheet for electronic device, an electronic component and an electronic device using the same. <P>SOLUTION: The adhesive composition for the electronic device comprises (a) a thermosetting resin, (b) a curing agent, (c) a polymer having an organopolysiloxane at a side chain, and (d) a copolymer comprising an acrylate having a side chain with 1-8C and/or a methacrylate as essential copolymer components. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an adhesive composition for electronic equipment, an adhesive sheet for electronic equipment, an electronic component using the same, and an electronic equipment. More specifically, tape automated bonding (TAB) pattern processing tape, semiconductor grid connection substrates such as ball grid array (BGA) package interposers, lead frame fixing tape, which are used when mounting semiconductor integrated circuits, Die bonding materials, heat spreaders, reinforcing plates, shielding material adhesives, solder resists, anisotropic conductive materials used for bonding LOC fixing tapes, electronic components such as semiconductor elements, and supporting members such as lead frames and insulating support substrates Adhesive composition for electronic equipment, adhesive sheet for electronic equipment, and the like suitable for producing various electronic materials such as conductive films, copper-clad laminates, coverlays, semiconductor sealants, insulating layers between circuits The present invention relates to an electronic component and an electronic device using the.

  A method using a metal lead frame is most often used for mounting a semiconductor integrated circuit (IC). In recent years, a conductive pattern for IC connection is formed on an organic insulating film such as glass epoxy or polyimide. An increasing number of systems are provided via a semiconductor connection substrate called an interposer.

  As a package form, a package form such as a dual in-line package (DIP), a small outline package (SOP), a quad flat package (QFP) has been used. However, with the increase in the number of pins of ICs and the miniaturization of packages, the QFP that can increase the number of pins is approaching the limit. Therefore, BGA (ball grid array) and CSP (chip scale package) in which connection terminals are arranged on the back surface of the package have been used.

  Examples of the connection method of the substrate for semiconductor connection include a tape automated bonding (TAB) method, a wire bonding method, a flip chip method, and the like, and a tape with an adhesive for TAB can be used.

  Of course, the TAB method is advantageous for the connection method having the inner leads, but the BGA method is particularly suitable for the process of laminating the copper foil after mechanically punching the holes for solder balls and the device holes for IC. Is suitable. On the other hand, in the case of wire bonding and flip chip connection without an inner lead, it is possible to use not only a tape with an adhesive for TAB, but also a copper-clad laminate already laminated with copper foil and heat-cured adhesive. is there.

  FIG. 1 shows an example of a BGA type semiconductor device. The BGA system has solder balls (7) on the grid (grid array) corresponding to the number of pins of the semiconductor integrated circuit as an external connection part of the semiconductor integrated circuit connection substrate to which the semiconductor integrated circuit (1) is connected. It is characterized by. Connection to the printed circuit board is performed by placing the solder ball surface so as to coincide with the conductor pattern (4) of the printed circuit board on which the solder is already printed, and melting the solder by reflow. The greatest feature is that since the surface of the interposer can be used, many terminals can be arranged in a small space as compared with a package such as QFP that can use only the peripheral side. A chip scale package (CSP) is a further advancement of this miniaturization function. Micro BGA (μ-BGA), fine pitch BGA (FP-BGA), memory BGA (m-BGA), board on chip (BOC) ) Etc. have been proposed. An adhesive is used to bond the semiconductor integrated circuit of the package having these structures and the interposer.

  The semiconductor connection board is also laminated with components such as a reinforcing plate (stiffener) for imparting rigidity and flatness or a heat radiating plate (heat spreader) for heat dissipation. Is used. Moreover, an adhesive agent is used also for the sealing agent use as described in patent documents 1-3, and the use as an insulating layer between circuits.

  Recently, SiC (silicon carbide) having more excellent electrical characteristics has attracted attention in place of the conventional silicone (Si) wafer used as a semiconductor chip, and is being used in the field of power devices and the like. Since this SiC has excellent electrical characteristics, the voltage applied to the unit area becomes higher than that of Si, and accordingly, the temperature applied to the unit area also increases. Therefore, the temperature applied to the adhesive is also extremely high, and heat resistance exceeding 150 ° C. to 200 ° C., and more than 200 ° C. is required. Tolerance is required.

So far, an adhesive composition using an acrylic rubber or the like that hardly undergoes oxidative degradation at high temperatures has been proposed as an adhesive composition excellent in temperature cycle resistance (see, for example, Patent Documents 4 and 5). Further, an adhesive composition containing a thermosetting resin, a thermoplastic resin, an inorganic filler, and silicone oil has been proposed (see, for example, Patent Document 6). Further, an adhesive containing a comb-shaped graft polymer obtained by copolymerizing a silicone monomer and an acrylic monomer has been proposed as an adhesive for an additive method printed wiring board (see, for example, Patent Document 7). However, these known adhesive compositions also have insufficient heat resistance under high temperature conditions for a long period as described above.
JP 2004-327623 A JP 2006-32478 A JP 2003-277473 A Japanese Patent Laid-Open No. 3-181580 JP 2001-49221 A JP-A-2005-150421 JP-A-10-265552

  An object of the present invention is to solve such problems and to provide an adhesive composition for electronic equipment excellent in long-term high-temperature resistance, an adhesive sheet for electronic equipment using the same, an electronic component, and an electronic equipment. To do.

  That is, the present invention relates to a) a thermosetting resin, b) a curing agent, c) a polymer having an organopolysiloxane in the side chain, and d) an acrylic ester and / or methacryl having a side chain having 1 to 8 carbon atoms. It is the adhesive composition for electronic devices characterized by including the copolymer which uses an acid ester as an essential copolymerization component, The adhesive sheet for electronic devices, electronic components, and an electronic device using the same.

  Since the adhesive composition for electronic devices of the present invention has excellent heat resistance even under a high temperature condition for a long time, the reliability of a semiconductor device using the same can be improved.

  Hereinafter, the configuration of the present invention will be described in detail.

  The adhesive composition for electronic devices and the adhesive sheet for electronic devices of the present invention are tape automated used when mounting the above-mentioned stiffener, heat spreader, semiconductor integrated circuit for semiconductor elements and wiring boards (interposers). Bonding (TAB) pattern processing tapes, semiconductor connection substrates such as ball grid array (BGA) package interposers, lead frame fixing tapes, LOC fixing tapes, electronic components such as semiconductor elements and optical semiconductors, lead frames and insulation Die bonding materials, heat spreaders, stiffeners, shield material adhesives, solder resists, anisotropic conductive films, copper-clad laminates, coverlays, and semiconductor sealants used for bonding to support members such as conductive support substrates , Insulation layer between circuits, back side of organic / inorganic EL The adhesive composition suitable for producing electronic materials such as various Mamoruso and a adhesive sheet using the same, the shape and material of the adherend is not particularly limited. Among them, the adhesive composition for electronic devices of the present invention was cut after an element was formed on a semiconductor substrate such as silicone as shown in FIG. A semiconductor integrated circuit (bare chip) (1) is bonded to a wiring board layer composed of an insulator layer (3) and a conductor pattern (4) with an adhesive layer (2), and the semiconductor integrated circuit (1) and the wiring board layer are This is effective for use as an adhesive layer of a semiconductor device having a structure connected by a bonding wire (6).

  The adhesive composition for electronic equipment of the present invention has a) a thermosetting resin, b) a curing agent, c) a polymer having an organopolysiloxane in a side chain, and d) a side chain having 1 to 8 carbon atoms. It contains a copolymer having an acrylic ester and / or a methacrylic ester having a side chain having 1 to 8 carbon atoms as an essential copolymerization component.

  c) If the polymer having an organopolysiloxane in the side chain is a polymer having an organopolysiloxane in the side chain, the structure of the main chain is not particularly limited. Such a polymer (graft polymer) is said to be difficult to achieve compatibility by combining different functions in the main chain and side chain, such as soft / hard, crystalline / amorphous, release / adhesion, hydrophilic / hydrophobic, etc. Physical properties can be expressed simultaneously. For example, when an acrylic resin is used for the main chain, the heat resistance can be improved by the side chain organopolysiloxane while maintaining the film-forming property and hardness of the acrylic resin. The organopolysiloxane serving as the side chain is preferably polydimethylsiloxane. Furthermore, it is preferable to contain a phenyl group in an arbitrary ratio instead of a methyl group. By containing a phenyl group, compatibility with other organic resins and heat resistance can be further improved. The proportion of the phenyl group can be appropriately adjusted depending on the compatibility and heat resistance required. The molecular weight of the side chain is preferably a number average molecular weight of 1,000 to 30,000. By setting the molecular weight of the side chain within this range, the composition can be prepared without being separated from the thermosetting resin, the thermoplastic resin, and the curing agent. As for the structure of the main chain, various structures can be obtained by homopolymerization of a macromonomer or copolymerization of a macromonomer and another monomer. For example, when a macromonomer having a methacryloyl group at one end of polydimethylsiloxane and a styrene monomer are copolymerized, the main chain contains an acrylic component derived from a methacryloyl group and a component derived from styrene. Various structures can be selected according to the purpose, but an acrylic resin is preferable from the viewpoint of film-forming properties and compatibility with other resin components.

Such a polymer having an organopolysiloxane in the side chain is synthesized by, for example, a method of polymerizing an organosiloxane in the presence of a main chain polymer, a homopolymerization of a silicone macromonomer, or a copolymerization with another monomer. There is a way. In view of easy control of the side chain length, number, stereoregularity and the like, a synthesis method using a silicone macromonomer is preferred. Here, the macromonomer (or macromer) refers to a monomer having a high molecular weight (usually about several hundred to several tens of thousands) having a polymerizable functional group. The polymerizable functional group may have either one end or both ends. From the viewpoint of obtaining a graft polymer having a controlled structure, a copolymer having a one-end silicone macromonomer as a copolymerization component is more preferable. A graft polymer having a controlled structure and molecular weight can be obtained by using, as a copolymerization component, an oligomer that has been polymerized to some extent in advance or a polymer having a polymerizable functional group introduced at one end thereof. Examples of such one-end silicone macromonomers include AK-5 (segment part is dimethylsiloxane and one end is methacryloyl group, number average molecular weight 5,000), AK-32 (segment part), manufactured by Toa Gosei Co., Ltd. Is dimethylsiloxane, one end is a methacryloyl group, number average molecular weight 20,000), represented by the following general formula (1), manufactured by Shin-Etsu Chemical Co., Ltd., X-24-8201 (R = CH ₃ , n = _{25), X-22-174DX (R} = CH 3 (CH 2) 3, n = 60), X-22-2426 (R = CH 3 (CH 2) 3, n = 150) or, X-22- 2404 (structure: CH ₂ ═C (CH ₃ ) OCOC ₃ H ₆ Si (OSiMe ₃ ) ₃ ) and the like.

  Further, the both-end reactive silicone oil and the one-end reactive silicone oil are also included in the macromonomer. By copolymerizing these macromonomers and other monomers, a polymer having a graft polymer, that is, an organopolysiloxane in the side chain can be obtained. Other monomers to be copolymerized with the silicone macromonomer are not particularly limited, and can be appropriately selected so as to have physical properties to be expressed in the main chain. Examples of monomers include ethylene, propylene, styrene, tetrafluoroethylene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, allyl alcohol, allyl acetate, formaldehyde, trioxane, n-butyl isocyanate, ethylene oxide, tetrahydrofuran, ε-caprolactam, β -General-purpose ones such as propiolactone and (1) (meth) acrylates: isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butyl (meth) acrylate as vinyl monomers , Dicyclopentanyl methacrylate, dicyclopentenyloxyethyl (meth) acrylate, dipentaerythritol (penta) hexaacrylate, tripropylene glycol diacrylate, trimethylo Rupropane tri (meth) acrylate, polyethylene glycol diacrylate, glycidyl methacrylate, methyl methacrylate, acrylate ester having a side chain having 1 to 8 carbon atoms and / or methacrylate ester having a side chain having 1 to 8 carbon atoms, etc. (2) Acrylamide derivatives: N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, (3) Other unsaturated compounds: isoprenesulfonic acid soda, N-vinylacetamide, N-vinylformamide Non-vinyl monomers such as (poly) allylamine and (poly) p-vinylphenol include (1) polycarboxylic acid: 1,4-cyclohexanecarboxylic acid, CIC acid / Bis-CIC acid, 2,6- Naphthalenedicarboxylic acid ( Methyl), (2) polyhydric alcohol: 1,4-cyclohexanedimethanol, 4,4′-dihydroxybiphenyl, dimethylolbutanoic acid, hydrogenated bisphenol A, neopentyglycol, 1,3-propanediol, (3) Polyvalent amines: m-xylylenediamine, 1,4-diaminobutane, norbornanediamine, 1,3-bis (aminomethyl) cyclohexane, and other 2,2-bis (p-cyanatophenyl) propane, and recently Developed as (meth) acrylic, fluorine monomer, alicyclic monomer, monomer having reactive functional group, biocompatible monomer, and various vinyl compounds: p-chlorostyrene, vinyl sulfonic acid, vinyl oxazoline Other examples include bisoxazine (non-vinyl). Two or more of these monomers may be copolymerized. Among these, acrylic monomers such as methyl methacrylate, acrylic acid esters having a side chain having 1 to 8 carbon atoms, and / or methacrylic acid esters having a side chain having 1 to 8 carbon atoms, acrylonitrile, acrylamide and the like are preferable. By using these monomers, the polymer having an organopolysiloxane in the side chain is easily compatible with other acrylic resins (thermoplastic resins), so that the heat resistance and the stress relaxation effect can be improved. Such copolymerization may be performed using any method such as radical copolymerization or ionic copolymerization.

  The polymer having an organopolysiloxane in the side chain has at least one functional group selected from the group consisting of epoxy groups, hydroxyl groups, carboxyl groups, amino groups, alkoxy groups, vinyl groups, silanol groups and isocyanate groups. Is preferred. By having these functional groups, the crosslinked structure after curing of the adhesive composition can be made denser. Further, among them, those having a hydroxyl group, an epoxy group, or a carboxyl group are more preferable because the adhesive force and reflow resistance are improved. In order to impart these functional groups, for example, a monomer having a functional group such as glycidyl methacrylate or 2-hydroxyethyl methacrylate may be copolymerized.

  In the present invention, the polymer having such an organopolysiloxane in the side chain is classified as c) even if it is a thermosetting resin or a thermoplastic resin.

Examples of the polymer having an organopolysiloxane in the side chain include those represented by the following general formula (2). Specifically, manufactured by Shin-Etsu Chemical Co., Ltd., silicone graft acrylic resin, product names: X-24-798A, X-22-8004 (R ⁴ : C ₂ H ₄ OH, functional group equivalent: 3250 (g / mol) ^{)), X-22-8009 (R} 4: Si (OCH 3) 3 containing an alkyl group, the functional group equivalent: 6200 (g / mol)) , X-22-8053 (R 4: H, functional group equivalent: 900 (G / mol)), X-22-8084, X-22-8084EM, X-22-8195 (R ⁴ : H, functional group equivalent: 2700 (g / mol)), Toagosei Co., Ltd. Series (US-270, US-350, US-352, US-380, US-413, US-450, etc.), Reseta GS-1000 series (GS-1015, GS-1302, etc.) and the like.

In the above formula, R ¹ may be the same or different, and represents CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ or CH ₃ (CH ₂ ) ₃ . R ² may be the same or different and represents H, CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ or CH ₃ (CH ₂ ) ₃ . R ³ may be the same or different and represents H or CH ₃ . R ⁴ may be the same or different, and H, CH ₃ , C ₂ H ₅ , CH ₃ (CH ₂ ) ₂ , CH ₃ (CH ₂ ) ₃ , or an epoxy group, a hydroxyl group, a carboxyl group, an amino group, an alkoxy group An alkyl group having 1 to 6 carbon atoms substituted with at least one functional group selected from the group consisting of a group, a vinyl group, a silanol group and an isocyanate group.

  c) The content of the polymer having an organopolysiloxane in the side chain is preferably 10 parts by weight or more, more preferably 40 parts by weight or more, and preferably 100 parts by weight or more, based on 100 parts by weight of the thermosetting resin described later. It is 600 parts by weight or less, more preferably 450 parts by weight or less, and still more preferably 300 parts by weight or less. If it is this range, since flexibility and adhesiveness can be maintained, it is preferable.

  Although the adhesive composition for electronic devices of this invention contains at least 1 type of a) thermosetting resin, the kind is not specifically limited. The thermosetting resin has a function of realizing a balance of physical properties such as heat resistance, insulation at high temperature, chemical resistance, and adhesive layer strength.

  Examples of the thermosetting resin include known resins such as epoxy resins, phenol resins, melamine resins, xylene resins, furan resins, and cyanate ester resins. In particular, an epoxy resin and a phenol resin are preferable because of excellent insulation. 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, resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, dicyclopentadienedixylenol, etc. Alicyclic epoxy such as diglycidyl ether, epoxidized phenol novolak, epoxidized cresol novolak, epoxidized trisphenylol methane, epoxidized tetraphenylol ethane, epoxidized metaxylene diamine, cyclohexane epoxide, etc. . Among them, those having three or more epoxy groups in one molecule are preferably used in order to increase the crosslinking density of the adhesive composition. As these polyfunctional epoxy resins, orthocresol novolak type: Specifically, E180H65 manufactured by JER (Japan Epoxy Resin Co., Ltd.), ESCN195 manufactured by Sumitomo Chemical Co., Ltd., EOCN1020 manufactured by Nippon Kayaku Co., Ltd., EOCN102S, 103S, 104S, etc., DPP novolak type: specifically, J157 E157S65, etc., trishydroxyphenylmethane type: specifically Nippon Kayaku Co., Ltd. EPPN501H, JER E1032, etc., tetraphenylolethane type: specifically E1031S made by JER, dicyclopentadienephenol type: Specifically, HP7200 made by DIC (Dainippon Ink Chemical Co., Ltd.), other polyfunctional epoxy resins having a naphthalene structure, ESN made by Nippon Steel Chemical Co., Ltd. , YL6241 made by JER with special skeleton, etc. Epoxy resins have been sales. Two or more of these epoxy resins may be used. Moreover, an alicyclic epoxy is preferably used from the point which can maintain the transparency by reducing the coloring change of an adhesive composition. Examples of the alicyclic epoxy resin include Daicel Chemical Industries, Ltd. Celoxide 2021, Celoxide 2080, Celoxide 3000, Celoxide 2000, Epolide GT300, GT400, EHPE3150, Shin Nippon Rika Co., Ltd. Rikaresin HBE-100, 500, Rikaresin DME -100, 200, manufactured by Toto Kasei Co., Ltd .: ZX1702, ST-3000, ST-4000D, ERS-100, ZX-1658, manufactured by JER: YX-8034, YX-8000, RXE21, YL6753, YL7040, YL7170, etc. Can be mentioned. Two or more of these epoxy resins may also be used. From the viewpoint of handleability and less discoloration after standing at high temperature, for example, a solid alicyclic epoxy such as EHPE3150 is preferably used.

  Furthermore, it is effective to use a halogenated epoxy resin, particularly a brominated epoxy resin, for imparting flame retardancy. From the viewpoint of coexistence with the heat resistance of the adhesive composition, it is effective to use a mixed system of a brominated epoxy resin and a non-brominated epoxy resin. Examples of brominated epoxy resins include copolymerized epoxy resins of tetrabromobisphenol A and bisphenol A, or brominated phenol novolac type epoxy resins such as “BREN” -S (manufactured by Nippon Kayaku Co., Ltd.). . Two or more of these brominated epoxy resins may be used in consideration of bromine content and epoxy equivalent. Recently, from the viewpoint of environmental impact, epoxy resins that do not contain barogen are also often used, specifically phosphorus-containing epoxy resins and nitrogen-containing epoxy resins. These epoxy resins may be used for imparting flame retardancy.

  As the phenol resin, any known phenol resin such as novolak type phenol resin and resol type phenol resin can be used. For example, alkyl-substituted phenols such as phenol, cresol, p-t-butylphenol, nonylphenol, p-phenylphenol, cyclic alkyl-modified phenols such as terpene and dicyclopentadiene, hetero groups such as nitro groups, halogen groups, cyano groups, and amino groups Examples thereof include those having functional groups containing atoms, those having a skeleton such as naphthalene and anthracene, and resins composed of polyfunctional phenols such as bisphenol F, bisphenol A, bisphenol S, resorcinol, and pyrogallol.

  The adhesive composition for electronic devices of this invention contains b) hardening | curing agent. b) The content of the curing agent is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of a) thermosetting resin.

  Examples of the curing agent 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 Boron trifluoride amine complexes such as reethylamine complex, 2-alkyl-4-methylimidazole, imidazole derivatives such as 2-phenyl-4-alkylimidazole, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Known materials such as organic acids and dicyandiamide can be used, and these may be used alone or in combination of two or more. Among these, acid anhydride curing agents are useful from the viewpoints of transparency and coloring.

  The content of the acid anhydride curing agent is preferably (acid anhydride group number) / (epoxy group-derived epoxy group number), preferably 0.5 to 1.5, more preferably 0.6 to 1.2, and still more preferably 0. .9 to 1.0. When (acid anhydride group number) / (epoxy resin-derived epoxy group number) is 0.5 or more, the storage stability is stabilized, and when it is 1.5 or less, good adhesive force can be expressed.

  As the acid anhydride, commercially available products are tetrahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd .: TH), hexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd .: HH), methyltetrahydrophthalic anhydride (Shin Nippon) Rika Co., Ltd .: MT-500TZ, Hitachi Chemical Co., Ltd .: HN-2200, Nippon Zeon Co., Ltd .: QH-200), Methylhexahydrophthalic anhydride (Shin Nihon Rika Co., Ltd .: MH) -700, manufactured by Hitachi Chemical Co., Ltd .: HN-5500, manufactured by Dainippon Ink & Chemicals, Inc .: B-650), methyl nadic acid anhydride (manufactured by Nippon Kayaku Co., Ltd .: MCD, Hitachi Chemical Co., Ltd.) Co., Ltd .: MHAC-P), hydrogenated methyl nadic acid anhydride (Shin Nihon Rika Co., Ltd .: HNA, HNA-100), trialkyl tetrahydrophthalic anhydride (JER Co., Ltd .: YH-306, YH) 307), methylcyclohexene tetracarboxylic dianhydride (manufactured by Dainippon Ink Co., Ltd .: B-4400), benzophenone tetracarboxylic acid dihydrate, ethylene glycol bisanhydro trimellitate, glyceryl bis (anhydro trimelli Tate) monoacetate, dodecenyl succinic anhydride, aliphatic dibasic acid polyanhydride, chlorendic anhydride and the like. If it is an acid anhydride, the effect will be exhibited, but among them, a hydrogenated methyl nadic acid anhydride is preferable in that the blend or cured product has low moisture absorption and is excellent in colorless transparency.

  Further, known curing accelerators such as imidazole derivatives such as triphenylphosphine, 2-alkyl-4-methylimidazole, and 2-phenyl-4-alkylimidazole are also included in b) the curing agent in the present invention. Among them, imidazole silane represented by the following general formula (3) is useful.

In the above formula, ^{R 5} is a saturated hydrocarbon group having hydrogen or a C 1 to 20, ^{R 6} represents hydrogen, a vinyl group or an alkyl group having 1 to 5 carbon atoms. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms. X ¹ and X ² may be the same or different and each represents hydrogen, an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methylol group, an isocyanate group, a vinyl group, a silanol group, or an alkyl group having 1 to 3 carbon atoms. . p and q are integers of 1 to 10, l is an integer of 1 to 3, and r is an integer of 1 to 5.

In the imidazole compound represented by the general formula (3), the imidazole group has a curing accelerating action on the epoxy resin, and also has a high adsorption ability by forming a complex with copper and a copper alloy. Further, since the alkoxysilyl group strongly adsorbs to a substrate made of a metal or an inorganic material, the adhesion with the substrate is improved. Furthermore, when R ¹⁰ is a functional group that reacts with an epoxy group, the crosslink density is further increased, and the adhesion and reflow resistance are improved. Examples of the functional group that reacts with the epoxy group include an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methylol group, an alkoxy group, an isocyanate group, a vinyl group, and a silanol group.

  As for content of the imidazole compound represented by General formula (3), 0.1-2.0 mol% is preferable with respect to the epoxy group contained in an adhesive composition. Here, the epoxy group contained in the adhesive composition is d) a copolymer containing an acrylic acid ester and / or methacrylic acid ester having a side chain having 1 to 8 carbon atoms as an essential copolymerization component, which will be described later. When the epoxy group is contained in the component c), it indicates the total amount of the epoxy group contained in these components and the epoxy resin. By setting it to 0.1 mol% or more, a curing accelerating action is obtained and the adhesive force is improved. On the other hand, by setting it as 2.0 mol% or less, the elasticity modulus can be kept high and the strength and heat resistance of the adhesive film can be improved.

  Moreover, the well-known imidazole compound as mentioned above can be contained for adjustment of a curing rate etc. with imidazole silane. The content of these known imidazole compounds is preferably 20 to 100 parts by weight with respect to 100 parts by weight of the imidazole compound represented by the general formula (3).

  In addition, quaternary ammonium salts and organic phosphonium salt compounds are useful as a curing accelerator for obtaining a cured product having excellent colorless transparency after curing and after long-term heat resistance. Commercially available products include San Apro Co., Ltd .: U-CAT series, U-CAT SA series, POLYCAT8, Hokuko Chemical Co., Ltd .: Organic phosphine, Nippon Chemical Industry Co., Ltd .: Hishicolin (organic phosphonium salt compound), etc. Is mentioned.

  The adhesive composition for electronic devices of this invention contains the copolymer which uses acrylic acid ester and / or methacrylic acid ester which have d) C1-C8 side chain as an essential copolymerization component. As a result, c) compatibility with a polymer having an organopolysiloxane in the side chain, adhesion to a material such as a wiring board layer (A), flexibility, relaxation of thermal stress, insulation due to low water absorption Has functions such as improvement. These copolymers also preferably have a functional group capable of reacting with the aforementioned thermosetting resin. Specific examples include an amino group, a carboxyl group, an epoxy group, a hydroxyl group, an alkoxy group, an isocyanate group, a vinyl group, and a silanol group. In this case, it is more preferable to use a copolymer having a carboxyl group and / or a hydroxyl group as a functional group in combination with a copolymer having another functional group. The functional group content described above is preferably 0.07 eq / kg or more and 0.7 eq / kg or less, more preferably 0.07 eq / kg or more and 0.45 eq / kg or less, and further preferably 0.07 eq / kg or more and 0 or less. .14 eq / kg or less.

  d) The content of the copolymer having an acrylic ester and / or methacrylic ester having a side chain of 1 to 8 carbon atoms as an essential copolymer component is preferably a) relative to 100 parts by weight of the thermosetting resin. 50 parts by weight or more, more preferably 100 parts by weight or more, further preferably 200 parts by weight or more, preferably 800 parts by weight or less, more preferably 600 parts by weight or less, still more preferably 500 parts by weight or less, and still more preferably 400 parts by weight. Less than parts by weight. If it is this range, since flexibility and heat resistance can be maintained, it is preferable.

  Further, in addition to the component d), other thermoplastic resins may be contained. Examples of the thermoplastic resin include acrylonitrile-butadiene copolymer (NBR), acrylonitrile-butadiene-styrene resin (ABS), polybutadiene, styrene-butadiene-ethylene resin (SEBS), polyvinyl butyral, polyamide, polyester, polyimide, polyamideimide, Examples thereof include polyurethane. Moreover, these thermoplastic resins may have a functional group capable of reacting with the aforementioned thermosetting resin. Specific examples include an amino group, a carboxyl group, an epoxy group, a hydroxyl group, an alkoxy group, an isocyanate group, a vinyl group, and a silanol group. These functional groups are preferable because the bond with the thermosetting resin becomes stronger and the heat resistance is improved. In addition, polyamide resin is also preferably used because of its good deterioration at high temperatures and good electrical characteristics. Various known polyamide resins can be used. In particular, it is preferable that the adhesive layer has flexibility and a dicarboxylic acid (so-called dimer acid) having a low water absorption carbon number of 36 as an essential component. Polyamide resin containing dimer acid is obtained by polycondensation of dimer acid and diamine by a conventional method. At this time, dicarboxylic acid other than dimer acid, azelaic acid, sebacic acid and the like is contained as a copolymerization component. Also good. Known diamines such as ethylenediamine, hexamethylenediamine, and piperazine can be used, and two or more diamines may be used in terms of hygroscopicity and solubility.

  The adhesive composition for electronic equipment of the present invention preferably contains an antioxidant. When the adhesive film is left at a high temperature for a long period of time, the cross-linking of the resin gradually proceeds, the phenomenon that the adhesive film becomes brittle, and coloring occurs. In particular, NBR having a double bond is likely to be oxidatively deteriorated by such heat. Therefore, by containing an antioxidant, embrittlement and coloring of the film after long-term heat resistance of the adhesive composition for electronic equipment can be prevented. The antioxidant is preferably at least one selected from the group consisting of e) a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. Among these, a combination of a phenolic antioxidant and a phosphorus antioxidant, and a combination of a phenolic antioxidant and a sulfur antioxidant is preferable.

  Due to the oxidative degradation of the adhesive composition caused by the influence of heat, the adhesive composition tends to be colored. The phenolic antioxidant has an action of capturing peroxide radicals generated in the oxidation reaction and converting them into peroxides. That is, it has a function capable of terminating the radical chain in the oxidation reaction. However, the converted peroxide is easily decomposed into radicals by heat. Therefore, phosphorus antioxidants and sulfur antioxidants have the function of converting peroxides into stable alcohol compounds. Therefore, using a combination of a phenol-based antioxidant and a phosphorus-based antioxidant, or a phenol-based antioxidant and a sulfur-based antioxidant is more effective in preventing oxidative deterioration due to heat and preventing coloring of the adhesive composition. is there.

  Moreover, in the adhesive composition for electronic equipment of the present invention, from the viewpoint of the anti-coloring effect, at least one selected from the group consisting of e) a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. The content of the antioxidant is preferably 0.1 to 5% by weight of the entire adhesive composition.

  As the phenolic antioxidant, 2,6-di-t-butyl-4-methylphenol (manufactured by Yoshitomi Pharmaceutical Co., Ltd .: Yoshinox BHT), 2,2′-methylenebis- (4-methyl-6-t-) Butylphenol) (Yoshitomi Pharmaceutical Co., Ltd .: Yoshinox 2246), 2,2′-methylenebis- (4-ethyl-6-t-butylphenol) (Yoshitomi Pharmaceutical Co., Ltd .: Yoshinox 425), 4,4′-butylidenebis -(3-Methyl-6-tert-butylphenol) (Yoshitomi Pharmaceutical Co., Ltd .: Yoshinox BB), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) benzene (manufactured by Ciba Specialty Chemicals Co., Ltd .: IRGANOX 1330), octadecyl-3- (3,5-di-t-butyl-4-hydroxy Enil) propionate (Ciba Specialty Chemicals Co., Ltd .: IRGANOX 1076), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Ciba Specialty Chemicals Co., Ltd.) Manufactured by: IRGANOX 1010), tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (manufactured by Ciba Specialty Chemicals: IRGANOX 3114), 2,4-bis [(octylthio) methyl]- o-Cresol (Ciba Specialty Chemicals Co., Ltd .: IRGANOX1520L), 4,6-bis (dodecylthiomethyl) -o-Cresol (Ciba Specialty Chemicals Co., Ltd .: IRGANOX 1726), 2,4-bis (N-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (manufactured by Ciba Specialty Chemicals Co., Ltd .: IRGANOX565), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals Co., Ltd .: IRGANOX245), 1,6-hexanediol-bis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals, Inc .: IRGANOX259), isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ( Ciba Specialty Chemicals Co., Ltd .: IRGANOX 1135), 2, 2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals: IRGANOX1035), N, N′-hexane-1, 6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide] (manufactured by Ciba Specialty Chemicals Co., Ltd .: IRGANOX 1098) 3,9-bis {2- [3- ( 3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane (manufactured by ADEKA Corporation) : ADK STAB AO-80) and the like.

  Examples of phosphorus-based antioxidants include tris- (nonylphenyl) -phosphite (manufactured by Ouchi Shinsei Chemical Co., Ltd .: Nocrack TNP), tris (2,4-di-t-butylphenyl) phosphite (Ciba Specialty Chemicals, Inc .: IRGAFOS 168), Tris [2-[[2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6 -Il] oxy] ethyl] amine (manufactured by Ciba Specialty Chemicals: IRGAFOS12), bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid (Ciba・ Specialty Chemicals Co., Ltd .: IRGAFOS38), bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphine Ito (Ciba Specialty Chemicals Co., Ltd .: IRGAFOS 126), tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite (Ciba Specialty) Chemicals, Inc .: IRGAFOSP-EPQ), bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite (manufactured by ADEKA, Inc .: ADK STAB PEP-36), di Stearyl pentaerythritol-di-phosphite (manufactured by ADEKA: ADK STAB PEP-8) and the like can be mentioned.

  As the sulfur-based antioxidant, tetrakis [methylene-3- (dodecylthio) propionate] methane (manufactured by ADEKA: Adeka Stab AO-412S), bis [2-methyl-4- (3-n-alkyl (carbon number)) 12-14) Thiopropionyloxy) -5-t-butylphenyl] sulfide (manufactured by ADEKA: ADK STAB AO-23), dilauryl-3,3′-thiodipropionate (Ciba Specialty Chemicals) Manufactured by: IRGANOXPS800FL), dimyristyl-3,3′-thiodipropionate (manufactured by Yoshitomi Pharmaceutical Co., Ltd .: DMTP), distearyl-3,3′-thiodipropionate (manufactured by Ciba Specialty Chemicals): IRGANOXPS802FL), 2-mercaptobenzimidazole (Shin Ouchi) Chemical Co., Ltd.: NOCRAC MB), 2-mercaptomethyl benzimidazole (Ouchi Shinko Chemical Industrial Co., Ltd.: NOCRAC MMB), and the like.

  By including an inorganic filler in the adhesive composition for electronic devices of the present invention, processability such as reflow resistance and punching property, thermal conductivity, and flame retardancy can be further improved. The inorganic filler is not particularly limited as long as it does not impair the properties of the adhesive. Specific examples thereof include silica, aluminum oxide, magnesium oxide, silicon nitride, aluminum hydroxide, magnesium hydroxide, gold, silver, copper, Examples thereof include iron, nickel, silicon carbide, aluminum nitride, titanium nitride, and titanium carbide. Of these, silica, aluminum oxide, magnesium oxide, silicon nitride, silicon carbide, aluminum hydroxide, and magnesium hydroxide are preferably used. These may be used alone or in combination of two or more. Of these, silica is particularly preferable because it has a thermal decomposition temperature greatly exceeding 300 ° C., which is advantageous for the reflow resistance of the adhesive, the fluidity of the adhesive sheet can be easily adjusted, and the particle size stability. Here, the silica may be either amorphous or crystalline, and it is not limited that the silica can be properly used according to the characteristics of each. These inorganic fillers may be subjected to surface treatment using a silane coupling agent or the like for the purpose of improving heat resistance, adhesiveness and the like. The following silane coupling agents can be used. In addition, the shape of the inorganic filler is not particularly limited, and a crushing system, a spherical shape, a scale shape, and the like are used, but a spherical shape is preferably used from the viewpoint of dispersibility in the paint. The particle size of the inorganic filler is not particularly limited, but it is an average in terms of reliability such as dispersibility and coating property, reflow resistance, thermal cycle property and poor connection when the adhesive sheet of the present invention is laminated to a substrate. Those having a particle size of 3 μm or less and a maximum particle size of 10 μm or less are preferably used. In addition, it is more effective to use fillers having different average particle diameters in combination from the viewpoint of fluidity and dispersibility. The particle diameter can be measured with a Horiba LA500 laser diffraction particle size distribution meter. The average particle diameter here is defined by a particle diameter (median diameter) corresponding to 50% when a particle size distribution is measured with reference to a sphere equivalent volume and the cumulative distribution is expressed in percent (%). The particle size distribution referred to here is such that the particle size display is a 56-segment piece logarithm display (0.1 to 200 μm) on a volume basis. The maximum particle size is defined by a particle size corresponding to 100% when the cumulative distribution is expressed in percent (%) in the particle size distribution defined by the average particle size. In addition, the measurement sample is obtained by putting particles in ion-exchanged water so as to become cloudy and performing ultrasonic dispersion for 10 minutes. In addition, the refractive index is 1.1 and the light transmittance is measured according to a reference value (about 70%, which is already set in the apparatus). The content of the inorganic filler is preferably 5 parts by weight or more, and more preferably 10 parts by weight or more with respect to 100 parts by weight of a) thermosetting resin. Moreover, 200 weight part or less is preferable, 150 weight part or less is more preferable, and 100 weight part or less is further more preferable. By making content of an inorganic filler into 5 weight part or more, the improvement effect of reflow resistance is acquired, and adhesive force can be improved by being 200 weight part or less.

  By including a silane coupling agent in the adhesive composition for electronic equipment of the present invention, it is possible to improve the adhesive force with various metals including copper and rigid substrates such as glass epoxy substrates. Examples of the silane coupling agent include those represented by the following general formula (4).

X's may be the same or different and each has 1 to 1 carbon atoms substituted with a vinyl group, an epoxy group, a styryl group, an acryloxy group, an amino group, a methacryl group, a mercapto group, an isocyanate group and at least one functional group thereof. Selected from 6 alkyl groups. Among them, those containing an amino group or an epoxy group are preferable from the viewpoint of adhesiveness. R ¹¹ is selected from CH ₃ , C ₂ H ₅ , and CH ₃ OC ₂ H ₄ , and among them, a methyl group and an ethyl group are preferable.

  In addition to the above components, it is not limited at all to contain fine organic or inorganic components, ion scavengers and the like within a range that does not impair the properties of the adhesive.

  Examples of fine inorganic components include zirconium oxide, zinc oxide, titanium oxide, iron oxide, cobalt oxide, chromium oxide, inorganic oxides such as talc, inorganic salts such as calcium carbonate, metal fine particles such as aluminum, carbon black, Glass is mentioned. Moreover, the fluorescent substance etc. which are used in optical semiconductor fields, such as LED, can also be contained. Examples of the fine particle organic component include crosslinked polymers such as styrene, NBR rubber, acrylic rubber, polyamide, polyimide, and silicone.

  Inorganic ion exchangers are often used as ion scavengers. Inorganic ion exchangers (i) have high ion selectivity and can separate specific ions from a system in which two or more ions coexist, (ii) excellent heat resistance, (iii) organic solvents and resins (Iv) It is effective in trapping ionic impurities, and can be expected to suppress reduction in insulation resistance, prevent corrosion of aluminum wiring, prevent occurrence of electromigration, and the like. There are many types, a) aluminosilicate (natural zeolite, synthetic zeolite, etc.), b) hydroxide or hydrous oxide (hydrous titanium oxide, hydrous bismuth oxide etc.), c) acid salt (zirconium phosphate, phosphorus Titanium oxide, etc.), d) basic salts, complex hydrous oxides (hydrotalcite, etc.), e) heteropoly acids (ammonium molybdate, etc.), f) hexacyanoiron (III) salts, etc. (hexacyanozinc, etc.), g ) Antimony oxide, h) other, 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. Is mentioned. There are cation exchangers, anion exchangers, and both ion exchangers, but both ion exchangers are preferred because both positive and negative ionic impurities are present in the adhesive composition. By using these, when used for an insulating layer, it is possible to prevent migration of wiring and suppress a decrease in insulation resistance.

  These components may be used alone or in combination of two or more. In view of dispersion stability, the average particle size of the fine particle component is preferably 0.2 to 5 μm. Moreover, 0.1 weight part or more is preferable with respect to 100 weight part of a) thermosetting resin, and, as for content of said each component, 0.5 weight part or more is more preferable. Moreover, 50 weight part or less is preferable, 30 weight part or less is more preferable, and 10 weight part or less is further more preferable.

  The adhesive sheet for electronic devices of the present invention (hereinafter referred to as an adhesive sheet) has an adhesive layer made of the adhesive composition for electronic devices of the present invention and at least one peelable protective film layer. Say. For example, a two-layer structure of protective film layer / adhesive layer or a three-layer structure of protective film layer / adhesive layer / protective film layer shown in FIG. You may have layers other than an adhesive bond layer and a protective film layer, for example, structures, such as an adhesive bond layer / polyimide film / adhesive layer, are mentioned. The adhesive sheet may be adjusted in degree of curing by heat treatment. The adjustment of the curing degree has an effect of preventing excessive flow of the adhesive when adhering the adhesive sheet to the wiring board or IC, and preventing foaming due to moisture during heat curing. Although the thickness of an adhesive bond layer can be suitably selected by the relationship with an elasticity modulus and a linear expansion coefficient, 2-500 micrometers is preferable, More preferably, it is 20-200 micrometers.

  The protective film layer as used herein refers to an adhesive before bonding an adhesive layer 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. Although it will not specifically limit if it can peel without impairing the form and function of a layer, For example, polyester, polyolefin, polyphenylene sulfide, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol Plastic films such as polycarbonate, polyamide, polyimide, polymethyl methacrylate, silicone rubber, etc., films obtained by coating these with a release agent such as silicone or fluorine compound, and these films Paper laminated with Lum, paper and the like impregnated or coated with a releasing property of a certain resin. More preferably, the protective film layer is colored. Since it can be confirmed visually whether the protective film has been peeled off, forgetting to peel off can be prevented.

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 it as this range, a protective film layer can be peeled stably one side at a time. The peeling forces F ₁ and F ₂ are preferably ¹ to 200 Nm ⁻¹ , more preferably 3 to 100 Nm ⁻¹ . When it is lower than ¹ Nm ⁻¹ , the protective film layer falls off, and when it exceeds 200 Nm ⁻¹ , peeling is unstable and the adhesive layer may be damaged. Here, the peeling force with respect to the adhesive layer of a protective film layer means the value measured with the following method. An adhesive sheet having a protective film layer on both sides of the adhesive layer (test piece size is 30 × 200 mm) is prepared, and the double peeled protective film layer side is attached to a flat glass table with a double-sided tape. Using a digital force gauge (portable electronic spring balance), the light release protective film layer is peeled off in the 90 ° direction, and the gauge value at that time is defined as the light release protective film layer peeling force (F ₂ ). Subsequently, the adhesive layer single film is similarly peeled off in the 90 ° direction, and the gauge value at that time is defined as the heavy peel protective film layer peel force (F ₁ ). The peeling rate was measured as 350 mm / min.

  In the adhesive sheet of the present invention, the shear strength after heating of the adhesive layer is preferably 5 MPa or more, more preferably 10 MPa or more. It is preferable that the shear strength after heating is 5 MPa or more because peeling is unlikely to occur at the time of handling and handling the package. Further, the shear strength retention before and after the thermal cycle test is preferably 60% or more, and more preferably 80% or more. If it is this range, it will not drop out during handling. In order to obtain an adhesive layer having such a shear strength, for example, d) As a copolymer having an acrylic acid ester and / or methacrylic acid ester having a side chain having 1 to 8 carbon atoms as an essential copolymerization component It is preferable to contain a copolymer having a weight average molecular weight by GPC (gel permeation chromatography) of preferably 300,000 or more, more preferably 500,000 or more, and still more preferably 1,000,000 or more. Furthermore, it is more preferable that these copolymers have a functional group capable of reacting with the above-described thermosetting resin. Specific examples include an amino group, a carboxyl group, an epoxy group, a hydroxyl group, an alkoxy group, an isocyanate group, a vinyl group, and a silanol group. In this case, it is more preferable to use a copolymer having a carboxyl group and / or a hydroxyl group as a functional group in combination with a copolymer having another functional group. Here, the shear strength can be measured at room temperature using a bond tester MODEL SS-30WD (load cell 50 kg) manufactured by Seishin Shoji Co., Ltd. at a speed of 0.120 mm / sec. Specifically, as shown in FIG. 3, the adhesive sheet of the present invention was laminated on the back surface of the evaluation pattern tape (14) under the conditions of 130 ° C., 0.5 MPa, 0.3 m / min, and then protected. The film layer is peeled off, and the polyimide coating surface of the 2 mm square silicone wafer is heated and pressure-bonded to the adhesive layer (13) at 130 ° C., 3 MPa, and 10 seconds. Subsequently, heat curing is performed in an air oven at 150 ° C. for 2 hours, and the shear strength of the obtained sample is measured under the above conditions. Here, a silicone wafer is used in which a dummy wafer mirror surface is coated with a polyimide coating agent (manufactured by Toray Industries, Inc .: SP341) and cured at 350 ° C. for 1 hour.

  As for the haze value after heat-hardening the adhesive bond layer of the adhesive sheet of this invention at 150 degreeC for 1 hour, 15 or less are preferable, More preferably, it is 5 or less. If it is 15 or less, when used in an optical semiconductor such as an LED lamp, a chip LED, a semiconductor laser, a photo camera, and a photodiode, light from the light source can be efficiently taken. Furthermore, the haze of the adhesive layer after heat curing at 150 ° C. for 1 hour is 15 or less, the haze of the adhesive layer after heating and curing at 150 ° C. for 1 hour, and further heated at 150 ° C. for 500 hours is 30 or less. It is more preferable that This is because the light from the light source can be taken in efficiently as described above because the change in haze at a high temperature for a long time is small. Although the haze may be affected by the thickness, in the present invention, it is preferable that the entire adhesive layer satisfies the above-described haze value regardless of the thickness of the adhesive layer. In addition, the haze in this invention is used as a parameter | index of transparency (cloudiness value). Haze here excludes the influence of the scattering by the unevenness | corrugation of a surface, and when the adhesive agent surface is not smooth, it bonds together and measures on a glass plate. About a measuring method, it applies to JISK7105 (1981). As a method for obtaining an adhesive layer having such characteristics, for example, an adhesive layer containing an alicyclic epoxy resin as a thermosetting resin and an acid anhydride curing agent as a curing agent can be mentioned. In such applications, it is important not to be colored in addition to transparency for the reasons described above. Heat curing is usually performed in an air oven, but it is preferable to perform heat curing in a nitrogen atmosphere from the viewpoint that there is little color change of the adhesive layer after long-term storage at a high temperature.

The transmittance in the wavelength range of 330 nm to 2000 nm after the adhesive layer of the adhesive sheet of the present invention is heated and cured at 150 ° C. for 1 hour is preferably 70% or more, more preferably 80% at any wavelength. More preferably, it is 85% or more. Since the transmittance from the low wavelength region to the high wavelength region is 70% or more, the light from the light source can be taken in efficiently, which is useful for LED sealing applications and sensor applications that require high transmittance. is there. Furthermore, the transmittance in the wavelength range of 330 nm to 2000 nm after the adhesive layer is heat-cured at 150 ° C. for 1 hour is 70% or more at any wavelength, and after heat-curing at 150 ° C. for 1 hour, ultraviolet light is further emitted. The transmittance in the wavelength range of 330 nm to 2000 nm after irradiation for 88 hours at an irradiance of 81 mW / cm ² is preferably 70% or more at any wavelength, more preferably 80% or more, and even more preferably 85% or more. is there. For example, when used for LED sealing applications, when whitening is performed using a system that converts ultraviolet light, the ultraviolet light is irradiated onto the sealant for tens of thousands of hours. In that case, if the transmittance decreases with time, it becomes impossible to efficiently take light from the light source, so the reliability decreases. However, the transmittance after UV irradiation is 70% or more, so that high reliability is obtained. Can do. In the present invention, it is preferable that the adhesive layer as a whole satisfies the above-described transmittance regardless of the thickness of the adhesive layer. In order to obtain such an adhesive layer, it is preferable that a) an alicyclic epoxy resin as a thermosetting resin and b) an acid anhydride curing agent as a curing agent.

  The electronic component in the present invention refers to an electronic component manufactured using the adhesive sheet of the present invention, for example, a semiconductor integrated circuit connection substrate. FIG. 1 shows a cross-sectional view of one embodiment of a BGA type semiconductor device as an example using the electronic component of the present invention. The substrate for connecting a semiconductor integrated circuit is a layer having a conductor pattern for connecting an electrode pad of a bare chip and the outside of the package (printed circuit board, TAB tape, etc.), and a conductor is provided on one or both sides of the insulator layer (3). A pattern (4) is formed. 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 ceramic substrate such as an insulating film having a flexibility of 125 μm, alumina, zirconia, soda glass, and quartz glass is suitable, and a plurality of layers selected from these may be laminated and used. 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 conductor pattern is generally formed by either the subtractive method or the additive method, but any of them may be used in the present invention. In the subtractive method, a metal plate such as a copper foil is bonded to the insulator layer with an insulating adhesive (the adhesive composition of the present invention can also be used), or the insulator layer is bonded to the metal plate. A pattern is formed by etching a material prepared by a method in which precursors are stacked and an insulator layer is formed by heat treatment or the like by chemical treatment. Specific examples of the material herein include a rigid or copper-clad material for a flexible printed circuit board and a TAB tape. On the other hand, 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. The wiring board layer thus prepared may be provided with via holes as necessary, and the conductive patterns formed on both surfaces by plating may be connected by plating.

  The adhesive layer (2) is an adhesive layer mainly used for bonding the wiring board layer (5) and the semiconductor integrated circuit (1). However, it is not limited at all to be used for adhesion between the wiring board layer and other members (for example, an IC and a heat sink). This adhesive layer is usually laminated in a semi-cured state on a substrate for connecting a semiconductor integrated circuit. A pre-curing reaction is carried out at a temperature of 30 to 200 ° C. for an appropriate time before or after the lamination to increase the degree of curing. Can be adjusted.

  Next, the example of the manufacturing method of the adhesive sheet for electronic devices using the adhesive composition for electronic devices of this invention and an electronic component is demonstrated.

(1) Adhesive sheet for electronic equipment (a) A paint obtained by dissolving the adhesive composition for electronic equipment of the present invention in a solvent is applied onto a polyester film having releasability and dried. The thickness of the adhesive layer is preferably 10 to 200 μm. The drying conditions are generally 100 to 200 ° C. and 1 to 5 minutes. Solvents are not particularly limited, but aromatics such as toluene, xylene and chlorobenzene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aprotic polar solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone alone or a mixture are preferred. It is.

  (B) The adhesive sheet of the present invention is obtained by laminating a polyester or polyolefin-based protective film layer having a releasability with a lower peel strength than the above to the film of (a). In order to further increase the adhesive thickness, the adhesive layer may be laminated a plurality of times. Even when producing a composite structure in which an insulating film such as polyimide is laminated in addition to a single film, the adhesive sheet is laminated on the insulating film as described above, or it is produced by directly coating both surfaces of the insulating film. May be. After lamination, for example, the degree of curing may be adjusted by heat treatment at 30 to 70 ° C. for about 20 to 200 hours.

(2) Electronic component (a) 12-35 μm electrolytic copper foil is laminated on a tape with adhesive for TAB under the conditions of 130-170 ° C., 0.1-0.5 MPa, and then 80- A TAB tape with a copper foil is produced by sequentially heating and curing at 170 ° C. Photoresist film formation, etching, resist stripping, electrolytic nickel plating, electrolytic gold plating, and solder resist film fabrication are performed on the copper foil surface of the obtained TAB tape with copper foil by a conventional method to fabricate a wiring board.

  (B) The electronic device adhesive sheet obtained in (1) is thermocompression bonded to the wiring board of (a), and the IC is thermocompression bonded to the opposite surface of the adhesive sheet. In this state, heat curing at 120 to 180 ° C. is performed. Heat curing is usually performed in an air oven.

  (C) After the IC and the wiring board are connected by wire bonding under conditions of about 150 to 250 ° C. and about 100 to 150 kHz, they are sealed with resin.

  (D) Finally, a solder ball can be mounted by reflow to obtain 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. Prior to the description of the examples, an evaluation sample preparation method and an evaluation method will be described.

  (1) Sample preparation for evaluation: 18 μm electrolytic copper foil was applied to a tape with adhesive for TAB (# 7100, (type 31N0-00FS), manufactured by Toray Industries, Inc.) at 140 ° C., 0.3 MPa, 0.3 m / Laminate on the condition of minutes. Subsequently, a heat-curing treatment was sequentially performed in an air oven at 80 ° C. for 3 hours, at 100 ° C. for 5 hours, and at 150 ° C. for 5 hours to produce a TAB tape with copper foil. An evaluation pattern tape having a comb-shaped conductor pattern with a conductor width of 25 μm and a conductor distance of 25 μm is formed by performing photoresist film formation, etching, and resist peeling on the copper foil surface of the obtained TAB tape with copper foil by a conventional method. Produced.

  Next, the adhesive sheet for electronic equipment (thickness 25 μm) of the present invention was roll-laminated on the back surface of the pattern tape for evaluation produced by the above method under the conditions of 130 ° C., 0.5 MPa, 0.3 m / min. Then, the sample for evaluation was produced by the method described below using the silicone wafer (dummy wafer, 20 mm square) that looked like an IC. In addition, the silicone wafer used here coated the surface with a polyimide coating agent (manufactured by Toray Industries, Inc .: SP341) on the mirror surface, and used the one that was cured at 350 ° C. for 1 hour. The adhesive sheet bonded to the back surface of the evaluation pattern tape from which the coating surface of the silicone wafer and the protective film layer were peeled was attached under the conditions of 130 ° C., 3 MPa, and 10 seconds. The adhesive was cured at 150 ° C. for 2 hours.

  (2) Reflow resistance: 30 samples each having a 20 mm square for evaluation prepared by the method of (1) above were prepared, heat-dried at 120 ° C. for 12 hours, and then 168 in an atmosphere of 30 ° C. and 70% RH. After adjusting the humidity for a period of time, the sample was immediately passed twice continuously through an infrared reflow furnace at a maximum temperature of 260 ° C. and 15 seconds, and the peeled state was observed with an ultrasonic short-cut machine. The number of peeled pieces out of 30 pieces was examined.

  (3) Thermal cycle property: 30 samples each having a 20 mm square for evaluation prepared by the method of (1) above were prepared, and in a thermal cycle tester (Tabbayespekk Co., Ltd., PL-3 type), The treatment was carried out at −65 ° C. to 150 ° C. at the minimum and maximum temperatures for 40 minutes each, and the occurrence of peeling was evaluated. Samples were taken out at the end of each of 100 cycles, 300 cycles, 500 cycles, and 800 cycles, and the occurrence of peeling was evaluated using an ultrasonic short-cut machine. If it is confirmed that at least one of 30 pieces is peeled off, N. G. It was.

  (4) Shear strength: 2 mm after laminating the adhesive sheet of the present invention on the back surface of the evaluation pattern tape produced by the method of (1) above at 130 ° C., 0.5 MPa, 0.3 m / min. The polyimide coated surface of the square silicone wafer was thermocompression bonded to the adhesive sheet under conditions of 130 ° C., 3 MPa, and 10 seconds (FIG. 3). Subsequently, heat curing treatment was performed in an air oven at 150 ° C. for 2 hours. The shear strength of the obtained sample was measured. The shear strength was measured using a bond tester MODEL SS-30WD (load cell 50 kg) manufactured by Seishin Shoji Co., Ltd. at a speed of 0.120 mm / sec at room temperature. The silicone wafer used here was a dummy wafer mirror surface coated with a polyimide coating agent (manufactured by Toray Industries, Inc .: SP341) and cured at 350 ° C. for 1 hour.

  (5) Shear strength after thermal cycle: A sample for evaluation was prepared by the method described in (4) above, and heat-cured at 150 ° C. for 2 hours. Thereafter, 1000 cycles were performed in the same heat cycle tester as in (3) above, at -65 ° C to 150 ° C, with the minimum and maximum temperatures being held for 40 minutes each. The shear strength after the treatment was measured by the same method as in (4) above.

  (6) Share strength retention ratio: ((Share strength determined in (5) above) / (Share strength determined in (4) above)) × 100 (%) was determined.

  (7) Long-term high-temperature resistance: The electrolytic copper foil (1/2 ounce) was cleaned according to the standard procedure of copper foil surface cleaning of JPCA-BM02, and a 25 μm thick adhesive sheet was applied at 130 ° C., 0.5 MPa, Lamination was performed at 0.3 m / min to form a copper foil / adhesive layer and cured at 150 ° C. for 2 hours. They were placed in an air oven at 175 ° C. and a long-term standing test was conducted. In the middle, the sample was observed at a cycle of 10 hours. G. It was.

  (8) Transparency: A 20 μm thick adhesive layer obtained by applying the adhesive composition was laminated to a 50 μm thick PES film (total light transmittance: 92%, haze: 0.05%) at 100 ° C. Thus, a sample was prepared so as to have an adhesive layer / PES film configuration. This was appropriately cured in an air oven and stored at a high temperature to prepare a measurement sample. The haze value was measured according to JISK7105. When the total light transmittance (%) is Tt and the diffuse transmittance (%) is Td, the parallel light transmittance (%) Tp is expressed by Tp = Tt−Td, and the haze value (%) H is H = (Td / Tt) × 100. In addition, Suga Test Instruments Co., Ltd. direct reading haze computer (model | form: HGM-2DP) was used for the measuring instrument.

(9) Degree of yellowing: The measurement sample prepared in (8) above was visually observed. A visual comparison was made between what was heat-cured at 150 ° C. for 1 hour and what was heat-cured at 150 ° C. for 1 hour and then heated at 150 ° C. for 500 hours. The evaluation results are written as follows.
A: colorless and transparent, B: little yellowing, B: pale yellow, X: yellow, XX: dark yellow, XXX: brown.

(10) Transmittance: The 50 μm thick adhesive layer obtained by applying the adhesive composition was heat cured in an air oven at 150 ° C. for 1 hour, and the transmittance was measured. Moreover, after 50-micrometer-thick adhesive layer was heat-hardened at 150 degreeC for 1 hour, UV irradiation was performed for 88 hours, and the transmittance | permeability was measured. For UV irradiation, a weather resistance tester (metal weather, manufactured by Daipura Wintes Co., Ltd., model: KU-R5CI-A, light source: water-cooled jacket type metal halide lamp) was used, black panel temperature: 63 ° C., irradiance 81 mW / Irradiated with cm ² for 88 hours. The irradiance was measured at a spectral irradiance at 365 nm of 4042 μW / cm ² and measured at a wavelength range of 300 nm to 400 nm and a distance of 240 mm from the central axis of the light source. Transmittance was manufactured by Shimadzu Corporation, UV-3101PC type self-recording spectrophotometer (slit width 30 nm, light source (340 nm or more: halogen lamp, 340 nm or less: deuterium lamp), detector (860 nm or less: PMT, 860 nm or more). : PbS), sub-white plate: BaSO ₄ , incident angle 0 degree).

  The detail of the raw material used by each Example and the comparative example is shown below.

a) Thermosetting resin epoxy resin Ep1032S50: manufactured by Japan Epoxy Resin Co., Ltd., trifunctional type (trishydroxyphenylmethane type), epoxy equivalent 170
EOCN102S: Nippon Kayaku Co., Ltd., orthocresol novolak type, epoxy equivalent 210
EOCN103S: manufactured by Nippon Kayaku Co., Ltd., orthocresol novolac type EPICLON 1055: manufactured by Dainippon Ink & Chemicals, Inc., bis A type epoxy resin, epoxy equivalent 485
Ep828: Japan Epoxy Resin Co., Ltd., bis A type epoxy resin, epoxy equivalent 190
Ep1001: manufactured by Japan Epoxy Resin Co., Ltd., bis A type epoxy resin, epoxy equivalent 470
EHPE3150: manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin, epoxy equivalent 180
YX-8034: Japan Epoxy Resin Co., Ltd., alicyclic epoxy resin, epoxy equivalent 295
Ep834: manufactured by Japan Epoxy Resin Co., Ltd., bis A type epoxy resin, epoxy equivalent 250
Phenol resin YLH129: manufactured by Japan Epoxy Resin Co., Ltd., bis A phenol novolac KP-756P: manufactured by Arakawa Chemical Industries, Ltd., bis A novolak, softening point 95 ° C.
Hitanol 2500: Alkylphenol resol manufactured by Hitachi Chemical Co., Ltd.

b) Curing agent 4,4′-DDS: 4,4′-diaminodiphenylsulfone IS-1000: manufactured by Nikko Materials Co., Ltd., imidazolesilane C11Z: 2-undecylimidazole HNA-100: Shin Nippon Rika Co., Ltd. Manufactured, hydrogenated methyl nadic acid anhydride, acid anhydride equivalent 184
MH-700: manufactured by Shin Nippon Rika Co., Ltd., methylhexahydroacid anhydride, acid anhydride equivalent 163
PX-4MP: manufactured by Nippon Chemical Industry Co., Ltd., organic phosphonium salt compound U-CAT-5003: manufactured by San Apro Co., Ltd., organic phosphonium salt compound 2E4MZ: 2-ethyl-4-methylimidazole.

c) Polymer X-24-798A having an organopolysiloxane in the side chain: manufactured by Shin-Etsu Chemical Co., Ltd., silicone graft acrylic resin, no reactive group X-22-8004: manufactured by Shin-Etsu Chemical Co., Ltd., silicone graft Acrylic resin, reactive group OH, Tg (glass transition temperature) = 80 ° C.
X-22-8009: manufactured by Shin-Etsu Chemical Co., Ltd., silicone graft acrylic resin, reactive group Si (OCH ₃ ) ₃
X-22-8053: manufactured by Shin-Etsu Chemical Co., Ltd., silicone graft acrylic resin, reactive group COOH
X-22-8195: manufactured by Shin-Etsu Chemical Co., Ltd., silicone graft acrylic resin, reactive group COOH
X-22-8287: manufactured by Shin-Etsu Chemical Co., Ltd., silicone graft acrylic resin, reactive group epoxy group, Tg (glass transition temperature) = 40 ° C.
US270: Toa Gosei Co., Ltd., silicone graft acrylic resin, reactive group OH.

d) Copolymer SG-P3 having an acrylic acid ester and / or methacrylic acid ester having a side chain of 1 to 8 carbon atoms as an essential polymerization component: Epoxy based on butyl acrylate, manufactured by Nagase ChemteX Corporation Group-containing acrylic, epoxy equivalent 4700, Mw = 850000
XF-3388: Tope Co., Ltd., hydroxyl group-containing acrylic rubber mainly composed of ethyl acrylate, Mw = 1300,000
XF-3777: manufactured by Toupe Co., Ltd., hydroxyl group-containing acrylic rubber mainly composed of ethyl acrylate, Mw = 1300,000
SG-811: manufactured by Nagase ChemteX Corp., epoxy group-containing acrylic rubber mainly composed of butyl acrylate, Mw = 420,000.

e) Antioxidant ADK STAB AO-80: manufactured by ADEKA Corporation, phenolic antioxidant ADK STAB PEP-36: manufactured by ADEKA Corporation, phosphorus antioxidant ADK STAB AO-412S: manufactured by ADEKA Corporation, sulfur series Antioxidant.

Other inorganic filler SO-C2 (surface treatment product): manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, spherical silica, silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) is dry-treated. SO-C1: manufactured by Admatechs Co., Ltd., average particle size 0.3 μm, spherical silica SO-C2: manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, spherical silica silicone oil KF-412 : Shin-Etsu Chemical Co., Ltd., alkyl-modified silicone oil thermoplastic resin Nipol 1072J: Nippon Zeon Co., Ltd., carboxyl group-containing acrylonitrile butadiene rubber.

Examples 1-24, Comparative Examples 1-9
(Preparation of adhesive sheet)
Each inorganic filler listed in Tables 1 to 5 was mixed with toluene, and then ball milled to prepare a dispersion. In this dispersion, each thermosetting resin, a polymer having an organopolysiloxane in the side chain, a copolymer having an acrylic acid ester and / or methacrylic acid ester having a side chain having 1 to 8 carbon atoms as an essential polymerization component Then, an equal weight of methyl ethyl ketone and a curing agent, a curing accelerator, other additives and a dispersion were added so as to have the composition ratios shown in Tables 1 to 5, and stirred and mixed at 30 ° C. to prepare an adhesive solution. When an inorganic filler is not included, each thermosetting resin, a polymer having an organopolysiloxane in the side chain, an acrylate ester and / or a methacrylic ester having a side chain having 1 to 8 carbon atoms are essential polymerization components. Methyl ethyl ketone is added to the copolymer, curing agent, curing accelerator, and other additives so that the solid content is 20% by weight, so that the composition ratio is as shown in Tables 1 to 5, and stirred and mixed at 30 ° C. Thus, an adhesive solution was prepared. This adhesive solution was applied with a bar coater to a dry thickness necessary for a 38 μm-thick polyethylene terephthalate film with a silicone release agent (“Film Vina” GT manufactured by Fujimori Kogyo Co., Ltd.) It dried for minutes and bonded the protective film and produced the adhesive sheet of this invention. Each composition and characteristic are shown in Tables 1-5. In addition, imidazole silane content of Example 13 and 14 is 1.6 mol% with respect to the epoxy group contained in an adhesive composition.

(Fabrication of semiconductor devices)
A pattern tape for evaluation was prepared by the method described in the section (1) Preparation of evaluation sample. The nickel plating thickness was 3 μm, and the gold plating thickness was 1 μm. The protective film of the adhesive sheet produced by the above method was peeled off and laminated on the back surface of the pattern tape for evaluation under the conditions of 130 ° C. and 0.1 MPa. Subsequently, the PET film of the adhesive sheet was peeled off, and an IC having an aluminum electrode pad was thermocompression bonded to the adhesive layer under the conditions of 170 ° C. and 0.3 MPa. Next, heat curing treatment was performed in an air oven at 150 ° C. for 2 hours. Subsequently, a 25 μm gold wire was bonded to this at 180 ° C. and 110 kHz. Further, it was sealed with a liquid sealing resin (“Chip Coat” 8118, manufactured by NAMICS Co., Ltd.). Finally, a solder ball was mounted to manufacture a semiconductor device having the structure of FIG.

  Tables 1 to 5 show the adhesive layer compositions and evaluation results of Examples and Comparative Examples.

  From the Examples and Comparative Examples in Tables 1 to 5, it can be seen that the adhesive composition for electronic devices obtained by the present invention is excellent in long-term high-temperature resistance. Furthermore, by using a combination of a thermosetting resin as an alicyclic epoxy and a curing agent as an acid anhydride curing agent, an adhesive composition for electronic equipment having excellent transparency and UV resistance and little yellowing can be obtained. The transmission spectra of Example 21 and Comparative Example 7 after curing at 150 ° C. for 1 hour and after heat curing at 150 ° C. for 1 hour and after UV irradiation for 88 hours are shown in FIGS.

FIG. 14 is a cross-sectional view of one embodiment of a BGA semiconductor device. Sectional drawing of the one aspect | mode of the adhesive agent sheet for electronic devices of this invention. Schematic of the sample for evaluation. The transmission spectrum of Example 21 after curing at 150 ° C. for 1 hour. The transmission spectrum after carrying out UV irradiation for 88 hours after 150 degreeC 1-hour hardening of Example 21. FIG. The transmission spectrum of Comparative Example 7 after curing at 150 ° C. for 1 hour. Transmission spectrum after UV irradiation for 88 hours after curing at 150 ° C. for 1 hour in Comparative Example 7.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor integrated circuit 2, 9 Adhesive layer 3 Insulator layer 4 Conductor pattern 5 Wiring board layer 6 Bonding wire 7 Solder ball 8 Sealing resin 10 Protective film layer 11 Silicone wafer 12 Polyimide coating layer 13 Adhesive layer 14 Evaluation pattern tape

Claims (11)

a) a thermosetting resin, b) a curing agent, c) a polymer having an organopolysiloxane in the side chain, and d) an acrylic acid ester and / or a methacrylic acid ester having a side chain having 1 to 8 carbon atoms. An adhesive composition for electronic equipment, comprising a copolymer as a polymerization component. The adhesive composition for electronic equipment according to claim 1, wherein the polymer having c) an organopolysiloxane in the side chain is a copolymer having at least one terminal-end silicone macromonomer as a copolymerization component. c) The polymer having an organopolysiloxane in the side chain has at least one functional group selected from the group consisting of epoxy groups, hydroxyl groups, carboxyl groups, amino groups, alkoxy groups, vinyl groups, silanol groups and isocyanate groups. The adhesive composition for electronic devices according to claim 1, comprising: 2. The adhesive composition for electronic equipment according to claim 1, wherein the polymer having an organopolysiloxane in the side chain is an acrylic resin. 2. The adhesive composition for electronic equipment according to claim 1, wherein the a) thermosetting resin contains an alicyclic epoxy resin. The adhesive for electronic equipment according to claim 1, comprising at least one kind of antioxidant selected from the group consisting of e) phenolic antioxidants, phosphorus antioxidants and sulfur antioxidants. Agent composition. 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 an at least 1 layer of peelable protective film layer. 8. The adhesive sheet for electronic equipment according to claim 7, wherein the adhesive layer has a haze of 15 or less after being heated and cured at 150 [deg.] C. for 1 hour. 8. The adhesive sheet for electronic equipment according to claim 7, wherein the adhesive layer has a haze of 30 or less after being heated and cured at 150 [deg.] C. for 1 hour and further heated at 150 [deg.] C. for 500 hours. The electronic component using the adhesive agent sheet for electronic devices in any one of Claims 7-9. An electronic device using the electronic component according to claim 10.

Images